A siderurgia vem sofrendo transformações que buscam inovação e matérias-primas alternativas. Dentro deste contexto, o uso de resíduos industriais para a formação de escórias sintéticas é tido como alternativa na busca de novos materiais e rotas de reaproveitamento de resíduos. Portanto, este trabalho teve como objetivo estudar o uso de escórias sintéticas na etapa de dessulfuração do ferro-gusa, aço e ferro fundido. Assim como, propor a utilização da sodalita e da alumina em substituição à fluorita e o resíduo de mármore em substituição à cal convencional. Inicialmente, o resíduo foi caracterizado utilizando as seguintes técnicas: análise química, análise granulométrica, área de superfície específica, difração de raios-X, microscopia eletrônica de varredura (MEV) e análise de espectroscopia por energia dispersiva (EDS). Os resultados da caracterização mostraram que aproximadamente 90% das partículas do resíduo de mármore estão abaixo de 100m e sua área superficial foi de 0,24m²/g. Através da difração de raios-X foi observado que o resíduo é composto por CaCO3, MgCO3 e SiO2. Na sequência, foram feitas simulações com o software Thermo-Calc para obter dados termodinâmicos das fases presentes nas misturas e compará-los com os resultados experimentais. Além disso, também foram calculados dados de capacidade de sulfeto (Cs), partição de enxofre (Ls) e basicidade ótica () das misturas iniciais. Posteriormente, foram realizados os ensaios experimentais em escala laboratorial para ferro-gusa, ferro fundido e aço, respectivamente nas temperaturas de 1400°C, 1550°C e 1600°C. Nos ensaios de dessulfuração do aço e do ferro-gusa, utilizou-se um rotor de alumina com o objetivo de favorecer a agitação no metal e aumentar a remoção de enxofre. Na etapa de dessulfuração do ferro-gusa, constatou-se que a fase sólida de CaO é a responsável pela remoção de enxofre e que a presença das fases silicato tricálcio e aluminato tricálcio (3CaO.SiO2 e 3CaO.Al2O3) limitam a reação, sendo maiores suas concentrações nas escórias que utilizaram o resíduo de mármore e sodalita, devido a presença de SiO2 e Al2O3 nestas matérias-primas. Já para o aço e o ferro fundido, que foram estudados com escórias à base de CaO e Al2O3, observou-se que o aumento da fase líquida favoreceu a dessulfuração. Verificou-se que a dessulfuração no ferro fundido foi por escória de topo e no aço por um processo misto, onde a fase líquida e fase sólida participaram da dessulfuração. / The steel industry is going through transformations aiming at innovation and use of alternative raw materials. In this context, the use of industrial waste in the production of synthetic slag is considered an important option on the search for new materials and waste reuse. Therefore, the aim of this work was to study the use of synthetic slags at the desulfurization of hot metal, steel and cast iron. It was proposed the use sodalite and alumina instead of fluorite and the use of marble waste instead of lime. Marble waste was characterized by chemical analysis, particle size analysis, specific surface area, X-ray diffraction (XRD), scanning electron microscopy (SEM), analysis with energy dispersive spectroscopy (EDS). The characterization results showed that almost 90% of the particles are smaller than 100 m and its specific surface area was 0.2406m²/g. The XRD has showed the presence of compounds such as CaCO3 and MgCO3 and SiO2. Further, simulations using Thermo-Calc were performed in order to obtain thermodynamic data of the present phases, and to compare with experimental data. Furthermore, sulfide capacity (Cs), sulfur partition (Ls) and optical basicity () were determined. The experimental procedures were carried out at 1400°C, 1550°C and 1600°C for hot metal, cast iron and steel, respectively. In addition, steel and hot metal tests were performed using an alumina rotor to raise the desulphurization. In hot metal desulphurization, solid CaO phase was responsible for sulfur removal. Furthermore, 3CaO.SiO2 and 3CaO.Al2O3 phases limited the reaction, being their concentration higher in the slags with marble waste and sodalite, due to the presence of SiO2 and Al2O3 in these raw materials. Slags composed mainly of CaO and Al2O3 were used in steel and cast iron desulphurization. It was observed that when increasing liquid phase, the reaction of desulphurization was favored. Besides, it was found that cast iron desulfurization occurs by top slag mechanism and steel desulfurization by a mixed process where the liquid phase and solid phase have influence on the desulfurization.

