Σκοπός της παρούσας εργασίας είναι η μελέτη του μηχανισμού καταβύθισης ανόργανων αλάτων μέσω της επί τόπου (in-situ) καταβύθισής τους σε πορώδη μέσα και η ανάπτυξη μιας περιβαλλοντικά φιλικής μεθόδου που θα οδηγήσει στη στεγανοποίηση και ενδυνάμωση (θεραπεία) των μηχανικών ιδιοτήτων των πετρωμάτων. Οι εφαρμογές στη βιομηχανία μπορεί να είναι ποικίλες, όπως για τη στεγανοποίηση σηράγγων και άλλων υπόγειων έργων, για τη σταθεροποίηση των κυματοθραυστών, για την προστασία των κατασκευών από τη διάβρωση εξ αιτίας της υγρασίας, για την προστασία των μνημείων πολιτισμικής κληρονομιάς. Πιο συγκεκριμένα, το σύστημα που μελετάται είναι το σύστημα των πυριτικών αλάτων. Έγινε μελέτη της αυθόρμητης καταβύθισης του πυριτικού ασβεστίου σε αντιδραστήρα διαλείποντος έργου. Επιπλέον, μελετήθηκε η επίδραση συγκεκριμένης ποσότητας κονιοποιημένης σκόνης (10γραμμάρια) πετρώματος στο μηχανισμό καταβύθισης του πυριτικού ασβεστίου. Κατά τη διάρκεια της πειραματικής διαδικασίας συλλέγονταν δείγματα από τον αντιδραστήρα σε τακτά χρονικά διαστήματα για να διαπιστωθεί η μείωση των ιόντων πυριτίου και ασβεστίου από το διάλυμα με τη μέθοδο του φωτομέτρου και της ατομικής απορρόφησης αντίστοιχα. Από τη μείωση της συγκέντρωσης των ιόντων υπολογίστηκε ο ρυθμός καταβύθισης και κατόπιν η φαινόμενη τάξη της αντίδρασης. Επίσης, με τη χρήση του ηλεκτρονικού μικροσκοπίου σάρωσης και της περιθλασιμετρίας των ακτίνων Χ ανιχνεύθηκαν οι καταβυθιζόμενες φάσεις στις διαφορετικές πειραματικές συνθήκες. Αυτές ήταν κυρίως το άμορφο διοξείδιο του πυριτίου, το ένυδρο πυριτικό ασβέστιο και ο βολλαστονίτης. Κατά την αυθόρμητη καταβύθιση του πυριτικού ασβεστίου ο κύριος μηχανισμός που την ελέγχει βρέθηκε ότι είναι το πολυπυρηνικό πρότυπο. Η εργασία χωρίζεται σε 6 κεφάλαια. Το πρώτο αναφέρεται γενικότερα στο πρόβλημα των διαβρώσεων και των προβληματικών κατασκευών, το δεύτερο δίνει πληροφορίες σχετικά με το στοιχείο του πυριτίου, τις ενώσεις που σχηματίζει και τις ιδιότητές του και το τρίτο είναι μια σύντομη αναφορά στη θεωρία της κρυστάλλωσης. Επίσης, αναφέρονται σύντομα οι θεωρίες που έχουν διατυπωθεί για την πυρηνογένεση και την κρυστάλλωση από υπέρκορα διαλύματα. Στη συνέχεια, στο τέταρτο κεφάλαιο παρουσιάζονται τα πειράματα που πραγματοποιήθηκαν σε αντιδραστήρα διαλείποντος έργου για διαφορετικές συγκεντρώσεις και τιμές pH. Πραγματοποιήθηκαν πειράματα σε pH=9 και pH=10 και σε εύρος συγκεντρώσεων 2mM to 50mM, απουσία και παρουσία σκόνης πετρώματος. Τα υδατικά διαλύματα που χρησιμοποιήθηκαν είναι χλωριούχο ασβέστιο (CaCl2) και οξείδιο του πυριτίου (Na2Si3O7). Στο πέμπτο κεφάλαιο, παρουσιάζεται η μέθοδος που αναπτύχθηκε με σκοπό να μειωθεί το πορώδες των πετρωμάτων. Χρησιμοποιήθηκαν κυλινδρικά δοκίμια φυσικού πετρώματος (υπόστρωμα), πάνω στα οποία εφαρμόστηκαν διαλύματα πυριτικού ασβεστίου σε διάφορες συγκεντρώσεις. Η επιλογή του πετρώματος ως υπόβαθρο εφαρμογής έγινε γιατί η σταθεροποίηση πετρωμάτων βρίσκει εφαρμογή σε αρκετά πεδία, όπως η προστασία των μνημείων και των έργων τέχνης, η βιομηχανία πετρελαίου και τα τεχνικά έργα. Πραγματοποιήθηκαν πειράματα υδατικής εισρόφησης (water absorption test) σε διαφορετικές συγκεντρώσεις. Το επιθυμητό προϊόν καταβύθισης ανάμεσα στους πόρους του πετρώματος είναι το Ca-Si-O και η καταβύθιση είναι επιθυμητό να πραγματοποιείται στην επιφάνεια αλλά και μερικά χιλιοστά κάτω από αυτή. Τέλος, στο τελευταίο κεφάλαιο παρατίθενται συνολικά τα συμπεράσματα που εξήχθησαν από την εργασία. / The main motivation for the present work is the investigation of the precipitation mechanisms through in-situ mixing and the precipitation of soluble salts in porous media. The proposed method may be applicable for the prevention of sand entrainment into well bores during oil production in poorly consolidated oil reservoirs. The work done concerning the development of the methodology of calcium silicate salts involved the following steps: i) investigation of the mechanism via growth rate