Interventi di efficientamento energetico nell’industria ceramica

Questa tesi di laurea si occupa di valutare degli interventi di miglioramento dell’efficienza energetica per un’industria ceramica. In coerenza con gli impegni assunti nel pacchetto Clima Energia, il Decreto legislativo n° 102 del 4 luglio 2014, stabilisce l’obiettivo nazionale di risparmio energetico che consiste nella riduzione, entro il 2020, di 20 milioni di tonnellate equivalenti di petrolio dei consumi di energia primaria, conteggiati a partire dal 2010. Inoltre tale decreto stabilisce un regime obbligatorio di efficienza energetica costituito dal meccanismo dei certificati bianchi, il quale dovrebbe contribuire al raggiungimento del 60% dell’obiettivo. Sulla base di queste direttive è stato effettuato presso uno stabilimento ceramico uno studio di fattibilità che si articola nelle seguenti fasi: 1.Analisi energetica del sistema attuale finalizzata all’identificazione delle richieste energetiche in termini di produzione e consumi. 2.Analisi impiantistica finalizzata alla scelta delle macchine e delle soluzioni tecniche di dettaglio. 3.Analisi economica finalizzata alla valutazione del costo di generazione di energia elettrica e termica relativamente ai sistemi oggetto di studio. 4.Valutazione della sostenibilità dell’investimento per ogni opzione considerata, mediante l’applicazione del metodo economico del valore attuale netto (VAN), per ottimizzare il tempo di rientro dall’investimento. Le tipologie di intervento proposte sono: 1)Recupero dell’aria di raffreddamento del forno, che scaldandosi a contatto con la piastrella, ha un contenuto entalpico elevato e quindi può essere utilizzata nel reparto di essiccazione. 2)Sostituzione dei bruciatori esistenti ed obsoleti del forno di cottura bicanale con 192 nuovi kit di bruciatori "autorecuperativi". 3)Implementazione di un impianto di cogenerazione costituito da un motore a combustione interna, recuperando i gas esausti e parte dell’acqua del circuito di raffreddamento ad alta temperatura.

Avaliação da influência de cinza da casca de arroz em cimentos para poços de petróleo submetidos à injeção de vapor

Reservoirs that present highly viscous oils require methods to aid in their recovery to the surface. The elev ated oil viscosity hinders its flow through porous media and conventional recovery methods have not obtained significant efficiency. As such, the injection of steam into the reservoir through an injection well has been the most widely used method of therma l recovery, for it allows elevated volumes of recovery due to the viscosity reduction of the oil, facilitating the oil’s mobility within the rock formation and consequently into the production well where it will be exploited. On the other hand, the injecti on of vapor not only affects the fluids found in the rock pores, but the entire structure that composes the well where it is injected due to the high temperatures used in the process. This temperature increment is conducted to the cement, found in the annu lus, responsible for the isolation of the well and the well casing. Temperatures above 110 ̊C create new fazes rich in calcium in the cement matrix, resulting in the reduction of its permeability and the consequential phenomenon of mechanical resistance ret rogression. These alterations generate faults in the cement, reducing the well’s hydraulic isolation, creating insecurity in the operations in which the well will be submitted as well as the reduction of its economic life span. As a way of reducing this re trograde effect, this study has the objective of evaluating the incorporation of rice husk ash as a mineral additive substitute of silica flour , commercially utilized as a source of silica to reduce the CaO/SiO 2 ratio in the cement pastes submitted to high temperatures in thermal recovery. Cement pastes were formulated containing 20 and 30% levels of ash, apart from the basic paste (water + cement) and a reference paste (water + cement + 40% silica flour) for comparison purposes. The tests were executed th rough compression resistance tests, X - Ray diffraction (XRD) techniques, thermogravimetry (TG), scanning electron microscopy (SEM) and chemical anal ysis BY X - ray fluorescence (EDS) on the pastes submitted to cure at low temperatures (45 ̊C) for 28 days following a cure at 280 ̊C and a pressure of 2,000 PSI for 3 days, simulating vapor injection. The results obtained show that the paste containing 30% r ice shell ash is satisfactory, obtaining mechanical resistance desired and equivalent to that of the paste containing 40% silica flour, since the products obtained were hydrated with low CaO/SiO 2 ratio, like the Tobermorita and Xonotlita fases, proving its applicability in well subject to vapor injection.

