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A sílica obtida da queima de casca de arroz foi convertida nas fases α e β. A estabilização da fase β foi obtida pela introdução de alumínio e cálcio na rede de sílica, 10001100 °C, na proporção CaO:2Al2O3:38SiO2. Foi observado que a transição de fase α→β da cristobalita α tem sua temperatura de transição reduzida de 175°C bem como sua entalpia de transição, de 16,0 J/g para 7,0 J/g. Esse efeito é causado pela introdução de íon K+, presente na casca de arroz, na estrutura da sílica. O processamento empregado nessa conversão usa equipamentos normalmente encontrados em empresas de cerâmica tradicional moinho, atomizador, prensa e forno / Silica generated from burned rice shells has been converted to the β and &#945 phases of cristobalite. The β phase stabilization was acomplished by instilling aluminum and calcium into the silica structure, at 1000-1100 °C, in the following proportion CaO:2Al2O3:38SiO2. The phase transition α→β of the α-cristobalite has a lower transition temperature, as compared with cristobalite made from pure silica, from 270°C to 170°C. Also the transition entalphy was reduced from 16,0 J/g to 7,0 J/g. These changes were attributed to the K+ ion present in the silica structure of the burned silica. The process used in this convertion makes use of standard equipments, regularly used in ceramic producing companies mill, spray dryer, furnaces, and press.

Thesis (M.S.)--Virginia Polytechnic Institute and State University, 1994. / Vita. Abstract. Includes bibliographical references (leaves 36-38). Also available via the Internet.

A sílica obtida da queima de casca de arroz foi convertida nas fases α e β. A estabilização da fase β foi obtida pela introdução de alumínio e cálcio na rede de sílica, 10001100 °C, na proporção CaO:2Al2O3:38SiO2. Foi observado que a transição de fase α→β da cristobalita α tem sua temperatura de transição reduzida de 175°C bem como sua entalpia de transição, de 16,0 J/g para 7,0 J/g. Esse efeito é causado pela introdução de íon K+, presente na casca de arroz, na estrutura da sílica. O processamento empregado nessa conversão usa equipamentos normalmente encontrados em empresas de cerâmica tradicional moinho, atomizador, prensa e forno / Silica generated from burned rice shells has been converted to the β and &#945 phases of cristobalite. The β phase stabilization was acomplished by instilling aluminum and calcium into the silica structure, at 1000-1100 °C, in the following proportion CaO:2Al2O3:38SiO2. The phase transition α→β of the α-cristobalite has a lower transition temperature, as compared with cristobalite made from pure silica, from 270°C to 170°C. Also the transition entalphy was reduced from 16,0 J/g to 7,0 J/g. These changes were attributed to the K+ ion present in the silica structure of the burned silica. The process used in this convertion makes use of standard equipments, regularly used in ceramic producing companies mill, spray dryer, furnaces, and press.

The inversion temperature of cristobalite was investigated by incorporating TiO₂, AlPO₄, and BPO₄ into the cristobalite phase using solid state reactions. The combination of TiO₂ and AlPO₄ proved to be most effective in lowering the inversion temperature of cristobalite. Phase diagrams at the high silica corner were constructed for the respective systems. High cristobalite was stabilized for compositions prepared from the CaO-Al2₂O₃-SiO₂ and CuO-Al₂O₃-SiO₂ system using sol-gel processing. The stabilization mechanism is attributed to the surface energy effect resulting from the formation of fine crystals. The structural evolution from the x-ray amorphous gel to high cristobalite was examined by FTIR and Raman spectroscopy. The thermal expansion of the stabilized high cristobalite was characterized by high temperature x-ray. Changes in bond angle continue to dominate the thermal expansion of high cristobalite. / Ph. D.

A detailed understanding of fundamental material properties can be obtained through the study of atomic vibrations, performed experimentally with neutron scattering techniques and coupled with the two powerful new computational methodologies I have developed. The first approach involves phonon-based simulations of the pair distribution function - a histogram of localised atomic positions generated experimentally from total scattering data. This is used to reveal ordering behaviour, to validate interatomic models and localised structure, and to give insights into how far dynamic behaviour can be studied using total scattering techniques. Most importantly, the long-standing controversy over dynamic disorder in β-cristobalite is resolved using this technique. Inelastic neutron spectroscopy (INS) allows \emph{direct} study of vibrational modes through their interaction with the neutron beam, and is the experimental basis for the second strand of the new methodology. I have developed new simulation and refinement tools based on the next generation of spectrometers currently being commissioned at the ISIS pulsed neutron source. This allows a detailed powder spectroscopy study of cristobalite and vitreous silica demonstrating that the Bose peak and so-called 'fast sound' features can be derived from standard lattice dynamics in both the crystal and the amorphous counterpart, and allowing discussion of their origins. Given the controversy in the literature, this is a key result. The new methodology also encompasses refinement of interatomic models against powder INS data, with aluminium providing a successful test-case. A more complex example is seen in calcite, with experimental data collected during the commissioning of the new MERLIN spectrometer. Simulated one-phonon coherent INS spectra for the single crystal and powder (the latter including approximations to multi-phonon and multiple scatter) are fully convolved with experimental resolution functions. These are used in the analysis of the experimental data, yielding previously unpublished dispersion curves and soft mode information, as well as allowing the effectiveness of powder refinement of more complex materials to be assessed. Finally, I present further applications with technologically important materials - relaxor ferroelectrics and high temperature pnictide superconductors. The conclusions draw together the different strands of the work, discussing the importance of these new advances together with future developments and scientific applications.