measurements. ii) treatment of natural rock samples with the application of chemical solutions and testing of the method. In the present study, two series of experiments were conducted in order to investigate the kinetics of calcium silicate precipitation in batch reactors using calcium chloride and sodium trisilicate as the initials reagents in the absence and presence of silica sand and at pH=9 and 10 at 25oC. Different concentrations of the salts were tried, ranging from 2mM to 50mM. In all sets of lab experiments used in the present work the molar concentrations of the supersaturated solutions were equal (1:1). During the experiments, samples were taken, filtered by membrane filters and analyzed for total calcium by AAS (atomic absorption spectroscopy) and for total silica by UV spectrometry. Moreover, at the end of each experiment, the fluid suspension was filtered with a 0.22μm filter and the solid parts were collected, then dried and finally characterized by powder XRD (X-Ray diffraction) method and observed in SEM (scanning electron microscopy) for the identification of the mineral crystalline phases. The analysis of the kinetic data showed that in spontaneous precipitation experiments at pH=10, the crystal growth mechanism is best described by the polynuclear model (n=6) and the main crystalline phase recognized was calcium silicate hydrate. The effect of various parameters, such as temperature, salts concentration, pH, and the presence of sand was studied upon the rate of precipitation and the morphology of the precipitate. It was expected that precipitation would be favored for high concentrations of solutions. Finally, a set of experiments was carried out to test the efficiency of the method when applied inside porous media. The porous media that was used was natural rock that was cut and formalized in small cylindrical samples. The two soluble salts were applied either separately on the rock samples or after having been mixed for different concentrations and repeatedly with brushing or spraying. It was attempted to obtain qualitative and quantitative information concerning the deposition and growth of calcium silicate within the pores of the rock. After the treatment of the samples with the solutions water absorption test took place. It was found that precipitation of calcium silicate happened within porous material and indeed was favored by high concentrations and repeated applications

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T12:39:08Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T12:39:08Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

En dépit de l’importance considérable des matériaux alumino- et borosilicates pour la catalyse, l’origine moléculaire de leur activité demeure mal comprise. Ceci tient à la difficulté de caractériser le désordre structural local généré au sein du réseau silicaté par l’incorporation d’hétéroatomes. Le caractère local de la résonance magnétique nucléaire (RMN) à l’état solide en fait une technique adaptée pour résoudre cette question majeure. Les silicates en feuillés auto-assemblés en présence de surfactants sont d’excellents systèmes modèles pour l’étude de la structure locale autour d’hétéroatomes de B ou d’Al car la synthèse, la structure moléculaire et la signature RMN 29Si simple de leurs formes siliceuses sont parfaitement maîtrisées. L’incorporation dans leurs réseaux silicatés de différentes quantités d’Al ou de B et leurs conséquences ont été étudiées par des méthodologies avancées de RMN permettant de sonder les interactions à travers l’espace ou les liaisons chimiques entre noyaux de 29Si, 27Al, 11B et/ou 1H, une approche qui peut être étendue à la substitution atomique dans une argile aluminosilicate et un nouveau borosilicate de calcium. Ces résultats ont été combinés à la modélisation moléculaire pour construire et valider des modèles structuraux capables de décrire les distorsions et les