Incrustação em poço produtor de petróleo e gás natural: um estudo de caso

Water and gas is a common by - product of the oil production process. Production may be compromised by the precipitation of inorganic salts in both the reservoir and producing well, through scale formation. This precipitation is likely the cause of the formation damage. High temperatures and h igh pressures (HTHP) may favor the precipitation of insoluble salts. The most common types of scale in oil fields are calcium carbonate and calcium sulphate, strontium and barium sulphate. New types of scale formation have attracted special attention such as zinc sulphide and lead. This precipitation may occur in the pores of reservoir rocks, in the production string and in equipment, causing obstructions and consequent production losses. In this study, the influence of well depth on incrustation compositio n was investigated to design removal treatments and assess the behavior of these deposits along the string, through the analysis of pressure and temperature. Scale residues were recovered from the inside of the production string of an oil and gas well duri ng the string removal operation. A total of 10 samples from different depths (15.4 m to 4061.5 m) were obtained. Initially a dissolution test was conducted in weak acid, similar to that used in removal operations with this type of scale formation. Majority composition was defined and confirmed by dissolution tests using X - Ray Fluorescence Spectroscopy (XRF), X - Ray Diffraction (XRD) and Scanning Electron Microscope (SEM) techniques. Residues with distinct characteristics were observed in different proportion s, showing a tendency toward increased and/or decreased mass with depth. In the samples closest to the surface, typical sandstone residues were found, with calcium (45% Ca) as the metal of highest concentration. The obtained results indicate correlations o f the scale types studied with the depth and, consequently, with the thermodynamic conditions of pressure and temperature.

Compósitos NiO-CGO obtidos pelo método de síntese em uma etapa

Composite NiO-C0.9Gd0.1O1.95 (NiO-GDC), one of the materials most used for the manufacture of anodes of Cells Solid Oxide Fuel (SOFC) currently, were obtained by a chemical route which consists in mixing the precursor solution of NiO and CGO phases obtained previously by the Pechini method. The nanopowders as-obtained were characterized by thermal analysis techniques (thermogravimetry and Differential Scanning Calorimetry) and calcined materials were evaluated by X-ray diffraction (XRD). Samples sintered between 1400 and 1500 ° C for 4 h were characterized by Archimedes method. The effects of the composition on the microstructure and electrical properties (conductivity and activation energy) of the composites sintered at 1500 ° C were investigated by electron microscopy and impedance spectroscopy (between 300 and 650 ° C in air). The refinement of the XRD data indicated that the powders are ultrafine and the crystallite size of the CGO phase decreases with increasing content of NiO. Similarly, the crystallite of the NiO phase tends to decrease with increasing concentration of CGO, especially above 50 wt % CGO. Analysis by Archimedes shows a variation in relative density due to the NiO content. Densities above 95% were obtained in samples containing from 50 wt % NiO and sintered between 1450 and 1500 °C. The results of microscopy and impedance spectroscopy indicate that from 30-40 wt.% NiO there is an increase in the number of contacts NiO - NiO, activating the electronic conduction mechanism which governs the process of conducting at low temperatures (300 - 500 °C). On the other hand, with increasing the measuring temperature the mobility of oxygen vacancies becomes larger than that of the electronic holes of NiO, as a result, the high temperature conductivity (500-650 ° C) in composites containing up to 30-40 wt.% of NiO is lower than that of CGO. Variations in activation energy confirm change of conduction mechanism with the increase of the NiO content. The composite containing 50 wt. % of each phase shows conductivity of 19 mS/cm at 650 °C (slightly higher than 13 mS/cm found for CGO) and activation energy of 0.49 eV.