In the heart of a park, a path spirals up a hill. Follow it and the trees part to reveal a building halfway up. Its thick, rough walls are pulled apart at moments, allowing light and movement into the space. The path leads between the walls. The narrow passage continues in a counter-clockwise motion up a staircase, leading you towards the light; moving from opacity to transparency, darkness to light, thick to thin, and exploring the mo- ments between. The space marks the passage of time. You see sunrise, marked by three narrow slits oriented to capture the light on the Winter and Summer solstices, and Spring and Fall equinoxes. The curved walls leading from the white art glass windows cradle the light like a cupped hand. The midday sun illuminates the central core, translated through the medium of semi-circular, veneer screens. The light and wood interact, revealing what is hidden, allowing the glowing screens to illuminate the outer circle. On the opposite side of the space are similarly-oriented windows to capture the Summer, Spring, Fall, and Winter sunsets, completing the day. It is a space apart from the world into which only the light and the self may enter. The only view of the outside world is the changing sky at the center. It is a space looks at light and how it moves through, is captured by, or is reflected by material. Light changes the materials in the space, is changed by them and marks the passage of time -- days and the seasons. / Master of Architecture

Thesis (MSc) -- Stellenbosch University, 1973. / The Marble Delta is an area of approximately 40 sq. km in Natal (30°22' Long., 30°40' Lat.), occupied by Precambrian marble and associated granites. The deeply dissected country was geologically mapped on a scale of I : 6 000. A new lithostratigraphic classification of the metasediments is proposed. The base of the lowermost Le Joncguet Formation (composed of dolomitic marble and siliceous beds) is not exposed. This is followed by the predominantly ca.lcitic Oribi Formation with interbedded dolomite and graphitic layers. The marble is unconformably overlain by the Cherrywillingham Formation which comprises mainly amphibolite and granulite. The .three formations together constitute the Marble Delta Group. The main petrological units are calc-silicate marble, metaquartzite, dolomite marble, cluster serpen~ine marble and ce,lcite marble. Graphite layers are considered to have originated in situ from organic remains; there is occasional evidence of ionic transfer of carbon from this graphite by magmatic fluids. The common mineral assemblages are diopside + calcite + dolomite, tremolite + calcite + diopside + quartz, calcite + quartz + dolomite, forsterite + calcite + dolomite, plagioclase + cordierite + garnet + quartz, amphibole + clinopyroxene + plagioclase, hornblende + clinopyroxene + calcite, wollastor~te + calcite + diopside. Other minerals are graphite, antigorite, chrysotile, sphene, spinel, clinohumite, chondrodite, zoisite, clinozoisite, hedenbergite, phlogopite, ilmenite, hercynite, dravite, cummingtonite, talc, apatite, microcline, saponite. The mineral assemblages resulted from regional metamorphism and polyphase contact metamorphism.

Σημαντικός αριθμός μνημείων και έργων τέχνης είναι κατασκευασμένα από πέτρα, μάρμαρο κατά πρώτο λόγο, και έπειτα από ασβεστόλιθο και από άλλα πυριτικά υλικά. Η παρούσα εργασία επικεντρώθηκε στη μελέτη της διάλυσης του μαρμάρου σε διάφορες συνθήκες με απώτερο στόχο την αποκάλυψη του μηχανισμού της φυσικοχημικής αυτής διεργασίας τόσο για την περίπτωση ασβεστιτικών όσο και δολομιτικών μαρμάρων. Η κατανόηση του μηχανισμού του προβλήματος είναι απαραίτητη για την κατάλληλη προσέγγιση και επιλογή των μεθόδων προστασίας. Έτσι, στην παρούσα εργασία επιχειρήθηκε: α) Ο προσδιορισμός του μηχανισμού διάλυσης από πειράματα μέτρησης της κινητικής της διάλυσης του μαρμάρου σε ακόρεστα ως προς το βασικό συστατικό (ασβεστίτης, δολομίτης) διαλύματα και σε διαφορετικές συνθήκες ακορεστότητας. β) Η αναστολή της διάλυσης με την προσθήκη υδατοδιαλυτών τασιενεργών ουσιών και η διερεύνηση του μηχανισμού δράσης τους. γ) Η δημιουργία δυνητικά προστατευτικών επικαλύψεων των επιφανειών του (ασβεστιτικού) μαρμάρου με στρώματα ανόργανων αλάτων. δ) Η σύγκριση των αποτελεσμάτων μέτρησης του ρυθμού διάλυσης τόσο παρουσία όσο και απουσία προσθέτων ουσιών με βιβλιογραφικές αναφορές, και αποτελέσματα από πειράματα υπαίθριας έκθεσης και από πειράματα έκθεσης δοκιμίων σε συνθήκες επιταχυνόμενης διάβρωσης σε θάλαμο αλατονέφωσης (παρουσία και άλλων παραγόντων, όπως μικροοργανισμοί, μικροβιοκτόνες ενώσεις). Ο στόχος της σύγκρισης αυτής ήταν η επιλογή του καταλληλότερου μοντέλου για την αξιόπιστη δοκιμή νέων υλικών και μεθόδων προστασίας του μαρμάρου. Για τη διεξαγωγή των δοκιμών, επιλέχθηκαν τρεις τύποι μαρμάρου που απαντώνται σε μνημεία και γλυπτά στην Ευρώπη: Carrara (ασβεστίτης >98%), Πεντελικό (ασβεστίτης >98%) και Ekeberg (δολομίης ~93%). Τα διαλύματα που χρησιμοποιήθηκαν στις μετρήσεις, κινητικής της διάλυσης ήταν ακόρεστα ως προς ασβεστίτη και παρασκευάζονταν με την αραίωση κατάλληλων όγκων stock διαλυμάτων CaCl2, MgCl2, NaHCO3, NaCl, και η αρχική τιμή του pH ρυθμιζόταν στο 8.25 με προσθήκη 0.01N NaOH. Μετά την αποκατάστασης ισορροπίας στα ακόρεστα διαλύματα εργασίας, γινόταν προσθήκη ακριβώς ζυγισμένης σκόνης μαρμάρου ή η εμβάπτιση των δοκιμίων (στερεωμένων σε ειδικό στήριγμα). Τρεις μέθοδοι χρησιμοποιήθηκαν