réarrangements parfois profonds du réseau résultant de la substitution. Cela a révélé des différences frappantes entre les conséquences de l’incorporation d’Al ou de B dans deux matériaux de morphologie semblables mais de structures moléculaires différentes, et offre une occasion unique de comprendre les propriétés régissant l’incorporation d’hétéroatomes dans les silicates. / While alumino- and borosilicate materials have paramount importance in catalysis, the molecular origin of their activity is not completely understood. This is mainly because the incorporation of heteroatoms into the silicate framework deteriorates the molecular order by generating local disorder that is particularly difficult to establish. Because of its local vision of ordered and disordered environments, solid-state nuclear magnetic resonance (NMR) can play a key role to solve this long-standing issue. Surfactant-directed layered silicate materials with short-range molecular order are particularly interesting model systems to study the local structures around Al or B heteroatoms because the synthesis, molecular structures, and simple 29Si NMR signatures of their pure-silicate forms are well understood. Various amounts of Al and B atoms were incorporated into their frameworks, and their consequences on the local structure were investigated by state-of-the-art multidimensional NMR measurements probing spatial proximities or bonding interactions between 29Si, 11B, 27Al, and 1H nuclei, an approach that could be extended to atomic substitution in an aluminosilicate clay and a new calcium borosilicate. These results were combined with molecular modeling to build and evaluate structural models that capture the local framework distortions and sometimes profound rearrangements resulting from the atomic substitutions. This reveals remarkable differences between the consequences of the incorporation Al or B in two distinct frameworks of otherwise strongly-related materials, and offers a unique opportunity to understand the properties that drive heteroatom incorporation.

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T12:39:08Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T12:39:08Z (GMT). No. of bitstreams: 0 / Estudo realizado acerca da utilização de dois resíduos sólidos industriais (RSI) gerados em grande quantidade no Brasil, na obtenção de vidros soda-cal destinados à produção de embalagens. Os resíduos avaliados foram a cinza de casca de arroz (CCA) e resíduo do catalisador usado das unidades de Craqueamento Catalítico Fluido das Petroquímicas (ECAT), ambos podem ser classificados como resíduos sólidos de classe II de acordo com a norma NBR 10.004. Esta nova proposta para destinação desses resíduos é uma alternativa às atuais disposições, buscando não apenas minimizar os impactos ambientais gerados, mas também a valorização dos mesmos como matérias-primas. Para a produção das amostras, além da utilização dos RSIs, foram também utilizados óxidos fundente (Na2CO3) e estabilizante (CaO). Os resultados obtidos demonstraram que ambos podem ser usados como recebidos (sem tratamento prévio) substituindo matérias-primas importantes, fontes de Al2O3 e SiO2, necessárias para a formação de vidros. As amostras obtidas apresentaram a cor âmbar devido a presença de níquel (íons Ni2+) proveniente do ECAT e transmitância óptica de 18%. Estas, ainda demonstraram boa homogeneidade, i.e., ausência de bolhas e estriais e, resistências hidrolíticas média de 1,33x10-8 g/cm²·dia (superior à um vidro comercial de composição semelhante) de acordo com a ISO695-1984. O vidro obtido é adequado para aplicações que exigem baixa transmitância como embalagens de vidros em geral, os quais não requerem perfeita visibilidade e transparência. O teor de incorporação na composição final das amostras foi de aproximadamente 78% em massa. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

No description available.

