Rare earth ion doped glasses find applications in optical and photonic devices such as optical windows, laser, and optical amplifiers, and as model systems for immobilization of nuclear waste. Macroscopic properties of these materials, such as luminescence efficiency and phase stability, depend strongly on the atomic structure of these glasses. In this thesis, I have studied the atomic level structure of rare earth doped silicate and aluminophosphate glasses by using molecular dynamics simulations. Extensive comparisons with experimental diffraction and NMR data were made to validate the structure models. Insights on the local environments of rare earth ions and their clustering behaviors and their dependence on glass compositions have been obtained. In this thesis, MD simulations have been used to investigate the structure of Eu2O3-doped silica and sodium silicate glasses to understand the glass composition effect on the rare earth ions local environment and their clustering behaviors in the glass matrix, for compositions with low rare earth oxide concentration (~1mol%). It was found that Eu–O distances and coordination numbers were different in silica (2.19-2.22 Å and 4.6-4.8) from those in sodium silicate (2.32 Å and 5.8). High tendencies of Eu clustering and short Eu-Eu distances in the range 3.40-3.90 Å were observed in pure silica glasses as compared to those of silicate glasses with much better dispersed Eu3+ ions and lower probability to form clusters. The results show Eu3+ clustering behavior dependence on the system size and suggest for low doping levels, over 12,000 atoms to obtain statistical meaningful results on the local environment and clustering for rigid silica-based glasses. The structures of four cerium aluminophosphate glasses have also been studied using MD simulations for systems of about 13,000 atoms to investigate aluminum and cerium ion environment and their distribution. P5+ and Al3+ local structures were found stable while those of Ce3+ and Ce4+ ions, through their coordination numbers and bond lengths, are glass composition-dependence. Cerium clusters were found in the high cerium glasses.P5+ coordination numbers around cerium revealed the preference of phosphorus ions in the second coordination shell. Total structure factors from MD simulations and experimental diffraction results show a general agreement from comparison for all the cerium aluminophosphate glasses and with compositional changes up to 25 Å-1. Aluminum enters the phosphate glass network mainly as AlO4 and AlO5 polyhedra only connected through corner sharing to PO4 tetrahedra identified by Q11(1 AlOx), Q12(2 AlOx), Q21(1 AlOx), and Q22(2 AlOx) species.

Neste trabalho, o complexo de cério (Ce(hdacac)6·xH2O, x0-2) foi sintetizado a fim de se produzir um aditivo redutor de fuligem emitida pela queima de diesel, biodiesel e suas misturas em motores a compressão. Os complexos foram feitos a partir de um novo ligante, a 3-hexadecilpentano-2,4-diona (hdacac), que possui uma longa cadeia alquílica e o dois grupos carbonílicos em posições , permitindo a complexação de cério e sua dissolução em ambientes hidrofóbicos. Com o objetivo de se avaliar as propriedades estruturais do Ce(hdacac)6·xH2O, bem como o seu comportamento em solução, complexos com o íon Eu3+ (que apresenta propriedades luminescentes particulares) foram sintetizados. O ligante e seus complexos foram caracterizados por espectroscopia de ressonância magnética nuclear, titulação complexométrica, análise termogravimétrica, análise elementar, espectroscopia vibracional na região do infravermelho e espectroscopia de luminescência. A miscibilidade dos complexos sintetizados e a influência do Ce(hdacac)6·xH2O sobre a queima da fuligem foram estudadas. Seqüencialmente, o Ce(hdacac)6·xH2O foi adicionado aos novos combustíveis e sua capacidade redutora de fuligem comprovada em um grupo gerador, por comparação da refletância difusa de filtros expostos aos efluentes emitidos. Além disso, filmes de Langmuir-Blodgett com o Eu(hdacac)n .xH2O foram produzidos e, conhecendo-se a eficiência da hdacac na homogeneização do Eu3+ sobre a superfície investigada, comprovou-se a possibilidade de estudos futuros na produção de substratos inorgânicos com sítios de CeO2. / In the work, the complex Ce(hdacac)6·xH2O (x0-2) was synthesized in order to produce an additive capable of reducing soot, that is emitted from the combustion of diesel, biodiesel and its mixtures in compression engines. The complexes were produced from a new ligand, 3-hexadecylpentane-2,4-dione (hdacac), that has a long alkyl chain and two carbonyl groups in the position, thus allowing the complexation of cerium and its dissolution in hydrophobic environments. With the aim to evaluate the structural properties of Ce(hdacac)6·xH2O, as well as its behavior in solution, complexes with the Eu3+ ion (that has particular luminescent properties) were synthesized. The ligand and its complexes were characterized by nuclear magnetic resonance spectroscopy, complexometric titration, thermogravimetry, elementary analysis, and infrared and luminescence spectroscopies. The miscibility of the complexes and the influence of Ce(hdacac)6·xH2O on soot combustion were studied. Subsequently, Ce(hdacac)6·xH2O was added to the new fuels and its soot reducing capacity attested in a generating group by comparison of the diffuse reflectance of filters exposed to the emitted effluents. Moreover, LB films with Eu(hdacac)n .xH2O were produced and, by knowing the efficiency of hdacac in the homogenization of Eu3+ over the investigated surface, one can predict the possibility of future studies on the production of inorganic substrates having CeO2 sites.