Assinatura estrutural e geofísica da porção norte (fronteira Ceará-Piauí) no lineamento transbrasiliano: reativação na bacia do Parnaíba

The Transbrasiliano Lineament is a major shear zone trending NE-SW, related to the Brasiliano orogeny and evolved through high to low temperature stages. In this study, the structural and geophysical signature of the northern segment of Transbrasiliano Lineament was studied in its northern border, between Ceará and Piauí states, involving the Brasiliano mylonite zone, the Jaibaras Graben and reactivations affecting the sedimentary sequences post-ordovician of Parnaíba Basin. In the literature, is commonly the phanerozoic reactivation of this structure referred, generating several late Brasiliano grabens predating the paleozoic Parnaíba syneclises, like the Jaibaras Graben. Faults that cut the stratigraphic units of the Parnaíba Basin along the entire length of the Transbrasiliano Lineament express its reactivation during younger events. The magnetic anomaly field reduced to the pole map exhibit anomalies NE-trending, interpreted as the signature of the Transbrasiliano Lineament (and Brasiliano structures of the Borborema Province) in its high-temperature expression. The Jaibaras Graben is marked by a straight anomalous track with high magnetic susceptibility (interpreted as a prevalence of ferromagnesian rocks, probably volcanic), apparently without significant continuity in the substrate of Parnaíba Basin. The geometric and kinematic analysis of the structures in the study area, using remote sensing and field data, led to the characterization of four deformation phases brittle the ductilebrittle Dn, D1, D2 and D3. The Dn deformation phase of ediacaran-cambrian age, occurs exclusively in the Jaibaras Graben, with the development of comparatively higher temperature (as regards to younger events) ductile-brittle structures. D1, D2 and D3 deformation phases affect both the Jaibaras Graben as well as the paleozoic sequences of the northeastern edge of Parnaíba Basin, generating structures developed at lower temperatures, basically brittle/cataclastic. The SRTM image analysis allowed mapping different NE, NW and E-W trending lineaments in Parnaíba Basin, whose correlation with mesoscopic structures is discussed in terms of the reactivation of Transbrasiliano Lineament in association with the stages of general Atlantic opening and separation between South America and Africa, or even the distal orogenic events in Paleozoic.

Tensoativo derivado do ácido cítrico: síntese e aplicação em fluidos de perfuração de emulsão inversa

This work describes the synthesis and study of the application of a new surfactant (Triester Lipophilic – TEL) obtained by citric acid with octanol. It is reaction was followed by thin layer chromatography (TLC) and after purification the product was characterized by proton and 13 – carbon nuclear magnetic resonance spectroscopy ( H and 13C NMR), thermogravimetric analysis (TGA) and surface tension analysis of oil-in-water emulsions. The TEL performance as surfactant in ester, n-paraffin and biodiesel based drilling fluids on the 70/30 and 60/40 water- oil rations (WOR) was evaluated by comparative tests of two commercial products used in the fields. These drilling fluids were aged in roller oven at 200 0 F during 16 h. The rheological and electric stability measurements were carried out at 135 ºF, the phase separation was evaluated after seven days at rest and the filtrate volume of drilling fluids was determined at high temperature and high pressure. The rheological behavior of the drilling fluids was evaluated by the flow curves. The results showed that the drilling fluids studied here presented Binghamian behavior as well as the used in the oil fields. The laboratory tests showed that the TEL reduced the filtrate volume and promoted the enhance of the thermal and mechanical stabilities.

