Thesis (M.S.)--Virginia Polytechnic Institute and State University, 1993. / Vita. Abstract. Includes bibliographical references (leaves 24-27). Also available via the Internet.

Techn. Universiẗat, Diss., 2005--Clausthal.

Les résines échangeuses d’ions (REI) sont communément utilisées dans l’industrie nucléaire pour purifier des effluents contaminés non-stockables. Les REI deviennent ainsi un déchet solide qu’il est possible de conditionner. L’une des méthodes de conditionnement consiste en un enrobage dans une matrice cimentaire. Ce procédé pose un certain nombre de questions quant à la stabilité dimensionnelle de l’enrobé. Le déchet, une fois enrobé, est en effet susceptible d’interagir chimiquement avec la matrice cimentaire ce qui peut, dans certains cas, entrainer son gonflement par le biais de pressions internes. C’est autour de cette problématique que ce travail de thèse a vu le jour avec pour objectif de développer une modélisation physico-chimique multi-échelle du composite afin d’en estimer le comportement mécanique macroscopique. Cette étude s’est exclusivement intéressée aux interactions chimie-mécaniques induites par des REI cationiques pouvant engendrer à long terme un comportement expansif de l’enrobé. / Ion exchange resins (IER) are widely used in the nuclear industry to purge non directly storable infected effluents. IER then become a solid waste which could be stored as any classical nuclear waste. One way of conditioning consists in embedding it into a cement paste matrix. This process raises some concerns regarding the cohesiveness of the composite. Once embedded, the IER might indeed interact with the cement paste which would lead, in some cases, to the swelling of the composite. This thesis has been set up to address this potential issue, with the aim to develop a numerical tool able to predict the mechanical behavior of this kind of material. This work only focuses on the long term behavior and more specifically on the potential degradations of the cement paste /IER composite due to cationic IER.

La production de nouvelles générations de béton avec des propriétés physiques, structurales et techniques améliorées est très importante, mais elle n'est pas possible sans utiliser divers types d'additifs. Les nanotubes de carbone sont des matériaux prometteurs qui possèdent des propriétés spécifiques permettant leurs utilisations pour une grande variété de matériaux composites, y compris le béton. Certaines études expérimentales ont révélé que les nanotubes de carbone peuvent améliorer les propriétés mécaniques du béton avec une petite quantité d'additifs, en fournissant une structure moins défectueuse de la matrice de ciment. Cependant, les résultats sont encore insuffisants et nécessitent d'être élucidés sur les processus se produisant à l'échelle nanométrique dans la structure en béton modifiée par les nanotubes de carbone. Ainsi, cette thèse, a pour objectif principal l'étude de l'amélioration des propriétés mécaniques du béton modifié par les nanotubes de carbone. Afin de modéliser la structure atomique du gel de la Silicate de Calcium Hydratée, nous avons choisi la tobermorite 11Å avec deux rapports différents de Ca/Si correspondants à 0,83 et 1. Divers types de nanotubes incorporés sont testés pour étudier les propriétés mécaniques du nouveau composite résultant. En outre, l'effet de la concentration de nanotubes de carbone dans le ciment est également détaillé. Enfin, nous étudions l'effet de la pression uniaxial sur la structure du béton incluant des nanotubes de carbone. Nos travaux montrent qu'il possible d'améliorer les caractéristiques mécaniques du béton en insérant des nanomatériaux en général, et des nanotubes de carbone en particulier. / The production of new generations of concrete with improved physical, structural and technical properties is very important, but it is not possible without the use of various types of additives. Carbon nanotubes are promising materials that possess specific properties allowing their uses for a wide variety of composite materials, including concrete. Some experimental studies have revealed that carbon nanotubes can improve the mechanical properties of concrete with a small amount of additives, providing a less defective structure of the cement matrix. However, the results are still insufficient and need to be elucidated on the processes occurring at the nano-scale in the concrete structure modified by carbon nanotubes. Thus, this thesis has as main objective the study of the improvement of the mechanical properties of the concrete modified by the carbon nanotubes. In order to model the atomic structure of the Calcium Silicate Hydrates gel, tobermorite 11Å was selected with two different Ca/Si ratios corresponding to 0.83 and 1. Various types of nanotubes incorporated into the tobermorite 11Å structure were tested to study mechanical properties of the resulting new composite. In addition, the effect of the concentration of carbon nanotubes in the cement was also detailed. Finally, we studied the effect of uniaxial pressure on the concrete structure including carbon nanotubes. The work concludes that it is possible to improve the mechanical characteristics of concrete by inserting nano-materials in general, and carbon nanotubes in particular.