Assuming that its deformation is both static and homogeneous, a method was devised within the framework of finite strain theory to calculate the elastic constants of a crystal at zero pressure as well as functions of pressure. As this method can be used for a crystal of any symmetry with a variety of potentials, elastic constant calculations were completed for both quartz and cristobalite using the potentials derived by Lasaga and Gibbs (1987, 1988), Tsuneyuki et al. (1988), van Beest et al. (1990) and Boisen and Gibbs (1993). Among the four theoretical potentials derived from force fields calculated for molecule H₆Si₂Q₇, two potentials associated with the SiO bond stretching as well as the OSiO and the SiOSi bond angle bending terms yield reasonable agreements with the experimental data, supporting the assumption that the binding forces in crystals are similar to those in small molecules (Gibbs 1982). Using the semi-empirical potentials, including the SQLOO potential derived with the covalent model (Boisen and Gibbs 1993) and two derived with the ionic model (Tsuneyuki et al. 1988; van Beest et al. 1990), calculations of the elastic constants reproduce the experimental results for both quartz and cristobalite. The pressure derivatives of the elastic constants calculated with these potentials also agree with the experimental results measured for quartz at low pressures and yield pressure derivatives of the bulk modulus that are in close agreement with that observed for quartz. Using the SQLOO potential, although the results of the calculations do not agree with the experimental data as well as those calculated using the two ionic potentials, the agreement of the calculations made with the theoretical potentials was improved significantly. Finally, using the three semi-empirical potentials, the elastic constants were calculated as functions of pressure for quartz and cristobalite up to their transitional pressures. Calculated for both quartz and cristobalite, different behaviors of the elastic constants were found using different potentials. For cristobalite, the variations of its elastic constants and bulk modulus are better modeled by the SQLOO potential as its structural behaviors calculated with the SQLOO potential are consistent with the X-ray diffraction studies. / Master of Science