Currently in the UK, spent nuclear fuel is reprocessed using the PUREX (Plutonium Uranium Reduction Extraction) process. This process generates large amounts of aqueous nitric acid based waste which is reduced in volume by evaporation before being stored in stainless steel tanks pending eventual disposal to a repository after conversion into a solid wasteform. The corrosivity of nitric acid solutions towards these stainless steel storage tanks is strongly affected by the presence of oxidants that can form in situ if certain dissolved metals such as cerium, chromium, ruthenium and neptunium are present, which is invariably the case in nuclear reprocessing plant liquors. Such liquors are, however, subject to radiolysis leading to the formation of nitrous acid and NOx species in equilibrium with nitric acid and water. The redox chemistry of irradiated reprocessing plant liquors is therefore complex, depending on a large number of factors including acidity, nitrate ion concentration, temperature, pressure, radiation dose rate and the nature/concentration of dissolved species. High acidities, high temperatures and low dose rates favour the oxidation of species such as Ce(III). For example, when Ce(IV) forms, the corrosion rate of stainless steel is strongly increased since the reduction of Ce(IV) forms a kinetically-favoured path way. Furthermore, the presence of nitrous acid (which is radiolytically formed from nitrate/nitric acid) can act to reduce potential corrosion accelerators (e.g. Ce(IV)) to their non-oxidising valency states. These dependencies are only semi-quantitatively understood at present, hampering useful prediction of actual effects when conditions are changed. The research presented within this thesis is divided between two experimental campaigns which are interrelated by their applicability to highly active storage tank conditions; I. An investigation into the conditions which effect the radiolytic production of nitrous acid in nitric acid based solutions was undertaken. This included the quantitative measurement of the steady state concentration of nitrous acid experienced under different conditions. The conditions investigated include temperature, dose rate, gaseous headspace and liquor composition in order to elucidate which factors are of importance in estimating the concentration of nitrous acid which can be expected at the base of a highly active storage tank. The major result of this campaign was that nitrous acid data collected could be used to formulate a g-value of nitrous acid formation (which was found to be 0.71) and this value was used to calculate the nitrous acid production rate expected within a highly active storage tank which is a pre-requisite of underpinning the corrosion chemistry within. II. Investigation into the potential formation of in situ corrosion accelerators in a reprocessing liquor simulant was undertaken. For this, a bespoke experimental rig has been designed, built and operated in order to identify the valency of potential corrosion accelerators at high temperatures while closely representing the conditions expected at the base of a highly active storage tank. This included the simulation of nitric acid radiolysis by means of an appropriate nitrite addition underpinned by the radiolysis studies described above in (I). It was found that none of the conditions investigated were oxidising enough to promote the generation of Ce(IV), which is contrary to the current understanding and should be favourable with regards to the storage tank remnant life expectations. Results reported in this thesis provide insight into the corrosivity of reprocessing liquors under representative storage tank conditions at various temperatures (up to the local liquor saturation temperature) and this knowledge will help improve remnant life predictions of the highly active storage tanks on the Sellafield site.