<p> Chan and Riley (1967) developed a colorimetric method for the determination of tungsten in natural waters and silicate rocks. Applied to silicate rocks this method contains the following stages: evaporation of silica with hydrofluoric acid, co-precipitation of tungsten and some other elements, with hydrous manganese dioxide and cation-exchange separation of vanadium, molybdenum and tungsten. When applying this method on standard solutions and the new U.S.G.S. standard rocks, the results obtained are lower than those suggested by the authors. The results obtained recently with neutron activation analysis of the same standard rocks by Johansen and Steinnes (1970), although different from the results of the present work, also disagree with Chan and Riley. The method was abandoned since a tungsten loss is believed to occur throughout the procedure.</p> / Thesis / Master of Science (MSc)

The accretion of the Earth was marked by the high-pressure segregation of most of its core, accompanied by dissolution of about 10% of one or more “light” elements into the metallic phase. Various light elements have been proposed including S, Si, C and O, with each having an effect on the partitioning behaviour of the trace elements. Metallurgical data indicate that dissolution of even small amounts of light elements in liquid Fe can have profound effects on the activities of some trace components. For instance, significant partitioning of Si into the core of the growing Earth should have affected the observed Mo content of the mantle (Ono-Nakazato et al., 2007). Here, I use the epsilon model of non-ideal interactions in Fe liquids (ε. I present interaction parameters (ε, derived from 1.5GPa, 1550-1650oC metal-silicate equilibration experiments, for W, Ni, Co and Mo in liquid Fe alloyed with C, and W, Ni, Co, Mo, Cu, Mn, Ag, Sb, Cd, In, Tl, Pb, Ga, Ge, Cr, V and Zn in liquid Fe alloyed with S. Additional epsilon values were taken from the steelmaking sourcebook when necessary. I used this new data in conjunction with published metal–silicate partitioning results to develop a model of continuous accretion and core segregation taking explicit account of the partitioning of Si (this study) and O (from Ozawa et al., 2008) between metal and silicate and their effects on metal–silicate partitioning of siderophile elements. The best model for explaining the Earth’s formation including the Mo:W ratio of the silicate Earth posits that the Earth’s oxidation state increased in steps from 1 to 6.26% FeO, increasing Si in the Earth’s core and the light elements C and S being added to the planet in the last ~20% of accretion material.