Geoquímica de emanaciones difusas y termografía en sistemas volcánicos: implicaciones para la exploración geotérmica y la vigilancia volcánica en Canarias

En la presente tesis doctoral, titulada “Geoquímica de emanaciones difusas y termografía en sistemas volcánicos: implicaciones para la exploración geotérmica y la vigilancia volcánica en Canarias”, se ha evaluado el uso conjunto de técnicas geoquímicas (prospecciones geoquímicas de gases y volátiles en el ambiente superficial del suelo) y geofísicas (campañas de exploración magnetotelúrica y estudio de imágenes térmicas) como herramientas para la monitorización volcánica y la exploración geotérmica. Las Islas Canarias fueron el marco de estudio elegido para lograr este objetivo, debido a que en dichas islas ha habido actividad volcánica holocénica (a excepción de La Gomera), habiéndose registrado erupciones históricas en las islas de Tenerife, La Palma, Lanzarote y El Hierro. El archipiélago canario en su conjunto se puede considerar como un área volcánicamente activa, siendo el riesgo volcánico hoy día mayor que hace 40 años, como resultado de un drástico aumento poblacional y socio-económico, expuesto a los peligros volcánicos inherentes a la naturaleza volcánica del archipiélago. En la historia reciente de las Islas Canarias existe una carencia de esfuerzos para la explotación de uno de los beneficios del fenómeno volcánico, como podría ser el desarrollo de la energía geotérmica: Canarias es la única región del territorio nacional con recursos geotérmicos de alta temperatura como consecuencia de la presencia de un volcanismo activo. Por lo tanto, es necesario un mayor esfuerzo para desarrollar la energía geotérmica en Canarias y mejorar los sistemas de detección de señales de alerta ante futuros procesos de reactivación volcánica. Este trabajo de tesis doctoral persigue (i) reducir los impactos negativos de la actividad volcánica en las islas Canarias a través de un avance en la comprensión de la dinámica de las emisiones de gases volcánicos como una poderosa técnica de vigilancia volcánica y (ii) promover el desarrollo de la energía geotérmica a través un avance en el conocimiento de los recursos geotérmicos que pudieran existir en el subsuelo de las Islas Canarias...

Evaluación de tenacidad a la fractura e integridad estructural de tubos de generadores de vapor nucleares.