Orientador: Renato de Mello Prado / Coorientador: Gilmara Pereira da Silva / Banca: Joaquim José Frazão / Banca: Claudenir Facincani Franco / Resumo: O mineral silício (Si) é considerado um elemento essencial para o ser humano, tendo diversas funções, especialmente a para formação óssea. O tomate é amplamente consumido no mundo, mas apresenta baixo teor de Si, não atendendo a exigência do ser humano. A pulverização foliar de Si em plantas tomate pode promover a biofortificação associada à melhora na qualidade pós-colheita, dependendo da fonte e da concentração do elemento na calda. Neste estudo, objetivou-se obter tomates biofortificados via pulverização foliar com Si, em diferentes fontes e concentrações, e avaliar sua qualidade tecnológica. O experimento foi conduzido em casa de vegetação, em sistema de cultivo hidropônico, em vasos (8 dm3) preenchidos com areia, contendo uma planta por vaso. Os tratamentos consistiram da combinação de quatro fontes de Si (silicato alcalino estabilizado; nanossílica; ácido silícico estabilizado e silicato de potássio) e quatro concentrações de Si (0,0; 0,2; 0,4 e 0,6 g L-1), dispostos em blocos casualizados, com cinco repetições. Realizaram-se cinco pulverizações com Si nas plantas de tomate cultivar Micro Tom, iniciando-se no florescimento, uma vez por semana. A pulverização foliar de Si durante a fase reprodutiva das plantas de tomate foi eficiente para biofortificar o fruto e incrementar o teor de ácido ascórbico, a acidez titulável e a firmeza do fruto, destacando-se a fonte nanossílica e ácido silícico na concentração próxima de 0,4 g L-1. / Abstract: The mineral silicon (Si) is considered an essential element for humans, having several functions, especially for bone formation. Tomato is a fruit widely consumed in the world but the low Si content does not meet the standard requirements for human beings. To this end, foliar spraying of tomato plants with Si may promote biofortification associated with improved post-harvest quality, depending on the source and concentration of Si used in the spraying mixture. This study aimed at producing tomatoes biofortified with Si at varying concentrations from different sources via foliar spraying, and evaluating their technological quality as well. The experiment consisted of pots (8 dm3) filled with sand containing one Micro-Tom cultivar tomato plant per pot in a greenhouse, in a hydroponic culture system. The treatments consisted of a combination of four Si sources (stabilized alkali metal silicate, nano silica, stabilized silicic acid, and potassium silicate) and four Si concentrations (0.0; 0.2; 0.4; and 0.6 g L-1), arranged as a randomized block design, with five replications. Five spraying mixtures containing Si were applied to the tomato plants once a week as the flowering stage started. Foliar spraying of Si during the reproductive phase of tomato plants effectively biofortified the fruit, increasing the ascorbic acid content, titratable acidity and fruit firmness, highlighting as particularly effective the nano silica and silicic acid sources at the approximate concentration o... (Complete abstract click electronic access below) / Mestre

Lapis Lazuli é um mineral de silicato, que foi objeto do presente estudo. Trata-se de uma solução sólida complexa de outros quatro minerais de silicato, a saber: sodalita, noselita, huainita, e lazurita. Essa composição da solução sólida não permite estimar a porcentagem de cada mineral componente, no analise de fluorescência de raios X, onde se obteve que os principiais óxidos componentes do lapis lazuli são, (em % mol) SiO_2 (33,2), CaO (16,3), MgO (12,1) e Al_2 O_3 (10,1) e, em menor concentração , Na_2 O (6,10), SiO_3 (5,90), Fe_2 O_3 (2,05), K_2 O (1,90) e outros óxidos em concentrações menores. Para a caracterização da amostra de lapis lazuli, foram utilizados termoluminescência (TL), ressonância paramagnética