για τις μετρήσεις της κινητικής της διάλυσης του μαρμάρου: συνθήκες ελεύθερης μεταβολής (free drift), συνθήκες σταθερού pH (pH-stat), συνθήκες σταθερού κορεσμού. Για τα ασβεστιτικά μάρμαρα, οι μετρήσεις του ρυθμού διάλυσης τόσο του μαρμάρου (κονιοποιημένου ή δοκιμίων) όσο και της πρότυπης ένωσης αναφοράς (ασβεστίτης) συναρτήσει της ακορεστότητας των διαλυμάτων έδειξαν γραμμική εξάρτηση. Σε όλες τις περιπτώσεις, οι ρυθμοί που υπολογίσθηκαν ήσαν της αυτής τάξης μεγέθους με τους αντίστοιχους ρυθμούς του καθαρού ασβεστίτη. Η θερμική κατεργασία του Πεντελικού μαρμάρου οδήγησε σε σημαντική αύξηση του ρυθμού διάλυσης, και η εξάρτηση των μετρούμενων ρυθμών, R, από τον σχετικό υπερκορεσμό, σ, ήταν μη γραμμική, με n>1. Για το δολομιτικό μάρμαρο Ekeberg, από το διάγραμμα του ρυθμού διάλυσης συναρτήσει της σχετικής ακορεστότητας σ, η προσαρμογή των δεδομένων στην R=kdσn έδωσε την τιμή n=2, οπότε εξήχθη το συμπέρασμα, ότι το στάδιο που καθορίζει τη διάλυση του δολομιτικου μαρμάρου είναι η επιφανειακή διάχυση. Μετρήθηκε και η διαλυτότητα τόσο του δολομιτικού όσο και των λοιπών τύπων μαρμάρου. Τα ασβεστιτικά μάρμαρα Πεντελικό και κρυσταλλίνα Θάσου έδωσαν τιμές για το γινόμενο διαλυτότητας κοντά στην αντίστοιχη τιμή για τον καθαρό ασβεστίτη (8.48) ενώ τα υπόλοιπα ασβεστιτικά (Carrara, Σπηλιά, Διονύσου) έδωσαν υψηλότερες τιμές διαλυτότητας. Τα δύο δολομιτικά μάρμαρα έδωσαν την αυτή τιμή για τη σταθερά διαλυτότητας, η οποία ευρίσκεται εντός των ορίων τιμών που έχουν αναφερθεί στην βιβλιογραφία για στοιχειομετρικό δολομίτη. Σε όλες τις περιπτώσεις ο ρυθμός διάλυσης του μαρμάρου βρέθηκε ότι ελέγχεται από την επιφανειακή διάχυση των δομικών λίθων στο οριακό στρώμα του υγρού. Η ρόφηση κάποιας ουσίας πάνω στο στερεό θα μπορεί να δεσμεύει τα ενεργά κέντρα και θα έχει αποτελεσματική δράση στην επιβράδυνση της διάλυσης. Έγινε μελέτη ρόφησης ουσιών με ιοντιζόμενες φωσφορικές και φωσφονικές ομάδες σε σκόνες των μαρμάρων Πεντελικού, Carrrara και Ekeberg (ισόθερμοι ρόφησης). Το HEDP μελετήθηκε σε μεγαλύτερη έκταση, τόσο γιατί η παρουσία του στα ακόρεστα διαλύματα είχε ως αποτέλεσμα τη σημαντικότατη αναστολή της διάλυσης, όσο και διότι ως ουσία με ιονιζόμενες δραστικές ομάδες αποτελεί μοντέλο για την μελέτη της επίδρασης ανάλογων ουσιών σε κρυσταλλικά στερεά τα οποία διαθέτουν κατιόντα μετάλλων στην επιφάνειά τους. Η προσθήκη του αναστολέα HEDP στα ακόρεστα διαλύματα είχε ως αποτέλεσμα τη μείωση του ρυθμού διάλυσης σε ανάλογο βαθμό με την προ-ρόφησή του. Η προσθήκη του HΕDP στα ακόρεστα διαλύματα, έδωσε μικρότερους ρυθμούς διάλυσης σε σύγκριση με τους αντίστοιχους ρυθμούς οι οποίοι ελήφθησαν από δείγματα στα οποία η ουσία αυτή είχε προ-ροφηθεί στο στερεό (πειράματα σε σκόνες και δοκίμια ασβεστιτικών μαρμάρων). Το HEDP εκτός από την επιβράδυνση της διάλυσης (ακόμα και κατά 80-90 %), βρέθηκε ότι είχε αρνητική επίδραση στη μορφολογία των κρυστάλλων του μαρμάρου. Ο στόχος της επόμενης σειράς πειραμάτων ήταν η δημιουργία επικαλύψεων σε συμπαγή δοκίμια μαρμάρου. Οι επικαλύψεις αυτές, αποτελούντο από ανόργανα άλατα, μικρότερης διαλυτότητας σε υδατικά διαλύματα, σε σύγκριση με τον ασβεστίτη. Τα διαλύματα αντιδραστηρίων κατεργασίας (HCl, ΕDTA, γαλακτικού οξέος, oξικού οξέος, H3PO4, HEDP, NTMP , N(phosphomethyl-) imino diacetic acid) εφαρμόσθηκαν με: α) επίχριση με πινέλο, β) επίθεση εμποτισμένων υφασμάτων, γ) εμβάπτιση των δοκιμίων στα αντίστοιχα διαλύματα. Αποτελεσματικότερος τρόπος εφαρμογής ήταν η εμβάπτιση. Ο χαρακτηρισμός των επιφανειών, και των αντίστοιχων επιστρώσεων και η ταυτοποίησή τους έγινε με XRD, FΤ-IR και SEM. Στην συνέχεια, τα σύνθετα υλικά (μάρμαρο+επικάλυψη), υποβλήθηκαν σε πειράματα διάλυσης σε διαλύματα ακόρεστα ως προς ασβεστίτη προκειμένου να δοκιμασθεί η αποτελεσματικότητά τους στην προστασία της επιφάνειας του μαρμάρου από τη διάβρωση. Η επεξεργασία με φωσφορικό οξύ, είχε ως αποτέλεσμα την δημιουργία παχέος στρώματος διένυδρου, όξινου φωσφορικού ασβέστιου (CaHPO42H2O, DCPD). Με δεύτερη εμβάπτιση σε διάλυμα όξινου φωσφορικού νατρίου η υδρόλυση των αρχικά σχηματισθέντων κρυστάλλων DCPD, οδήγησε στον σχηματισμό ψευδομορφικών κρυστάλλων OCP οι οποίοι και σχηματίζουν στρώμα περίπου 100 μm, το οποίο καλύπτει πλήρως την επιφάνεια του μαρμάρου και παρουσιάζει εξαιρετική πρόσφυση στην επιφάνεια. Οι δοκιμές διάλυσης σε ακόρεστα διαλύματα, έδειξαν ότι διαλύεται μόνο η επικάλυψη. Υπαίθρια Έκθεση. Επαληθεύθηκε η ανασταλτική δράση του HΕDP στην διάλυση των δοκιμίων του μαρμάρου τα οποία εκτέθηκαν στους σταθμούς υπαίθριας έκθεσης. Γενικά, οι τασιενεργές ουσίες που δοκιμάσθηκαν προστάτευσαν τα δοκίμια του μαρμάρου σε μεγαλύτερο βαθμό από τις υδρόφοβες ουσίες γεγονός το οποίο υπογραμμίζει την σημασία της αλληλεπίδρασης ουσίας-υποστρώματος και το οποίο είναι σε συμφωνία με τα ευρήματα από τα πειράματα που διεξήχθησαν στους αντιδραστήρες batch.. Θάλαμος αλατονέφωσης. Σε συνθήκες επιταχυνόμενης διάβρωσης, επαληθεύθηκε για μια ακόμα φορά η ανασταλτική δράση ουσιών όπως το HΕDP, οι οποίες μπορούν να αλληλεπιδράσουν με το μάρμαρο. Είναι αξιοσημείωτο ότι τα αποτελέσματα των μετρήσεων της κινητικής της διάλυσης τα οποία ελήφθησαν από την υπαίθρια έκθεση δοκιμίων ήσαν συγκρίσιμα με τα αποτελέσματα των μετρήσεων σε αντιδραστήρες τύπου batch. . Η μέθοδος μέτρησης της κινητικής της διάλυσης σε ακόρεστα διαλύματα και σε συνθήκες σταθερού κορεσμού, έχει τη δυνατότητα σε μικρό σχετικά χρονικό διάστημα να δώσει ικανοποιητικές πληροφορίες σχετικά με τη συμπεριφορά