Dado el impacto negativo asociado a la ocurrencia de fallas en tubos de generadores de vapor (TGVs) en centrales nucleares, el estudio de la integridad estructural de éstos ha comenzado a recibir mayor atención recientemente. Diversas metodologías basadas en análisis de carga límite han sido propuestas para asegurar la integridad estructural de los tubos, según los requerimientos establecidos por las autoridades regulatorias. Éstas han conducido, sin embargo, a la definición de criterios de reparación o taponado de TGVs excesivamente conservativos. Por lo tanto, con el objetivo de reducir la cantidad de tubos innecesariamente removidos de servicio, nuevos criterios de evaluación de integridad han sido propuestos recientemente en la literatura. En este contexto, la mecánica de fractura elastoplástica se presenta como una alternativa para la evaluación de la integridad de TGVs, requiriéndose dos elementos para su aplicación: la estimación de la fuerza impulsora en términos del parámetro elastoplástico (por ejemplo, la integral J) y la medición experimental de la tenacidad a la fractura del material de los tubos (por ejemplo, a través de la curva de resistencia J-R). Este trabajo presenta el desarrollo de técnicas experimentales no normalizadas para la determinación de curvas J-R para TGVs con fisuras pasantes circunferenciales y longitudinales. Debido a las dimensiones reducidas de los TGVs, diferentes probetas no normalizadas fueron propuestas. Además, en los ensayos se utilizaron condiciones de carga de tracción y flexión con el objetivo de modelar más adecuadamente los estados tensionales y las condiciones de constraint reales en TGVs. Los valores de la integral J fueron estimados utilizando el método del factor η. La aptitud del método fue evaluada a partir de simulaciones numéricas de los ensayos propuestos mediante análisis elastoplásticos con la técnica de elementos finitos. Se encontró que condiciones de mayor constraint asociadas con fisuras profundas y cargas de flexión favorecen la validez del método del factor η, mientras que configuraciones de menor constraint dan como resultado factores η que exhiben una mayor dependencia con el nivel de carga aplicada. También se observó que los factores η basados en la apertura de la boca de la fisura (Crack Mouth Opening Displacement o CMOD) presentan una dependencia mucho menor con el nivel de carga respecto a los factores η definidos a partir del desplazamiento del punto de aplicación de la carga (Load Line Displacement o LLD). Se presentan los valores del factor η para las probetas estudiadas con fisuras profundas (a/W ≥ 0,40). Se realizaron ensayos de fractura a temperatura ambiente y 300 °C con probetas obtenidas de TGVs nucleares fabricados a partir de las aleaciones 690 (Ni: 61; Cr: 29; Fe: 8,95, % en peso) y 800 (Ni: 33; Cr: 21,6; Fe: 42,2, % en peso). Durante los ensayos de fractura a temperatura ambiente, la extensión estable de fisura fue medida mediante una técnica óptica utilizando un microscopio digital. Para estos ensayos también se aplicó el método de normalización que propone la norma ASTM E1820-15 en el Anexo 15, encontrándose una buena coincidencia entre las longitudes estimadas por éste y las medidas ópticamente. De esta manera, el método de normalización fue utilizado para los ensayos a alta temperatura. Los resultados experimentales mostraron que ambos materiales tienen elevadas tenacidades a la fractura, siendo la aleación 800 la que presentó curvas J-R más elevadas que la aleación 690 tanto para fisuras circunferenciales como longitudinales. Las curvas J-R para ambas aleaciones mostraron un efecto marcado con la orientación de la fisura, es decir que existe una importante anisotropía en las propiedades de fractura: las fisuras circunferenciales presentaron curvas J-R más elevadas que las fisuras longitudinales. El nivel de constraint desarrollado en los ensayos, dado por las condiciones de carga de tracción y flexión, evidenció poco efecto sobre las curvas J-R para probetas con fisuras profundas (a/W ~ 0,50). A su vez, la temperatura de ensayo (temperatura ambiente y 300 °C) presentó un efecto prácticamente nulo para ambas aleaciones. Usando las propiedades de fractura obtenidas en este trabajo, la metodología FAD (Failure Assessment Diagram) fue propuesta y utilizada para la predicción de las condiciones de falla de TGVs fisurados para diferentes geometrías de fisura y condiciones de carga. La comparación entre análisis teóricos y datos experimentales muestra la potencialidad del FAD como una metodología capaz de predecir adecuadamente las fallas de estos componentes.

Evaluación de tenacidad a la fractura e integridad estructural de tubos de generadores de vapor nucleares.