eletrônica (EPR) e técnicas de espectroscopia de reflectância. Em TL, é claro, as curvas de emissão da amostra natural, irradiada ou com tratamento térmico têm sido utilizadas. Uma curva de emissão da amostra natural apresentou picos em 296°C e a 372°C , mas as amostras irradiadas mostraram picos em 140°C, 250°C e 350°C. Logo mostrou - se que o pico em 140°C, é na verdade, uma sobreposição dos picos em 116°C e 160°C. O segundo pico cresce linearmente com a dose até cerca de 7000-8000 Gy. O lápis-lazúli apresenta um decaimento anômalo. O primeiro pico decaiu a partir de 3400 (u.a) para 1700 (u.a), em 45 horas, o segundo pico decaiu a partir de 8500(u.a) para 3000 (u.a), nas mesmas 45 horas. Para a Avaliação da parâmetros E e s, o método de forma de pico e Tm- Tstop. O terceiro método com base em diversas taxas de aquecimento para a leitura TL, com a utilização direta do método resultou em valores de E e s irrealistas. Não se encontrou a explicação por que, mas ao fazer deconvolução das curvas de emissão para cada taxa de aquecimento encontramos resultados mais realistas. A deconvolução mostrou quatro picos em 110°C, 146°C, 191°C 245°C, com valores E, respectivamente iguais a 1,229 eV ; 1,23eV; 1,24eV e 1,25eV . O espectro de EPR da amostra experimental apresentou seis sinais de Mn^(2+) e um sinal grande de Fe^(3+) com g= 2,0. A irradiação da ordem de dezenas de kGy produzido um sinal em torno de g=2,003 devido ao centro em F induzido pela radiação. O espectro de refletância mostra um vale em torno de 600 a 800 nm, que corresponde a uma banda de absorção do mesmo comprimento de onda e é responsável pela coloração azul. / Lapis Lazuli is a natural silicate mineral investigated in the present work. It is a complex solid solution of four other silicate minerals, sodalite, Nosean, Hanyne and Lazurite. This compositon of solid solution does not allow the estimate of the percentage of each mineral component from the result of X ray fluorescence analysis, which has revealed as main oxide components of lapis lazuli as (in mol % ) SiO_2 (33,2), CaO (16,3), MgO (12,1) and Al_2 O_3 (10,1) and in smaller concentrations Na_2 O (6,10), SiO_3 (5,90), Fe_2 O_3 (2,05), K_2 O (1,90) plus others in even smaller concentration. For the characterization of the lapis lazuli sample, we used thermoluminescence (TL), electronic paramagnetic resonance (EPR) and reflectance spectroscopy techniques. In TL, of course, glow curves of natural or irradiated or annealed samples have been used.\\\\ A typical glow curve presented peaks at 296.5°C and at 372°C, but irradiated sample has shown peaks at 140°C, 250°C and 350°C. Later it was shown that 140 °C peak is actually a superposition of 116°C and 160°C peaks. The second peak is the prominent one and its height grows linearly with the dose up to about 7000 to 8000 Gy. Lapis lazuli presents an anomalous fading. The first peak decays from 3400 (a.u.) to 1700 (a.u.) in 45 hours, the second peak decays from 8500 (a.u.) to 3000 (a.u.) in the same 45 hours. For the evalution of parameters E and s, peak shape method and Tm-Tstop methods have been used. The third method based on various heating rates for TL reading, with the direct use of method yielded unrealistic E and s values. We did not find explanation why, but doing the deconvolution of glow curves for each heating rate we found more realistic results. The deconvolution has shown four peaks at 110°C, 146°C, 191°C ands 245°C with E-values, respectively equal to 1.229eV, 1,23eV, 1.24eV and 1,25 eV. The EPR spectrum of natural sample consisted of six signals of Mn^(2+) and strong Fe^(3+) signal at g=2,0. The irradiation of the order of tens of kGy produced a signal around g=2,003 due to radiation induced F-center. The reflectance spectrum shows a dip around 600- 800nm which corresponds to an absorption band of the same wavelength and is responsible for blue colour.