των δοκιμίων μαρμάρου σε διαβρωτικό περιβάλλον αλλά και να χρησιμεύσει σε δοκιμές ελέγχου και προκαταρκτικής αξιολόγησης (screening) σειράς υποψήφιων για την προστασία του μαρμάρου ουσιών. / A significant number of historic monuments and artworks have been made of stone, mainly of marble, lime and silicate materials. The work in the present thesis, is focused on the investigation of the kinetics of marble dissolution under various conditions. These studies contribute to the understanding of the mechanism of dissolution, for of calcitic and dolomitic marbles. Understanding the mechanism of the problem is essential for the selection and the implementation of methods for the protection of monuments. More specifically, in the present work it was attempted to achieve the following tasks: a) Determination of dissolution mechanism, through measurements of the kinetics of marble dissolution in solutions undersaturated with respect to the main component (calcite, dolomite) under various undersaturation conditions at controlled conditions. b) Dissolution inhibition by addition of water soluble compounds and investigation of the mechanism of their interaction with the calcitic surfaces. c) Formation of potentially protective coatings on marble surface consisting of sparingly soluble inorganic salts. d) Comparison of marble dissolution rates (in the presence and in the absence of different water soluble substances) with the respective values reported in the literature and with results from marble specimens exposed outdoors or under accelerated weathering conditions in a salt spray chamber (with or without other agents, including colonization with microorganisms, treatment with biocides). The aim of this comparison was the selection of the best model for the reliable testing of novel methods and materials for the protection of marble. Three marble types were selected in the present investigation. These types have been frequently used as building materials in monuments and sculptures in Europe: Carrara (>98% calcite), Pentelic (>98% calcite) and Ekeberg (>93% dolomite). A number of compounds were selected for the investigation of their effectiveness of protection against marble weathering due to wet precipitation: VPA3-7 (surfactant) and HEDP (organophosphorus compounds), Hydrophase superfici (hydrophobic substannce) and Algophase  (biocide). To study the effect of microorganisms on the weathering of marble specimens exposed outdoors, they were inocculated with a bacteria culture consisting of (Geodermatophilus sp BC 508 isolated from limestone rock (Noto, Syracuse, Italy) , Micromonospora sp. BC 562 isolated from Pentelic marble), fungi (Coniosporium apolliniis MC518 isolated from marble from Tarragona Cathedral (Spain) and Coniosporium uncinatum MC557 isolated from Carrara marble statue (Messina, Italy).) The aim of the measurements of the rates of marble dissolution in solutions undersaturated with respect to calcite, as a function of the relative undersaturation was the attainment of a better understanding for the mechanism underlying marble dissolution. Undersaturated working solutions were prepeared by dilution of proper stock solutions of CaCl2, MgCl2, NaHCO3, NaCl, and pH was initially adjusted to 8.25 with 0.01N NaOH. After equilibration of undersaturated solutions in the reactor, known amount of marble was introduced, either in powder form (suspension) or in rod form (fixed on special scaffold). Depending on the control of the parameters possible the following types of experiments were done and the dissolution rates were measured: free drift (all variables change with the exception of temperature), constant pH (pH only is kept constant), constant undersaturation (the activities of all species in the undersaturated solutions are kept constant). The dissolution rates of calcitic marble (both in powders and slabs) and calcite powder showed linear dependence on the relative undersatutation. In all cases, the rates of dissolution were of the same order of magnitude with the rates corresponding to (synthetic) calcite powder. Thermal pretreatment of pentelic marble powder resulted to higher dissolution rates. In this case, the dependence of the rates measured with respect to the relative undersatutation was found to be non-linear, (R=Kdσn , n>1). In the case of Ekeberg marble, the dependence of the rates of dissolution on the relative undersatutation was found to be non-linear, as well with n = 2. It may therefore be concluded that the dissolution is surface diffusion controlled. In the present work, solubilities for different types of marbles investigated in aqueous solutions were calculated from measurements of specimens equilibrated with electrolyte solutions over a time period exceeding the 2 years. For Pentelic and Crystallina Thassou marbles, values of solubility products were close to the value of pure calcite, while those for the rest of the calcitc marbles (Carrara, Spilia, Dionysoy) were higher. For the dolomitc marbles Ekeberg and Thassos White, the values obtained were almost identical and close to the values reported for stoichiometric dolomite. In all cases, the rate of dissolution was found to be controlled by surface diffusion. The adsorption of a substance on marble surface could possibly affect the dissolution process. The adsorption of substances posessing ionisable phosphate and phosphonate groups on marble powders (Pentelic, carrara, Ekeberg) was investigated through the respective adsorption isotherms. HEDP was mainly studied in this section, because its presence in undersaturated solutions inhibited dissolution to a large extent, and also because it could be considered as a model substance for the investigation of the effect of substances with similar functional groups on crystalline solids with metal cations on their surface. The presence of HEDP in the undersaturated solutions resulted in the reduction of the marble dissolution rates, proportionally to the extent of HEDP adsorption on the substrate. The dissolution rates obtained were lower than those obtained in experiments were HEDP was pre-adsorbed on the substrate (both in marble powder and in marble rod tests). HEDP showed strong inhibition effect (even by 80-90%) but also showed negative effect on the morphology marble crystallites. The aim of the next series of experiments was the formation of coatings on pentelic marble slabs. The coatings tested in the present investigation, consisted of inorganic salts , less soluble than calcite. Treatment solutions (HCl, ΕDTA, lactic acid, H3PO4, HEDP, NTMP , N(phosphomethyl-) imino diacetic acid) were applied by:a) brush, b) impregnated patch and c) immersion. The most effective way was impregnation. XRD, FT-IR and SEM were used for the characterization of the surfaces and of the composition of the coatings. The “new” composite (marble + coating) materials were then subjected to dissolution experiments in solutions undersaturated with respect to calcite. Treatment of marble with phosphoric acid resulted in formation of a thick layer of CaHPO42H2O, DCPD. Following a second treatment with sodium hydrogen phosphate solution, the iniatially formed DCPD crystals were hydrolyzed to pseudomorfic OCP crystals, resulting to a layer of 100 um thickness with complete coverage of the surface and good adhesion on the substrate. Dissolution experiments showed that only the coating was dissolved. T Outdoors exposure. The inhibiting effect of HEDP on dissolution was verified in the case of the exposed marble specimens. The surfactant substances tested seemed to protect the specimens more than the hydrophobic compounds, which empasizes the importance of substance-substrate interaction and is in good agreement with batch experiment results. Salt spray chamber. The inhibiting effect of HEDP on dissolution was again verified in the case of the marble specimen exposedunder accelerated weathering conditions. Results of the measurements of the kinetics of marble dissolution obtained from outdoors exposure tests of marble slabs, were comparable to those obtained from batch reactor experiments. Measurement of dissolution kinetics in working solutions under constant undersaturation conditions is a method capable of providing satisfactory information on the behaviour of marble specimen under weathering conditions and a useful tool on testing and evaluating the efficiency of candidate protective methods and products in a short time (suitable as preliminary screening tool).

Through a close study of Hawthorne's four major romances--The Scarlet Letter, The House of the Seven Gables, The Blithedale Romance, and The Marble Faun-—this thesis singles out all significant references to apparel or accessories and evaluates the use he makes of them.

This thesis is a study of the four long romances, The Scarlet Letter, The House of the Seven Gables, The Blithedale Romance, and The Marble Faun, with emphasis upon Hawthorne's use of symbolism as a means of presenting the basic moral and spiritual truths of human life. The first chapter explains the nature of symbolism and the reasons why Hawthorne used it so extensively. In each of the last four chapters, the symbolism in a single romance is considered for the purpose of discovering the manner and effectiveness of its use in exemplifying the central theme of that particular story. Although Hawthorne's short stories are extremely rich in symbolism, it was not possible to include them in the present study.

The works contained in "Raubeaux Scientician" are about a triadic relationship between people, science, and art. The obsessions, of individuals and the apparent change brought about by their physical presence guide my artistic research. I am awestruck at the capabilities of the individual to overcome conventional thought and through creative action yield a new vision. Some of the people I am fascinated by put forth theories and inventions that continue to affect myriad aspects of our world today. Among those at the forefront are, Robert Oppenheimer, and Edward Teller. Their contributions to science and mathematics remain almost unmatched. These and many others on the Manhattan Project team were employing cutting edge physics in their atomic research. The decisions to go through with the testing and the resulting construction of atomic weapons quite simply changed the face of humanity forever. With the knowledge of how to obliterate mankind, however, came a closer understanding of nature and the universe. But was it all worth it? And what about the not so famous men and women on this project, those such as Stanislaw Ulam who felt the calculations for atomic testing were all wrong and traveled the scientific community to try and stop the making of the bomb. What if he had been successful in ending the use of these postulates?