Η Τέφρα Φλοιού Ρυζιού (ΤΦΡ) είναι ένα από τα κυριότερα γεωργικά απόβλητα και προέρχεται από την καύση του φλοιού ρυζιού (ΦΡ) στις ορυζοβιομηχανίες για παραγωγή ενέργειας ή και μείωσης του όγκου των αποβλήτων. Η τέφρα φλοιού ρυζιού αποτελεί περίπου το 18-20% του φλοιού του ρυζιού, ο οποίος αποτελεί περίπου το 20% του ακατέργαστου ρυζιού ενώ συνήθως είναι κρυσταλλική. Καθώς ο παγκόσμιος όγκος της ετήσιας παραγωγής σε ρύζι και κατ’ επέκταση σε τέφρα φλοιού ρυζιού αυξάνεται διαρκώς, εγείροντας περιβαλλοντικά και οικονομικά ζητήματα, η ανεύρεση ενός αποδοτικού και οικολογικού τρόπου εκμετάλλευσης της είναι θέμα μείζονος σημασίας. Παράλληλα, τα υψηλά ποσοστά της ΤΦΡ σε διοξείδιο του πυριτίου την καθιστούν πιθανή πηγή πυριτίου για πολλές εφαρμογές, μία από τις οποίες είναι και οι σύνθεση ζεόλιθων. Στην παρούσα εργασία μελετήθηκε η αξιοποίηση κρυσταλλικής ΤΦΡ στην σύνθεση τεσσάρων τύπων ζεόλιθων και συγκεκριμένα των MFI, FAU, BEA και LTA. Για τον σκοπό αυτό αρχικά χαρακτηρίστηκε η πρώτη ύλη, δηλαδή η ΤΦΡ, τόσο ως προς την χημική της σύσταση και περιεκτικότητα σε άκαυτο άνθρακα όσο και ως προς την κρυσταλλική δομή της. Στη συνέχεια εξακριβώθηκαν οι συνθήκες καύσης του ΦΡ οι οποίες οδηγούν στην μετατροπή από την άμορφη στην κρυσταλλική δομή του διοξειδίου του πυριτίου, η οποία ονομάζεται χριστοβαλίτης. Εφόσον αυτή η κρυσταλλική δομή είναι ακατάλληλη για την παραγωγή ζεόλιθων, μελετήθηκε η δυνατότητα διαλυτοποίησης της ΤΦΡ σε υδατικό διάλυμα καυστικού νατρίου ώστε να καταστραφούν οι κρύσταλλοι και να παραληφθεί άμορφο διοξείδιο του πυριτίου. Για το σκοπό αυτό, επιλέχθηκαν οι μοριακές αναλογίες των πρώτων υλών που οδηγούν στη σύνθεση καθενός από τους τέσσερεις τύπους ζεόλιθων και η ΤΦΡ επεξεργάστηκε με την κατάλληλη αναλογία καυστικού νατρίου σε υδατικό διάλυμα σε διάφορες θερμοκρασίες και συνθήκες. Παρατηρήθηκε κρυστάλλωση του επιθυμητού τύπου ζεόλιθου σε κάθε μία από τις περιπτώσεις που εξετάστηκαν, ενώ το ποσοστό της διάλυσης του χριστοβαλίτη βρέθηκε ότι είχε την σημαντικότερη επίδραση στην απόδοση της διεργασίας και την καθαρότητα του προϊόντος. Ταυτόχρονα διαπιστώθηκε ότι το ποσοστό της διάλυσης του χριστοβαλίτη εξαρτάται κυρίως από την αναλογία μαζών RHA/NaOH και βρέθηκαν οι κατάλληλες τιμές. Καθώς το μεγαλύτερο ποσοστό διαλυμένου χριστοβαλίτη παρατηρήθηκε στην περίπτωση της σύνθεσης του ζεόλιθου LTA, η οποία επιπλέον δεν χρειάζεται οργανικό παράγοντα δομής ούτε υψηλές θερμοκρασίες, επιλέχθηκε να χρησιμοποιηθεί για την μελέτη και την βελτιστοποίηση της διεργασίας. Συγκεκριμένα, εξετάστηκαν διαφορετικές μέθοδοι επεξεργασίας της ΤΦΡ με καυστικό νάτριο, σε μεγάλο θερμοκρασιακό και χρονικό εύρος, ώστε να μελετηθεί η κινητική της διάλυσης του χριστοβαλίτη και να βρεθεί η ενέργεια ενεργοποίησης της. Στη συνέχεια μελετήθηκε η επίδραση της θερμοκρασίας και της διάρκειας στην κρυστάλλωση του ζεόλιθου LTA ώστε να μελετηθεί η κινητική της αντίδρασης και να βρεθεί η ενέργεια ενεργοποίησης της καθώς και οι βέλτιστες συνθήκες απόδοσης της διεργασίας και καθαρότητας του τελικού προϊόντος. Τέλος, εξετάστηκε η επίδραση δύο σημαντικών παραμέτρων, της θερμοκρασίας σύνθεσης και της ταχύτητας ανάδευσης στην ποιότητα του τελικού προϊόντος και βρέθηκαν οι βέλτιστες τιμές τους. Τα αποτελέσματα και τα συμπεράσματα από την παρούσα εργασία, έχουν κατατεθεί στον Οργανισμό Βιομηχανικής Ιδιοκτησίας (Ο.Β.Ι.), για την χορήγηση Διπλώματος Ευρεσιτεχνίας (Δ.Ε.), με αριθμό αίτησης: 20120100391. / Rice husk ash (RHA) is one of the major agricultural wastes and results from the combustion of rice husk (RH) at rice in milling facilities for energy production or waste volumes reduction. Rice husk ash is about 18-20% of the cortex of the rice, which is approximately 20% of raw rice and is usually in its crystalline form. As the global volume of annual production in rice and hence rice husk ash is increasing, raising environmental and economic issues, finding an efficient and ecological way of RHA exploitation is a major issue. In addition, the high rates of RHA on silica render possible silicon source for many applications, one of which is the synthesis of zeolites. In this study, the use of crystalline RHA in the synthesis of four zeolite types, namely MFI, FAU, BEA and LTA was investigated. For this purpose, the raw material, i.e. RHA, was characterized both in terms of its chemical composition and unburned carbon content as well as its crystalline structure. Afterwards, the combustion conditions of RH which lead to the conversion from the amorphous to the crystalline structure of silica, called cristobalite, were determined. Since this crystalline structure is unsuitable for the production of zeolites, the possibility of solubilizing RHA in aqueous sodium hydroxide solution was investigated, in order to destroy the crystals and receive amorphous silica. For this purpose, the molar ratios of the raw materials which would result in the synthesis of each of the four types of zeolites were selected and RHA was treated with the appropriate amount of sodium hydroxide in aqueous solution at various temperatures and conditions. The crystallization of the desired zeolite type in each of the cases examined was verified, while the rate of dissolution of cristobalite was found to have the most significant effect on the process efficiency and the product purity. Simultaneously, it was found that the rate of dissolution of cristobalite mainly depends on the mass ratio of RHA / NaOH and the most suitable values were determined. As the majority of dissolved cristobalite was observed in the case of LTA synthesis, which moreover does not require organic structure directing agent nor high temperatures, it was chosen to be used for the study of design and optimization process. Specifically, several methods of RHA treatment with sodium hydroxide at high temperature and time range were examined, in order to study the kinetics of dissolution of cristobalite and to find the activation energy. Then, the influence of temperature and duration on the crystallization of LTA was examined in order to study the kinetics of the reaction and to determine the activation energy as well as the optimum conditions of the process in terms of efficiency and final product purity. Finally, the effect of two important parameters, the temperature of the synthesis and the stirring speed, on the final product quality was investigated and the optimal values were found. The results and the conclusions of this study, have been submitted to the Hellenic Industrial Property Organization for the grant of Patent with application number: 20120100391.