Cristais naturais de pumpelita Ca8Al8(Mg,Fe,Mn,Al)[(SiO4)4/(Si2O7)4/(OH)8(H2O, OH)4]), provenientes da mina de Brejui, município de Currais Novos, Rio Grande do Norte, foram investigados através das técnicas de termoluminescência (TL), absorção óptica (AO) e ressonância paramagnética eletrônica (EPR) com o intuito de entender os efeitos da radiação ionizante e de recozimento em altas temperaturas sobre estes cristais. As curvas TL obtidas apresentaram cinco picos, 90, 145, 220, 315 e 390 oC, após terem sido irradiadas para uma taxa de quecimento de 4 °C/s. A decomposição espectral da luz TL foi obtida para todos os picos e presentou uma emissão centrada em 575 nm e largura à meia altura de 75 nm e outras duas emissões menores em 470 nm e 660 nm indicando que o processo TL pode possuir mais de um centro de recombinação, independentemente das temperaturas dos picos. Em um segundo momento, foi investigado o efeito de diferentes tratamentos térmicos pré-irradiação (500, 600, 700, 800 e 900 °C) nas propriedades TL dos cristais. Somente a intensidade das emissões mostrou ser dependente da temperatura destes tratamentos térmicos, a posição dos quatro picos não foi alterada. Os picos em 220 e 390 °C apresentaram grande sensibilidade ao tratamento térmico. Uma análise termogravimétrica mostrou que entre 650 e 800 °C houve grande perda de massa envolvida num processo endotérmico, sugerindo uma provável mudança de estado. O espectro de ressonância paramagnética eletrônica mostra um sinal muito intenso que se estende de 1000 a 6000 Gauss e seis linhas típicas hiperfinas de Mn2+ entre 3000 e 4000 Gauss. O sinal EPR gigante é devido à interação dipolo (magnético) dipolo magnético) de Fe3+. Os espectros de AO de amostras recozidas em 600 °C, 700 °C e 900 °C mostram num resultado muito interessante, a banda em torno de 1060 nm, que, é devida a Fe2+ muda pouco com o tratamento térmico até 800 °C, mas, entre 800 °C e 900 °C a banda decresce. Nessa região de temperatura, ocorre a reação: Fe2+ temperaturae + Fe3+ Fe2+ perde um elétron e se torna Fe3+. Este processo é, também, responsável pelo aumento muito grande da intensidade EPR na região de g = 2,0, em amostras que sofreram recozimentos em temperaturas acima de 850 °C, Nestas temperaturas, a coloração da pumpelita é também afetada. Todos os picos TL sofrem fotoesvaziamento (bleaching), quando a amostra irradiada é exposta a luz UV. / Natural mineral of pumpellyite, one of the members of epidote group has been investigated. With chemical formula (Ca8Al8(Mg,Fe,Mn,Al)[(SiO4)4/(Si2O7)4/(OH)8(H2O, OH)4]), the sample here studied was collected from Brejui Mine, Currais Novos County, state of Rio Grande do Norte. The work was aimed to investigate its thermoluminescence (TL), color centers and electron paramagnetic properties. Annealing at high temperatures, heavy irradiation and UV irradiation techniques have been used. The physical properties of interest are due to the elements composing crystal structure such as Si, Al, Mg, Fe and Mn, however among about twenty elements that can be considered impurities; only Na, K and Cr participate. The TL glow curve obtained from 600 °C for one hour pre-annealed and then - irradiated sample has shown 90, 145, 220, 275 and 390 °C peaks. A heating rate of 4 °C has been used for TL read out. The lowest 90 °C peak is very unstable, however, it is by far the most sensitive one to the irradiation; at 50 Gy -dose its peak height is almost 100 times larger. Among others, the 315 °C peak grows faster. Heat treatments before irradiation increase the sensitivity of TL peaks slowly from 500 to 800 °C, but such increase becomes very large above 800 °C. For example the 390 °C peak sensitivity increases by a factor 100 on going from 500 C to 900 °C annealing. The spectral analysis of the emitted TL light has shown that there are 470, 575 and 600 nm bands indicating that there are at least three recombination centers. The 575 nm is by far the dominating one. The UV light bleaching has shown that all the TL peaks decay fast up to 10 minutes exposure and a residual TL is left after long time exposure. The optical absorption spectrum is characterized by four absorption bands in the visible region, one strong and broad band around 1060 nm and several in near IR region. The 1060 nm band is due to Fe2+ which around 850 900 °C annealing decreases indicating that Fe2+ liberates electrons leaving Fe3+. The EPR spectrum is dominated by Fe3+ spin spin interaction. Mn2+ six hyperfine lines superpose Fe line around g = 2,0. Under 850 900 °C heating, that broad Fe3+ lines becomes stronger and broader due to Fe2+ changing to Fe3+. The EPR intensity of 800 °C annealed sample and then irradiated to 1 kGy - dose increases with microwave power, but start saturation around 30 to 40 mW power.