The Marble Springs homestead in south Knox County serves as a significant heritage site for the state of Tennessee because it was the final home of one of our nation’s most important founding statesmen and first governor of Tennessee (1796 to 1801, 1803 to 1809), John Sevier. Recent archaeological and historical research had called into question the authenticity of the original John Sevier log cabin located at the Marble Springs homestead. We used tree-ring dating to determine the year(s) of construction of the Governor John Sevier cabin and the adjacent Walker Springs log cabin (which had been relocated to the site later and has no ties to Gov. John Sevier) by first extracting cores from all accessible logs in the cabins and then evaluating the cutting dates of these logs. A nearby reference chronology at Norris Dam anchored the Gov. John Sevier cabin chronology from 1720 to 1834 and the Walker Springs cabin chronology from 1675 to 1826. The cutting dates obtained from six logs in the Gov. John Sevier cabin suggest construction of the cabin was completed sometime between late 1835 and early 1836. We were able to date cores from 29 logs from the Walker Springs cabin, which strongly support final construction between late 1827 to early 1828. Our dendrochronological analyses suggest that the cabin at Marble Springs long thought to be the original cabin occupied by Gov. John Sevier was instead likely built during the occupancy of the property by a later tenant, George Kirby, in the early to mid-1830s, well after the death of Sevier in 1815.

Neste trabalho foram determinadas as concentrações dos radionuclídeos naturais 226Ra, 232Th e 40K em amostras de granitos e mármores, abrangendo as principais lavras de extração do estado do Espírito Santo, sudeste do Brasil. Para cada sítio de estudo, três amostras foram seladas em frascos de 100 ml de polietileno de alta densidade. Após espera de aproximadamente 4 semanas para atingir o equilíbrio secular das séries do 238U e 232Th, as amostras foram medidas por espectrometria gama de alta resolução e o espectro analisado com o software WinnerGamma. A correção da auto-absorção foi realizada para todas as amostras utilizando expressão e método desenvolvidos para este fim. A concentração do 226Ra foi determinada pela média ponderada das concentrações do 214Pb e 214Bi, a concentração de 232Th pela média ponderada das concentrações dos 228Ac, 212Pb e 212Bi e a concentração de 40K pela sua transição única de 1460 keV. O equivalente em rádio e o índice gama foram obtidos a partir das concentrações de 226Ra, 232Th e 40K. O radônio emanado foi medido em câmera de exalação usando a técnica de detectores passivos de estado sólido (SSNTD) sendo estes expostos em monitor NRPB/SSI-H. Na exposição foi utilizado um detector comercial CR-39® e um plástico de fabricação nacional denominado Durolon® sendo caracterizado para este fim pela técnica desenvolvida denominada dupla exposição e fator de sensibilidade intrínseca. O plástico caracterizado mostrou-se eficiente para a aplicação e o fator de calibração correspondendo a 1,6±0,1 traços cm²(kBq m³dia)¹ em relação ao fator para o CR-39 que equivale a 2,8±0,2 traços cm²(kBq m³dia)¹. O detector mostrou maior eficiência para doses mais elevadas. A atividade determinada por detecção passiva mostrou atividades variando de 100±10 Bq·m³ até 2400±300 Bq·m³, destacando-se a maior taxa de exalação para o granito Iberê Mombasa. Para os mármores foram determinados valores variando entre 80±10 Bq·m³ até 200±25 Bq·m³ destacando os mármores Cintilante e Branco com maiores valores determinados. Os valores determinados para a taxa de exalação superficial apresentam-se aproximadamente iguais com exceção dos granitos Iberê Mombasa e Iberê Prado que apresentaram valores acima de 1 Bqm-2h-1. As medidas por espectrometria gama mostraram que as concentrações de 226Ra variaram de 1,9 0,2 Bq.kg-1 a 483 55 Bq.kg-1, com o maior valor para o granito Iberê Mombasa. As concentrações de 232Th variaram de 3,2 0,4 Bq.kg-1 a 224 6 Bq.kg-1, com o maior valor determinado para o granito Cinza Corumbá. As concentrações de 40K variaram de 8,8 1,8 Bq.kg-1 a 1642 167 Bq.kg-1, com o maior valor determinado para o granito Iberê Vitara. O cálculo do equivalente em rádio mostrou que a maioria das amostras podem ser definidas como categoria-I (aplicação civil) abaixo de 370 Bq.kg-1, exceto para os granitos Cinza Corumbá, Iberê Crema Bordeaux e Iberê Mombasa que podem ser classificados como categoria II (até 740 Bq.kg-1). A maioria dos granitos avaliados mostraram índices de exposição interno e externos abaixo de 1,0 mSv·ano¹, exceto os granitos Cinza Corumbá, Iberê Crema Bordeaux e Iberê Mombasa que superaram este valor entre 1,0 a 3,2 mSv·ano¹ deste índice. Para a exposição anual, apenas os granitos Cinza Corumbá, Iberê Crema Bordeaux e Iberê Mombasa superaram o limite de 1,5 mSv·ano¹. Para os índices de exposição alfa apenas os granito Iberê Crema Bordeaux e Iberê Mombasa são limitados a confecção de material de construção para aplicações superficiais. Entretanto, se considerando o índice de exposição gama, os granitos Cinza Corumbá, Cinza Andorinha, Amarelo Icarai, Cinza Ocre, Iberê Crema Bordeaux e Iberê Mombasa terão aplicação controlada. Conclui-se que os granitos em sua maioria e todos os mármores avaliados apresentam aplicações possíveis em diferentes setores de atividade e para diferentes finalidades e que os granitos que excedem os índices não devam ser aplicados em interiores de residências. / In this work, the concentrations of natural radionuclides 226Ra, 232Th and 40K in granite and marble samples were determined, considering the main extraction mining of