Dado el impacto negativo asociado a la ocurrencia de fallas en tubos de generadores de vapor (TGVs) en centrales nucleares, el estudio de la integridad estructural de éstos ha comenzado a recibir mayor atención recientemente. Diversas metodologías basadas en análisis de carga límite han sido propuestas para asegurar la integridad estructural de los tubos, según los requerimientos establecidos por las autoridades regulatorias. Éstas han conducido, sin embargo, a la definición de criterios de reparación o taponado de TGVs excesivamente conservativos. Por lo tanto, con el objetivo de reducir la cantidad de tubos innecesariamente removidos de servicio, nuevos criterios de evaluación de integridad han sido propuestos recientemente en la literatura. En este contexto, la mecánica de fractura elastoplástica se presenta como una alternativa para la evaluación de la integridad de TGVs, requiriéndose dos elementos para su aplicación: la estimación de la fuerza impulsora en términos del parámetro elastoplástico (por ejemplo, la integral J) y la medición experimental de la tenacidad a la fractura del material de los tubos (por ejemplo, a través de la curva de resistencia J-R). Este trabajo presenta el desarrollo de técnicas experimentales no normalizadas para la determinación de curvas J-R para TGVs con fisuras pasantes circunferenciales y longitudinales. Debido a las dimensiones reducidas de los TGVs, diferentes probetas no normalizadas fueron propuestas. Además, en los ensayos se utilizaron condiciones de carga de tracción y flexión con el objetivo de modelar más adecuadamente los estados tensionales y las condiciones de constraint reales en TGVs. Los valores de la integral J fueron estimados utilizando el método del factor η. La aptitud del método fue evaluada a partir de simulaciones numéricas de los ensayos propuestos mediante análisis elastoplásticos con la técnica de elementos finitos. Se encontró que condiciones de mayor constraint asociadas con fisuras profundas y cargas de flexión favorecen la validez del método del factor η, mientras que configuraciones de menor constraint dan como resultado factores η que exhiben una mayor dependencia con el nivel de carga aplicada. También se observó que los factores η basados en la apertura de la boca de la fisura (Crack Mouth Opening Displacement o CMOD) presentan una dependencia mucho menor con el nivel de carga respecto a los factores η definidos a partir del desplazamiento del punto de aplicación de la carga (Load Line Displacement o LLD). Se presentan los valores del factor η para las probetas estudiadas con fisuras profundas (a/W ≥ 0,40). Se realizaron ensayos de fractura a temperatura ambiente y 300 °C con probetas obtenidas de TGVs nucleares fabricados a partir de las aleaciones 690 (Ni: 61; Cr: 29; Fe: 8,95, % en peso) y 800 (Ni: 33; Cr: 21,6; Fe: 42,2, % en peso). Durante los ensayos de fractura a temperatura ambiente, la extensión estable de fisura fue medida mediante una técnica óptica utilizando un microscopio digital. Para estos ensayos también se aplicó el método de normalización que propone la norma ASTM E1820-15 en el Anexo 15, encontrándose una buena coincidencia entre las longitudes estimadas por éste y las medidas ópticamente. De esta manera, el método de normalización fue utilizado para los ensayos a alta temperatura. Los resultados experimentales mostraron que ambos materiales tienen elevadas tenacidades a la fractura, siendo la aleación 800 la que presentó curvas J-R más elevadas que la aleación 690 tanto para fisuras circunferenciales como longitudinales. Las curvas J-R para ambas aleaciones mostraron un efecto marcado con la orientación de la fisura, es decir que existe una importante anisotropía en las propiedades de fractura: las fisuras circunferenciales presentaron curvas J-R más elevadas que las fisuras longitudinales. El nivel de constraint desarrollado en los ensayos, dado por las condiciones de carga de tracción y flexión, evidenció poco efecto sobre las curvas J-R para probetas con fisuras profundas (a/W ~ 0,50). A su vez, la temperatura de ensayo (temperatura ambiente y 300 °C) presentó un efecto prácticamente nulo para ambas aleaciones. Usando las propiedades de fractura obtenidas en este trabajo, la metodología FAD (Failure Assessment Diagram) fue propuesta y utilizada para la predicción de las condiciones de falla de TGVs fisurados para diferentes geometrías de fisura y condiciones de carga. La comparación entre análisis teóricos y datos experimentales muestra la potencialidad del FAD como una metodología capaz de predecir adecuadamente las fallas de estos componentes.

Functional alkali tantalate 2D structures for microelectronics and related applications

Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.

Isolado protéico de farelo de arroz: obtenção, propriedades funcionais e aplicação