No mundo de hoje, onde o uso da radiação de diversas naturezas está generalizado, a quantificação da energia depositada por essas diferentes radiações se tornou uma atividade de grande importância, principalmente quando a faixa de energia é considerada elevada, estas altas energias de radiação estão presentes, geralmente, em aceleradores de partículas, reatores nucleares e em irradiadores industriais, por exemplo. Este trabalho tem como objetivo medir altas doses de radiação de raios gama, feixes de elétrons e feixes de prótons utilizando duas variedades de um silicato natural (água-marinha e goshenita) e medir altas doses de nêutrons epitérmicos de alta fluência utilizando dosímetros de Fluoreto de Lítio dopados com Mg, Cu e P (MCP). A técnica utilizada para medir a dose absorvida por esses materiais foi a termoluminescência. As irradiações com raios- γ provenientes de fontes de 60Co foram de 100 kGy a 2000 kGy para a água-marinha e de 600 kGy a 2000 kGy para a goshenita, os resultados de intensidade TL vs Dose mostram que a partir de certa dose - 250 kGy e 1234,8 kGy para água-marinha e goshenita, respectivamente - o sinal TL começa a decrescer. Foi observado neste trabalho que, estes materiais quando irradiados com tais doses e posteriormente irradiados com doses baixas de alguns Gys até cerca de 400-500 Gy, o sinal TL decresce regularmente, podendo ser utilizado na dosimetria das radiações nessa faixa de dose. Para a irradiação de feixe de prótons e de feixe de elétrons foram utilizados dosímetros em placa de goshenita e dosímetros de pastilhas de água-marinha, a carga do feixe de prótons vai de 20 a 216 μC e a dose do feixe de elétrons vai de 10 kGy a 70 kGy. As irradiações com nêutrons epitérmicos utilizando LiF: Mg, Cu, P foram realizadas no reator IEA-R1/IPEN com fluências de 1014 a 1017 n/cm² e a quantificação das doses absorvidas foram realizadas utilizando o método UHTR (Ultra High Temperature Ratio). / In the present days the usage of ionizing radiation from several different sources is spread all over the world. The measurement of the absorbed energy from these radiations became a very important task, mainly when the dose range is considered being in a very high level. These high energies of radiation are associated with particles accelerators, nuclear reactors and industrial irradiators, for example. This work is concerned for measuring high-doses of gamma radiation, electron beams and proton beams using two varieties of a natural silicate (aqua-marine and goshenite) and measuring effects of high-fluence neutrons using LiF: Mg, Cu, P (MCP) detectors. Thermoluminescence was employed to measure the absorbed dose for irradiations with gamma rays ranging from 100 kGy up to 2000 kGy for aquamarine and from 600 kGy and 2000 kGy for goshenite. The TL intensity reaches maximum at 250 kGy in aquamarine and at 1234 kGy for goshenite; this means that for doses larger than 250 kGy in aquamarine and 1234 kGy in goshenite the TL intensity drops. However, the descending part can be used in very high dose dosimetry. Furthermore, has been observed in this study that starting with aquamarine irradiated with 250 kGy and goshenite with 1234 kGy, the subsequent irradiation with doses from low to 400-500 Gy produces a regularly decreasing TL intensity, so that it can be used in radiation dosimetry from low to 400-500 Gy doses. For proton beams, goshenite were used. The beam charge ranges from 20 a 216 μC. For electron beams small pressed pellets of aquamarine were used. The dose ranges from 10 kGy to 70 kGy. The epithermal neutron irradiation was performed at IEA-R1 research reactor at IPEN and MCP-LiF detectors were used to measure the absorbed dose. A method called UHTR (Ultra High Temperature Ratio) was employed for calculating the amount of energy absorbed by the dosimeter. The fluence of epithermal neutrons ranges from 1014 a 1017 n/cm².