Espirito Santo state, southeastern Brazil. For all study sites, three samples were sealed in 100 ml high density polyethylene bottles. Each sample rested for 4 weeks to reach the secular equilibrium of 238U and 232Th series before measured by high resolution gamma spectrometry, and the acquired spectra were analyzed with the software WinnerGamma. The self-absorption correction was considered for all samples, using an expression and method specially developed for this purpose. The concentration of 226Ra was determined by the weighted arithmetic mean of the concentrations of 214Pb and 214Bi, the concentration of 232Th by the weighted arithmetic mean of the concentrations of 228Ac, 212Pb and 212Bi and the concentration of 40K by its single 1460 keV transition. The radium equivalent and gamma index were calculated from the activity concentrations of 226Ra, 232Th, and 40K. The emanated radon was measured using an exhalation chamber and the passive detector technique, with a solid state nuclear tracks detectors (SSNTD) being exposed in NRPB/SSI-H dosimeters. During exposure, a commercial detector CR-39® and a national plastic called Durolon® were used, the last was characterized for this purpose using a technique called double exposure and sensitivity intrinsic factor. The characterized plastic was efficient for the application and the calibration factor corresponded to 1.60 ± 0.10 trackscm²(kBqm³day)¹ in relation to the CR-39 factor, equivalent to 2.8 ± 0.2 trackscm²(kBqm³day)¹. The detector showed a higher efficiency at a higher dose. The activities determined by passive detection varyed from 100 ± 10 Bqm-³ up to 2400 ± 300 Bqm-³, highlighting the biggest exhalation rates for granite Iberê Mombasa. Considering the marbles, activity values varyed from 80 ± 10 Bqm-³ up to 200 ± 25 Bqm-³ highlighting only the Cintilante and Branco Extra with higher values. The values obtained for surface exhalation rate were approximately equal, except for granites Iberê Mombasa and Iberê Prado with values above 1 Bqm-2h-1. The measures by gamma spectrometry showed that the 226Ra concentrations varyed from 1.9±0.2 Bq.kg-1 up to 483±55 Bq.kg-1, with the highest value for granite Iberê Mombasa. The 232Th concentrations ranged from 3.2±0.4 Bq.kg-1 to 224±6 Bq.kg-1, whose largest value was observed for the gray granite Corumbá. The 40K concentrations ranged from 8.8±1.8Bq.kg-1 up to 1642±67 Bq.kg-1, with the largest value observed for granite Iberê Vitara. The radio equivalent value showed that most samples can be defined as category I, below 370 Bq.kg-1, except for the granites Cinza Corumbá, Iberê Crema Bordeaux and Iberê Mombasa that can be classified as class II (up to 740 Bq.kg-1). The evaluated granites show internal and external exposure rates below 1.0 mSv·y¹ except the granites Cinza Corumbá, Iberê Crema Bordeaux and Iberê Mombasa that exceed the value range of 1.0 to 3.2 mSv·y¹ for this index. For the annual exposure dose, only the granites Gray Corumbá, Iberê Crema Bordeaux and Iberê Mombasa exceeded the 1.5 mSv·y¹. For the alpha exposure index only the Iberê Crema Bordeaux and Iberê Mombasa granites indicate limitations when applying as surface material. However, considering the gamma exposure index, the granites Cinza Corumbá, Cinza Andorinha, Amarelo Icarai, Cinza Ocre, Iberê Crema Bordeaux and Iberê Mombasa have controlled application. In conclusion, the evaluated granites and all marbles evaluated have viable applications in different activity sectors and for different purposes and the granites that exceeded the proposed limits should not be applied in the interior of residences

Neste trabalho foram determinadas as concentrações dos radionuclídeos naturais 226Ra, 232Th e 40K em amostras de granitos e mármores, abrangendo as principais lavras de extração do estado do Espírito Santo, sudeste do Brasil. Para cada sítio de estudo, três amostras foram seladas em frascos de 100 ml de polietileno de alta densidade. Após espera de aproximadamente 4 semanas para atingir o equilíbrio secular das séries do 238U e 232Th, as amostras foram medidas por espectrometria gama de alta resolução e o espectro analisado com o software WinnerGamma. A correção da auto-absorção foi realizada para todas as amostras utilizando expressão e método desenvolvidos para este fim. A concentração do 226Ra foi determinada pela média ponderada das concentrações do 214Pb e 214Bi, a concentração de 232Th pela média ponderada das concentrações dos 228Ac, 212Pb e 212Bi e a concentração de 40K pela sua transição única de 1460 keV. O equivalente em rádio e o índice gama foram obtidos a partir das concentrações de 226Ra, 232Th e 40K. O radônio emanado foi medido em câmera de exalação usando a técnica de detectores passivos de estado sólido (SSNTD) sendo estes expostos em monitor NRPB/SSI-H. Na exposição foi utilizado um detector comercial CR-39® e um plástico de fabricação nacional denominado Durolon® sendo caracterizado para este fim pela técnica desenvolvida denominada dupla exposição e fator de sensibilidade intrínseca. O plástico caracterizado mostrou-se eficiente para a aplicação e o fator de calibração correspondendo a 1,6±0,1 traços cm²(kBq m³dia)¹ em relação ao fator para o CR-39 que equivale a 2,8±0,2 traços cm²(kBq m³dia)¹. O detector mostrou maior eficiência para doses mais elevadas. A atividade determinada por detecção passiva mostrou atividades variando de 100±10 Bq·m³ até 2400±300 Bq·m³, destacando-se a maior taxa de exalação para o granito Iberê Mombasa. Para os mármores foram determinados valores variando entre 80±10 Bq·m³ até 200±25 Bq·m³ destacando os mármores Cintilante e Branco com maiores valores determinados. Os valores determinados