Silica bricks is a refractory building material which contains at least 93 % of silicon dioxide in polymorphic forms, mostly -tridymite, -cristobalite and unreacted -quartz. In glass industry is used for building crowns of glass tanks and in coke industry is used for building coke oven batteries. The advantage is the high refractoriness under load, high resistance to acidic melts. The disadvantage is the low resistance to changes in temperature below 600 °C. The thesis deals with the influence of repeated firing on the silica bricks and to its porous structure and mineralogical composition.

Orientador: Sílvio Rainho Teixeira / Resumo: A falta de sincronismo entre o desenvolvimento industrial e a conscientização ambiental trouxe inúmeros impactos adversos ao meio ambiente. A quantidade de resíduos industriais gerados diariamente aumenta, enquanto a adoção de sistemas de gerenciamento ainda falha em muitos aspectos. Assim, o objetivo principal deste trabalho é desenvolver materiais vitrocerâmicos através da mistura de Areia Descartada de Fundição (ADF) com resíduos sólidos oriundos da indústria de papel e celulose (grits e lama de cal), visando o desenvolvimento de novos produtos que sejam ecologicamente corretos. Os materiais vitrocerâmicos obtidos a partir da cristalização do vidro com os resíduos de ADF, grits e lama de cal foram preparados utilizando o método tradicional, de fusão do composto, para a produção dos vidros; e, posterior cristalização, para obtenção das vitrocerâmicas. De acordo com a composição química dos materiais precursores e das misturas, os vidros foram obtidos à temperatura de 1450 °C. O trabalho foi desenvolvido em duas etapas principais: caracterização dos materiais precursores e preparação e caracterização dos vidros e vitrocerâmicas. Os estudos de caracterizações foram feitos através das técnicas de análises granulométrica, morfológica, mineralógica, química, térmicas e tecnológicas. Foram obtidos 6 materiais vítreos distintos, intitulados de vidros I, II, III, IV, V e VI. Os vidros foram caracterizados por Difração de Raios X (DRX), Fluorescência de Raios X (FRX) e análise de ca... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The lack of synchronism between industrial development and environmental awareness has brought numerous adverse impacts to the environment. The amount of industrial waste generated daily increases, while the adoption of management systems still fails in many ways. Thus, the main objective of this work is to develop glass-ceramic materials by mixing Waste Foundry Sand (WFS) with solid residues from the cellulose and paper industry (grits and lime mud), aiming at the development of new products that are environmentally friendly. The glass were obtained using the traditional melting-quenching method. The produced glasses were controlled by the crystallization process to obtain the glass-ceramics materials. According to the chemical composition of the precursor materials and the chemical composition of the mixtures, the glasses were fused at 1450 °C. The work was developed in two main stages: characterization of the precursor materials and preparation and characterization of glasses and glass-ceramics. The characterization studies were made through the techniques of particle size, morphological, mineralogical, chemical, thermal and technological analysis. Six distinct vitreous materials were obtained, entitled glasses I, II, III, IV, V and VI. The glasses were characterized by the analysis of X-Ray Diffraction (XRD), X-Ray Fluorecence (XRF) and differential scanning calorimetry. After identifying the crystallization peaks of each glass, heat treatment was given (temperatures high... (Complete abstract click electronic access below) / Doutor