Studies various nanostructured materials have gained considerable interest within the past several decades. This novel class of materials has opened up a new realm of possibilities, both for the fundamental comprehension of matter, but also for innovative applications. The size-dependent effect observed for these systems often lies in their interaction with the surrounding environment and understanding such interactions is the pivotal point for the investigations undertaken in this thesis. Three families of nanoparticles are analyzed: semiconductor quantum dots, metallic silver nanoparticles and rare-earth oxide nanomaterials. The radical scavenging ability of cerium oxide nanoparticles (CeO2) is quite controversial since they have been labeled as both oxidizing and antioxidant species for biological systems. Here, both aqueous and organic stabilized nanoparticles are examined in straightforward systems containing only one reactive oxygen species to ensure a controlled release. The apparent absence of their direct radical scavenging ability is demonstrated despite the ease at which CeO2 nanoparticles generate stable surface Ce3+ clusters, which is used to explain the redox activity of these nanomaterials. On the contrary, CeO2 nanoparticles are shown to have an indirect scavenging effect in Fenton reactions by annihilating the reactivity of Fe2+ salts. Cadmium selenide quantum dots (CdSe QD) constitute another highly appealing family of nanocolloids in part due to their tunable, size-dependent luminescence across the visible spectrum. The effect of elemental sulfur treatment is investigated to overcome one of the main drawbacks of CdSe QD: low fluorescence quantum yield. Herein, we report a constant and reproducible quantum yield of 15%. The effect of sulfur surface treatment is also assessed following the growth of a silica shell, as well as the response towards a solution quencher (4-amino-TEMPO). The sulfur treated QD is also tested for interaction with pyronin Y, a xanthene dye that offers potential energy and electron transfer applications with the QD. Interaction with the dye molecule is compared to results obtained with untreated quantum dots, as well as CdSe/ZnS core shell examples. In another chapter of this thesis, the catalytic potential of silver nanoparticles is addressed for the grafting of polyhydrosiloxane polymer chains with various alkoxy groups. A simple one-pot synthesis is presented with silver salts and the polymer. the latter serves as a mild reducing agent and a stabilizing ligand, once silver nanoparticles are formed in-situ. We evaluate the conversion of silane into silyl ethers groups with the addition of several alcohols, whether primary, secondary or tertiary, and report the yields of grafting under the mildest conditions: room temperature, under air and atmospheric pressure.

Studies various nanostructured materials have gained considerable interest within the past several decades. This novel class of materials has opened up a new realm of possibilities, both for the fundamental comprehension of matter, but also for innovative applications. The size-dependent effect observed for these systems often lies in their interaction with the surrounding environment and understanding such interactions is the pivotal point for the investigations undertaken in this thesis. Three families of nanoparticles are analyzed: semiconductor quantum dots, metallic silver nanoparticles and rare-earth oxide nanomaterials. The radical scavenging ability of cerium oxide nanoparticles (CeO2) is quite controversial since they have been labeled as both oxidizing and antioxidant species for biological systems. Here, both aqueous and organic stabilized nanoparticles are examined in straightforward systems containing only one reactive oxygen species to ensure a controlled release. The apparent absence of their direct radical scavenging ability is demonstrated despite the ease at which CeO2 nanoparticles generate stable surface Ce3+ clusters, which is used to explain the redox activity of these nanomaterials. On the contrary, CeO2 nanoparticles are shown to have an indirect scavenging effect in Fenton reactions by annihilating the reactivity of Fe2+ salts. Cadmium selenide quantum dots (CdSe QD) constitute another highly appealing family of nanocolloids in part due to their tunable, size-dependent luminescence across the visible spectrum. The effect of elemental sulfur treatment is investigated to overcome one of the main drawbacks of CdSe QD: low fluorescence quantum yield. Herein, we report a constant and reproducible quantum yield of 15%. The effect of sulfur surface treatment is also assessed following the growth of a silica shell, as well as the response towards a solution quencher (4-amino-TEMPO). The sulfur treated QD is also tested for interaction with pyronin Y, a xanthene dye that offers potential energy and electron transfer applications with the QD. Interaction with the dye molecule is compared to results obtained with untreated quantum dots, as well as CdSe/ZnS core shell examples. In another chapter of this thesis, the catalytic potential of silver nanoparticles is addressed for the grafting of polyhydrosiloxane polymer chains with various alkoxy groups. A simple one-pot synthesis is presented with silver salts and the polymer. the latter serves as a mild reducing agent and a stabilizing ligand, once silver nanoparticles are formed in-situ. We evaluate the conversion of silane into silyl ethers groups with the addition of several alcohols, whether primary, secondary or tertiary, and report the yields of grafting under the mildest conditions: room temperature, under air and atmospheric pressure.

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Thesis (Ph. D.)--Institute of Paper Chemistry, 1966. / Includes bibliographical references (p. 101-105).

Thesis (Ph. D.)--Institute of Paper Chemistry, 1974. / Includes bibliographical references (p. 86-89).

Thesis (Ph. D.)--Institute of Paper Chemistry, 1968. / Bibliography: leaves 89-93.

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