para a taxa de exalação superficial apresentam-se aproximadamente iguais com exceção dos granitos Iberê Mombasa e Iberê Prado que apresentaram valores acima de 1 Bqm-2h-1. As medidas por espectrometria gama mostraram que as concentrações de 226Ra variaram de 1,9 0,2 Bq.kg-1 a 483 55 Bq.kg-1, com o maior valor para o granito Iberê Mombasa. As concentrações de 232Th variaram de 3,2 0,4 Bq.kg-1 a 224 6 Bq.kg-1, com o maior valor determinado para o granito Cinza Corumbá. As concentrações de 40K variaram de 8,8 1,8 Bq.kg-1 a 1642 167 Bq.kg-1, com o maior valor determinado para o granito Iberê Vitara. O cálculo do equivalente em rádio mostrou que a maioria das amostras podem ser definidas como categoria-I (aplicação civil) abaixo de 370 Bq.kg-1, exceto para os granitos Cinza Corumbá, Iberê Crema Bordeaux e Iberê Mombasa que podem ser classificados como categoria II (até 740 Bq.kg-1). A maioria dos granitos avaliados mostraram índices de exposição interno e externos abaixo de 1,0 mSv·ano¹, exceto os granitos Cinza Corumbá, Iberê Crema Bordeaux e Iberê Mombasa que superaram este valor entre 1,0 a 3,2 mSv·ano¹ deste índice. Para a exposição anual, apenas os granitos Cinza Corumbá, Iberê Crema Bordeaux e Iberê Mombasa superaram o limite de 1,5 mSv·ano¹. Para os índices de exposição alfa apenas os granito Iberê Crema Bordeaux e Iberê Mombasa são limitados a confecção de material de construção para aplicações superficiais. Entretanto, se considerando o índice de exposição gama, os granitos Cinza Corumbá, Cinza Andorinha, Amarelo Icarai, Cinza Ocre, Iberê Crema Bordeaux e Iberê Mombasa terão aplicação controlada. Conclui-se que os granitos em sua maioria e todos os mármores avaliados apresentam aplicações possíveis em diferentes setores de atividade e para diferentes finalidades e que os granitos que excedem os índices não devam ser aplicados em interiores de residências. / In this work, the concentrations of natural radionuclides 226Ra, 232Th and 40K in granite and marble samples were determined, considering the main extraction mining of Espirito Santo state, southeastern Brazil. For all study sites, three samples were sealed in 100 ml high density polyethylene bottles. Each sample rested for 4 weeks to reach the secular equilibrium of 238U and 232Th series before measured by high resolution gamma spectrometry, and the acquired spectra were analyzed with the software WinnerGamma. The self-absorption correction was considered for all samples, using an expression and method specially developed for this purpose. The concentration of 226Ra was determined by the weighted arithmetic mean of the concentrations of 214Pb and 214Bi, the concentration of 232Th by the weighted arithmetic mean of the concentrations of 228Ac, 212Pb and 212Bi and the concentration of 40K by its single 1460 keV transition. The radium equivalent and gamma index were calculated from the activity concentrations of 226Ra, 232Th, and 40K. The emanated radon was measured using an exhalation chamber and the passive detector technique, with a solid state nuclear tracks detectors (SSNTD) being exposed in NRPB/SSI-H dosimeters. During exposure, a commercial detector CR-39® and a national plastic called Durolon® were used, the last was characterized for this purpose using a technique called double exposure and sensitivity intrinsic factor. The characterized plastic was efficient for the application and the calibration factor corresponded to 1.60 ± 0.10 trackscm²(kBqm³day)¹ in relation to the CR-39 factor, equivalent to 2.8 ± 0.2 trackscm²(kBqm³day)¹. The detector showed a higher efficiency at a higher dose. The activities determined by passive detection varyed from 100 ± 10 Bqm-³ up to 2400 ± 300 Bqm-³, highlighting the biggest exhalation rates for granite Iberê Mombasa. Considering the marbles, activity values varyed from 80 ± 10 Bqm-³ up to 200 ± 25 Bqm-³ highlighting only the Cintilante and Branco Extra with higher values. The values obtained for surface exhalation rate were approximately equal, except for granites Iberê Mombasa and Iberê Prado with values above 1 Bqm-2h-1. The measures by gamma spectrometry showed that the 226Ra concentrations varyed from 1.9±0.2 Bq.kg-1 up to 483±55 Bq.kg-1, with the highest value for granite Iberê Mombasa. The 232Th concentrations ranged from 3.2±0.4 Bq.kg-1 to 224±6 Bq.kg-1, whose largest value was observed for the gray granite Corumbá. The 40K concentrations ranged from 8.8±1.8Bq.kg-1 up to 1642±67 Bq.kg-1, with the largest value observed for granite Iberê Vitara. The radio equivalent value showed that most samples can be defined as category I, below 370 Bq.kg-1, except for the granites Cinza Corumbá, Iberê Crema Bordeaux and Iberê Mombasa that can be classified as class II (up to 740 Bq.kg-1). The evaluated granites show internal and external exposure rates below 1.0 mSv·y¹ except the granites Cinza Corumbá, Iberê Crema Bordeaux and Iberê Mombasa that exceed the value range of 1.0 to 3.2 mSv·y¹ for this index. For the annual exposure dose, only the granites Gray Corumbá, Iberê Crema Bordeaux and Iberê Mombasa exceeded the 1.5 mSv·y¹. For the alpha exposure index only the Iberê Crema Bordeaux and Iberê Mombasa granites indicate limitations when applying as surface material. However, considering the gamma exposure index, the granites Cinza Corumbá, Cinza Andorinha, Amarelo Icarai, Cinza Ocre, Iberê Crema Bordeaux and Iberê Mombasa have controlled application. In conclusion, the evaluated granites and all marbles evaluated have viable applications in different activity sectors and for different purposes and the granites that exceeded the proposed limits should not be applied in the interior of residences