This thesis contributes to the field of silicon chemistry, with a special emphasis on the chemistry of penta- and hexacoordinate silicon.The spirocyclic zwitterionic Lambda5Si-silicates 1–6 with a (2,2,6,6-tetramethylpiperidinio)- methyl group and two identical bidentate chelate ligands derived from glycine, (S)-alanine, (S)-phenylalanine, (S)-valine, (S)-tert-leucine, or (S)-proline bound to the silicon(IV) coordination center were synthesized and structurally characterized for the first time.The hitherto unknown spirocyclic zwitterionic Lambda5Si-silicates 7–12 with an (ammonio)- methyl group and two identical bidentate chelate ligands derived from (S)-lactic acid, (S)-3- phenyllactic acid, or (S)-mandelic acid were synthesized and structurally characterized in the solid state (elemental analyses (C, H, N), crystal structure analyses, 15N and 29Si VACP/MAS solid-state NMR experiments) and in solution (except 10; 1H, 13C, and 29Si NMR experiments)The spirocyclic zwitterionic Lambda5Si-silicates 13, 15, and 16 with an (ammonio)methyl group and two bidentate meso-oxolane-3,4-diolato(2–) ligands bound to the silicon(IV) coordination center were synthesized for the first time. The already existent compound 14 was resynthesized in order to perform a crystal structure analysis. All compounds were characterized by elemental analyses (C, H, N), 29Si VACP/MAS solid-state NMR experiments, and solution NMR studies (1H, 13C, 15N, and 29Si NMR experiments), and compounds 14–16 were additionally studied by single-crystal X-ray diffraction.The already existent zwitterionic Lambda5Si-silicate 17 was synthesized by new methods, including a remarkable Si–C cleavage reaction with benzoin. To investigate the dynamic behavior of the known zwitterionic Lambda5Si-silicate 18 in solution, VT 1H NMR experiments in CD2Cl2 were performed in the temperature range –100 °C to 23 °C.The hexacoordinate silicon compounds 19–22 containing multidentate ligands derived from citric acid or (S)-malic acid were synthesized for the first time. The anionic Lambda6Si-silicates 19–22 were structurally characterized in the solid state by single-crystal X-ray diffraction and VACP/MAS NMR spectroscopy (13C, 15N, 29Si). Upon dissolution in water at 20 °C, spontaneous hydrolysis of the Lambda6Si-silicate anions was observed. / Die vorliegende Arbeit stellt einen Beitrag zur Chemie des penta- und hexakoordinierten Siliciums dar.Erstmalig wurden die spirocyclischen zwitterionischen Lambda5Si-Silicate 1–6 synthetisiert und strukturell charakterisiert. In diesen Verbindungen des pentakoordinierten Siliciums sind eine (2,2,6,6-Tetramethylpiperidinio)methyl-Gruppe und zwei identische zweizähnige Chelat- Liganden, die sich von den &#945;-Aminosäuren Glycin, (S)-Alanin, (S)-Phenylalanin, (S)-Valin, (S)-tert-Leucin oder (S)-Prolin ableiten, an das Si(IV)-Koordinationszentrum gebunden.Die spirocyclischen zwitterionischen Lambda5Si-Silicate 7–12 mit einer (Ammonio)methyl- Gruppe und zwei identischen Chelat-Liganden, die sich von (S)-Milchsäure, (S)-3- Phenylmilchsäure oder (S)-Mandelsäure ableiten, wurden erstmals synthetisiert. Die strukturelle Charakterisierung erfolgte durch Elementaranalysen (C, H, N), Festkörper-NMRSpektroskopie (15N- und 29Si-VACP/MAS-NMR) und durch 1H-, 13C-, 15N- und 29Si-NMRExperimente in Lösung. Die Existenz dieser Verbindungen wurde zusätzlich mittels Röntgenbeugung an Einkristallen bestätigt.Die bisher unbekannten spirocyclischen zwitterionischen Lambda6Si-Silicate 13, 15 und 16 mit einer (Ammonio)methyl-Gruppe und zwei identischen zweizähnigen meso-Oxolan-3,4- diolato(2–)-Liganden wurden synthetisiert. Die bereits bekannte Verbindung 14 wurde zur Anfertigung einer Kristallstrukturanalyse resynthetisiert. Die &#955;5Si-Silicate 13–16 wurden mit Hilfe elementaranalytischer (C, H, N), NMR-spektroskopischer Methoden (29Si-VACP/MASNMR; 1H-, 13C-, 15N- bzw. 29Si-NMR) charakterisiert. Die Verbindungen 14–16 wurden zusätzlich durch Einkristall-Röntgenstrukturanalysen charakterisiert.Das bereits bekannte zwitterionische Lambda5Si-Silicat 17 war über neue Syntheserouten zugänglich, die neben Si–O- auch eine bemerkenswerte Si–C-Bindungspaltungsreaktion unter milden Bedingungen beinhalten. Um mehr über das dynamische Verhalten des bereits bekannten zwitterionischen Lambda5Si-Silicats 18 in Lösung zu erfahren, wurden 1H-VT-NMRExperimente in dem Temperaturbereich zwischen –100 °C und 23 °C durchgeführt.Die hexakoordinierten Verbindungen 19–22 mit mehrzähnigen Liganden, die sich von Zitronensäure oder (S)-Äpfelsäure ableiten, wurden erstmalig synthetisiert. Die anionischen Lambda6Si-Silicate 19–22 wurden durch Einkristall-Röntgenstrukturanalysen und Festkörper-NMRspektroskopische Untersuchungen (13C-, 15N- bzw. 29Si- VACP/MAS-NMR) strukturell charakterisiert. Beim Auflösen der Verbindungen 19–22 in Wasser bei 20 °C wurde jeweils eine spontane Hydrolyse der Lambda6Si-Silicat-Anionen beobachtet.