O arroz é o segundo cereal mais produzido no mundo e para que ele seja consumido é necessário o processo de beneficiamento, onde é retirada a casca, e com o polimento, o farelo. O farelo, após a retirada do óleo, é utilizado para alimentação animal, mas como corresponde a 8% do grão, são necessárias novas alternativas para o uso do mesmo, uma vez que contém em torno de 17% de proteína. As proteínas do farelo de arroz são consideradas de alta qualidade, hipoalergênicas e anticancerígenas. Devido ao excesso de fibras presentes no farelo, este não é utilizado diretamente na alimentação humana, podendo ser usado como fonte para a obtenção de extratos, concentrados ou isolados. A obtenção do isolado protéico pode ser por via química, que consiste na extração alcalina ou ácida, seguida de precipitação no ponto isoelétrico ou via enzimática, com o uso de enzimas amilolíticas, hemicelulases e carboidrases para a separação das proteínas. O objetivo deste estudo foi obter um isolado protéico a partir de farelo de arroz visando a inclusão deste em produto de panificação. Foi obtido isolado protéico pelo método químico que foi analisado pelo rendimento protéico, pelas propriedades funcionais, perfil aminoacídico, eletroforese e características térmicas. O isolado foi adicionado em bolos em diferentes concentrações sendo avaliado pelas características tecnológicas e sensoriais. O isolado protéico do farelo de arroz (IPFA) que apresentou maior rendimento protéico foi o obtido pelo método químico, com o farelo de granulometria de 42 mesh e desengordurado. Em relação às propriedades funcionais, foi verificado que o IPFA possui maior solubilidade e capacidade de retenção de água em pH 11, alta capacidade emulsificante e alta capacidade de formação de espuma. No aminograma, constatou-se que os aminoácidos encontrados no IPFA atendem as necessidades de bebês e crianças. No perfil eletroforético, o IPFA apresentou 3 grupos de proteínas. Na análise térmica com DSC, o IPFA apresentou alta temperatura de desnaturação e baixo valor de entalpia. Na elaboração dos bolos, à medida que foi adicionado o IPFA, aumentou o teor protéico, o pH e o volume específico e diminuiu o colapso, a luminosidade e a firmeza dos bolos. Na análise sensorial, os bolos com IPFA não apresentaram diferenças estatísticas do bolo controle (sem IPFA). Estes resultados indicam a potencialidade do IPFA em produtos de panificação.

Síntese e caracterização de NiO-CGO para anodo e eletrólitos sólidos e base de Céria para SOFC

The direct use of natural gas makes the Solid Oxide Fuel Cell (SOFC) potentially more competitive with the current energy conversions technologies. The Intermediate Temperature SOFC (IT-SOFC) offer several advantages over the High Temperature SOFC (HT-SOFC), which includes better thermal compatibility among components, fast start with lower energy consumption, manufacture and operation cost reduction. The CeO2 based materials are alternatives to the Yttria Stabilized Zirconia (YSZ) to application in SOFC, as they have higher ionic conductivity and less ohmic losses comparing to YSZ, and they can operate at lower temperatures (500-800°C). Ceria has been doped with a variety of cations, although, the Gd3+ has the ionic radius closest to the ideal one to form solid solution. These electrolytes based in ceria require special electrodes with a higher performance and chemical and termomechanical compatibility. In this work compounds of gadolinia-doped ceria, Ce1-xGdxO2-δ (x = 0,1; 0,2 and 0,3), used as electrolytes, were synthesized by polymeric precursors method, Pechini, as well as the composite material NiO - Ce0,9Gd0,1O1,95, used as anode, also attained by oxide mixture method, mixturing the powders of the both phases calcinated already. The materials were characterized by X ray diffraction, dilatometry and scanning electronic microscopy. The refinement of the diffraction data indicated that all the Ce1-xGdxO2-δ powders were crystallized in a unique cubic phase with fluorite structure, and the composite synthesized by Pechini method produced smaller crystallite size in comparison with the same material attained by oxide mixture method. All the produced powders had nanometric characteristics. The composite produced by Pechini method has microstructural characteristics that can increase the triple phase boundaries (TPB) in the anode, improving the cell efficiency, as well as reducing the mass transport mechanism effect that provokes anode degradation

Caracterização termo-mecânica de interconectores metálicos recobertos com filmes de LaCrO3