A forma isomórfica predominante nos biominerais (casca de ostra, coral, madrepérola e concha) estudados foi a aragonita. Contudo, o surgimento da fase calcita deu-se à temperatura de 500°C a uma taxa de aquecimento de 10°C/s para todas as amostras; e para a amostra de coral, à temperatura de 400°C, independente da taxa de aquecimento. O elemento mais abundante nas amostras de biominerais foi o Ca na forma de CaO e para os silicatos (tremolita, diopsídio e rodonita), o Si na forma de SiO. O elemento traço mais presente nas amostras de biominerais foi o Fe. A análise de ressonância paramagnética eletrônica mostrou as linhas de Mn2+ nas amostras de coral e madrepérola, antes da irradiação. Para amostras irradiadas, os defeitos encontrados foram os radicais CO2-, CO33-, CO3-, SO2-, SO3-, e num intervalo de g entre 2,0010 e 2,0062. Na análise por absorção óptica dos biominerais foram encontradas transições devido à presença de Mn nas amostras. Foi observado um pico termoluminescente (TL) em aproximadamente 140°C para os biominerais e em 180°C para os silicatos, cuja intensidade depende diretamente da dose. Para amostras expostas a diferentes tipos de radiações, o pico TL ocorre em temperaturas mais baixas. Para as curvas dose-resposta obtidas para esses materiais, foi possível determinar um intervalo de linearidade para o qual a sua aplicação em dosimetria de doses altas se torna possível. Levando-se em consideração o tipo de radiação, dentre os biominerais e os silicatos, obteve-se a menor dose detectável (40mGy), para a radiação gama em amostra de casca de ostra utilizando-se a técnica de medição de luminescência opticamente estimulada (LOE). Para radiação beta, as amostras de tremolita e diopsídio obtiveram a menor dose detectável (60mGy). No geral, obteve-se uma boa reprodutibilidade para as amostras, utilizando-se as técnicas TL, LOE e emissão exoeletrônica termicamente estimulada (TSEE) para as radiações alfa, beta e gama. Portanto, pode-se concluir que as amostras caracterizadas neste trabalho podem ser utilizadas como detectores/dosímetros de doses altas. / The predominant isomorphous form in the biominerals studied in this work (oyster shell, coral, mother of pearl and shell) was aragonite. The appearence of the calcite phase occurred at 500°C at a heating rate of 10°C/s for all samples except for the coral sample, which was 400°C, independent of the heating rate. The most abundant element in the biominerals samples was Ca in the CaO form, and in the silicates (tremolite, diopside and rhodonite) Si in the SiO form. The most common trace element observed in the biominerals samples was Fe. The analyses of electron paramagnetic resonance showed lines of Mn2+ in the coral and mother-of-pearl samples before irradiation. In the case of the irradiated samples, the defects found were CO2-, CO33-, CO3- and SO2-, in the g range between 2.0010 and 2.0062. In the analyses by optical absorption of biominerals, transitions due to the presence of Mn in the samples were found. A thermoluminescent (TL) peak at approximately 140°C was found for the biominerals and at 180°C for silicates, which intensity depends directly on the dose. For samples exposed to different types of radiation, the TL peak occurred at lower temperatures. From the dose-response curves obtained for these materials, it was possible to determine a linear range for which their application in high dose dosimetry becomes possible. Taking into account the radiation type, among biominerals and silicates, the lowest detectable dose (40mGy) to gamma radiation was achieved for oyster shell samples using the measuring technique of optically stimulated luminescence (OSL). Using beta radiation, for diopside and tremolite samples the lowest detectable dose of 60mGy was obtained. For all samples, using the TL, OSL and thermally stimulated exoelectron emission (TSEE) techniques in alpha, beta and gamma radiation beans a good response reproducibility was obtained. Therefore, the samples characterized in this work are suitable to be used as high dose detectors/dosimeters.