Trace elements are highly fractionated during large-scale melting associated with planetary differentiation events. The resulting partition coefficients are used to constrain a range of geological processes and are known to be influenced by pressure, temperature, and compositional changes in crystalline structures. Although recent studies have shown that melt compositional changes affect the partitioning of trace elements, the degree to which these ratios are influenced by alterations in the melt structure, especially with increasing pressure, is poorly constrained due to the difficulty of collecting structural information on bonding environments in situ. A basic understanding of how these elements are incorporated in silicate melts is critical to interpreting early planetary differentiation and crust forming events. This thesis presents results from both x-ray diffraction and absorption techniques on trace element (Y, Zr, Lu and Nd) incorporation in silicate melt structures. The structure of two rare Earth element doped model end member silicate liquids, a highly polymerised haplogranite (Si- Al-Na-K-O) and a less polymerised anorthite-diopside (Si-Al-Mg-Ca-O), have been studied. The results are the first to identify trace rare Earth element (REE) incorporation in silicate melts at high pressure using x-ray diffraction techniques. The local melt structure around Y and Zr in a highly polymerised haplogranite has been studied using x-ray absorption spectroscopy up to 8GPa and 1650 K. Both elements appear to adopt 8-fold coordination within the melt structure with no variation over the pressure range studied. This was also found for the Lu bonding environment in the same composition where the coordination number of Lu-O was found to be 8, with a bond distance rLu-O = 2:36A in the haplogranite melt. At low pressures, < 5GPa, the bonding environment of Lu-O was found to be dependent on composition with coordination decreasing to CNLu-O = 6 and rLu-O = 2:29A in the anorthite-diopside melt. This compositional variance in coordination number at low pressure is consistent with observations made for Y-O in glasses at ambient conditions and is coincident with a dramatic increase in the partition coefficients previously observed for rare Earth elements (REE) with increasing melt polymerisation. However, an abrupt change in both Lu-O coordination and bond distance is observed at 5GPa in the anorthite-diopside melt, with CNLu-O increasing from 6 to 8-fold and rLu-O from 2.29 to 2.39A. This occurs over a similar pressure range where a reduction in the reported heavy REE partition coefficients is observed. X-ray diffraction experiments up to 60GPa and 2000K have also been performed on the incorporation of the larger light REE, Nd, in basaltic-like melts. The results presented show that incorporation within the anorthite-diopside composition is dependent on the size of the REE. Nd-O initially shows the same 6-fold coordination as Lu-O at ambient conditions, although the change to 8-fold coordination appears to occur at considerably lower pressure between 1-2GPa. Coordination change in both cases can be attributed to collapse of the silicate network and an increase in the average number of available 'crystal like' sites in the liquid, with ionic radius of the REE controlling at which pressure the preference for these sites in the melt occurs. Published mineral-melt partition coefficients for Nd, with major mineral phases such as garnet, show very little variation with pressure, in contrast to Lu. The difference in structural incorporation of Lu and Nd in the melts presented in this thesis could explain this partitioning behaviour. Overall this thesis highlights that important structural changes of the trace element bonding environment in silicate melts occur with both compositional variation and pressure. Melt structural changes with pressure cannot be neglected in predictive models of trace element behaviour, and using a single melt term to normalise the effects of melt on trace element partitioning will not accurately predict partitioning behaviour at depth during magma formation or differentiation.

This study is to probe into the surface characteristics, crystalline identification and inner structural changes of the synthetic iron oxides which are synthesized from pure Fe(¢»), citrate/Fe(¢») and silicate/Fe(¢») solutions at different MRs respectively. This study is also to compare the adsorption capabilities of these synthetic iron oxides serving as the adsorptive materials in containing arsenic wastewater through adsorption experiments. By means of the XRD identification analysis, the synthetic iron oxides of pure Fe(¢») and silicate/Fe(¢») are non-crystal ferrihydrite, but the synthetic iron oxide of citrate/Fe(¢») is crystal magnetite with magnetism. By means of IR spectrum analysis and comparison with the IR spectrum of iron mineral, the FTIR spectrum of pure Fe(¢») and silicate/Fe(¢») synthetic iron oxide are similar to that of ferrihydrite; The FTIR spectrum of citrate/Fe(¢») synthetic iron oxide is similar to that of magnetite. The degree of pore volume and surface area for synthetic iron oxides are as follows: silicate/Fe(¢») > Fe(¢») > citrate/Fe(¢»). With the citrate/Fe(¢») MRs increasing, the pore volume and surface area of synthetic iron oxide will decrease. However, with the silicate/Fe(¢») MRs increasing, the pore volume and surface area of synthetic iron oxide do not make great difference. Results of kinetic adsorption experiments show that the synthetic iron oxides of citrate/Fe(¢») or silicate/Fe(¢») at different MRs will adsorb arsenic better at low pH. With the pseudo-first order and the second order kinetic adsorption model to simulate the adsorption experiment data, the results show that the simulation results are consistent with the pseudo-second order kinetic adsorption model. The equilibrium adsorption experiments show that the adsorption capacity of arsenic for synthetic iron oxides is as follows: citrate/Fe(¢») > Fe(¢») > silicate/Fe(¢»), and that the adsorption capacity will decrease with the pH increasing.

Zugl.: Berlin, Freie Univ., Diss., 2009