The cells unitaria of the solid oxide fuel cell are separated by means of interconnects, which serve as electrical contact between the cells. Lanthanum Chromite (LaCrO3) has been the most common material used as interconnect in solid oxide fuel cells. Reducing the operating temperature around 800 º C of cells to solid oxide fuel make possibilite the use of metallic interconnects as an alternative to ceramic LaCrO3. Metallic interconnects have advantages over ceramic interconnects such as high thermal conductivity, electricity, good ductility, low cost, good physical and mechanical properties. In this work evaluate the thermo-mechanical properties of the metallic substrate and coated metallic substrate with the ceramic LaCrO3 film via spray-pyrolysis, in order to demonstrate the feasibility of using this material as a component of a fuel cell solid oxide. The materials were characterized by X-ray diffraction, oxidation behavior, mechanical strength, optical microscopy (OM) and scanning electron microscopy (SEM). The X-ray diffraction proved the formation phase of the LaCrO3 on the metallic substrate and the identification of the phases formed after the oxidative test and mechanical strength at high temperature. The oxidation behavior showed the increased oxidation resistance of the coated metallic substrate. It was noted that the mechanical resistance to bending of the coated metallic substrate only increases at room temperature. The optical microscopy (OM) has provided an assessment of both the metallic substrate and the LaCrO3 film deposited on the metal substrate that, in comparison with the micrographs obtained from SEM. The SEM one proved the formation of Cr2O3 layer on the metallic substrate and stability of LaCrO3 film after oxidative test, it can also observe the displacement of the ceramic LaCrO3 film after of mechanical testing and mapping of the main elements as chromium, manganese, oxygen, lanthanum in samples after the thermo-mechanical tests.

Obtenção de nanopartículas de hexaferrita de bário pelo método pechini

In this study barium hexaferrite was (general formulae BaFe12O19) was synthesized by the Pechini method under different conditions of heat treatment. Precursors like barium carbonate and iron nitrate were used. These magnetic ceramic, with magnetoplumbite type structure, are widely used as permanent magnet because of its excellent magnetic properties, such as: high Curie temperature, good magnetic anisotropy, high coercivity and corrosion resistance. The samples were characterized by thermal analysis (DTA and TG), X- ray Diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Scanning Electron Microscopy (SEM) end Vibrating sample Magnetometer (VSM). The results confirm the expected phase, which was reinforced according to our analysis. A single phase powder at relatively high temperatures with particle sizes around 100 nm was obtained. The characteristic magnetic behavior one of the phases has been noted (probably superparamagnetic material), while another phase was identified as a ferrimagnetic material. The ferrimagnetic phase showed vortex configuration with two central and slightly inclined plateaus. In general, increase of heat treatment temperature and time, directly influenced the technological properties of the samples

Adição do resíduo de biomassa da cana-de-açúcar em pastas para cimentação de poços petrolíferos produtores de óleos pesados

The Potiguar basin has large fields of viscous oil where the used method for recovering is based on vapor injection; this operation is carried out by injecting vapor in the oilwell directly, without the protection of a revetment through thermal insulation, what causes its dilation and, consequently, cracks in the cement placed on the annular, and lost of hydraulic insulation; this crack is occasioned by the phenomenon of retrogression of the compressive resistance due to the conversion of the hydrated calcium silicate in phases calcium-rich, caused by the high temperatures in the wells, subjected to thermal recuperation. This work has evaluated the application of composite pastes with addition of residue of biomass of ground sugar-cane bagasse as anti-retrogression mineral admixture for cementation of oil-wells subjected to thermal recuperation. The addition of the mineral residue was carried out considering a relative amount of 10, 20, 30, 40 and 59% in relation to cement mass, trying to improve the microstructure of the paste, still being developed a reference paste only with cement and a paste with addition of 40% of silica flour - renowned material in the oil industry as anti-retrogression additive. Pozzolanic activity of the ash was evaluated through XRD, TG/DTG, as the resistance to compression, and it was also determined the physical and mechanical behavior of the pastes when submitted to cure at low temperatures (22 and 38º C); besides it was evaluated the behavior of the pastes when submitted to two cycles of cure at high temperature (280ºC) and pressure (7 MPa). It was verified that the ash of the sugar-cane biomass presents pozzolanic reaction and has great efficiency in decrease the permeability of the paste by filler effect, as well as that addition of ash in a relative amount of 10, 20 e 30% increases cured compressive resistance at low temperatures. It was also showed that the ash in a relative amount of 40% and 59% has very significant efficiency as anti-retrogression additive, since it prevents the decrease of compressive resistance and forms hydrated calcium silicate type xenotlita and tobermorita which have more resistance and stability in high temperatures