Although fluoride is used at low concentrations in drinking water as a means of promoting dental health, it poses a danger at high exposure levels where it can lead to skeletal fluorosis or other adverse effects. Cyanide is notoriously toxic, and its large scale use in industrial processes warrants the need for close monitoring to remain aware of potential contamination of water sources and other environmental resources. Based on these considerations, it is critical to continue to develop improved methods of monitoring fluoride and cyanide concentrations in water. However, molecular recognition of these anions in water poses considerable challenges. For fluoride, this is due largely to its high hydration enthalpy (Ho = -504 kJ mol-1), which drastically reduces its reactivity in water. Additionally, the strong basicity of cyanide (pKa of (HCN) = 9.3) may obscure its detection in neutral water due to protonation. In addition to achieving detection of these anions in water, it is most desirable to have information of the detection event relayed in the form of a positive, rather than negative, response (i.e., turn-on vs turn-off). The general strategy of appending cationic groups to triarylboranes imparts beneficial Coulombic, inductive, and sometimes chelate effects that have allowed a number of these Lewis acidic receptors to sense fluoride and cyanide in aqueous environments. With the goal of developing new triarylborane-based receptors that show enhanced affinities for these anions, as well as turn-on responses to detection, a series of pyridinium boranes were synthesized and studied. Having recognized that the inherent Lewis acidity of antimony(V) species might be exploited for anion sensing, we also describe initial studies on the ability of tetraorganostibonium ions (R4Sb+) and cationic transition metal-triarylstibine complexes (R3SbM+) to complex fluoride. Finally, the electropositivity of antimony and its ability to form stable compounds in both the +3 and +5 oxidation states have led us to begin investigations into the bonding and redox reactivity of novel metal stibine/stiborane complexes.

Rocks of the South Island of New Zealand are locally enriched in metalloids, namely arsenic (As), antimony (Sb) and boron (B). Elevated levels of As and Sb can be found in sulphide minerals mostly in association with mesothermal gold deposits, whereas B enrichment occurs in marine influenced coal deposits. The mobility of these metalloids is important because they can be toxic at relatively low levels (e.g. for humans >0.01 mg/L of As). Their mobilisation occurs naturally from background weathering of the bedrock. However, mining and processing of coal and gold deposits, New Zealand's most economically important commodities, can significantly increase metalloid mobility. In particular, historic mines and associated industrial sites are known to generate elevated metalloid levels because of the lack of site remediation upon closure. This work defines and quantifies geological, mining, post-mining and regional processes with respect to metalloid, especially As, mobility. At the studied historic gold mines, the Blackwater and Bullendale mines, Sb levels in mineralised rocks were generally negligible (<14 ppm) compared to As (up to 10,000 ppm). Thus, Sb concentrations in solids and in water were too low to yield any meaningful information on Sb mobility. In contrast, dissolved As concentrations downstream from mine sites were found to be very high (up to 59 mg/L) (background = 10⁻� mg/L). In addition, very high As concentrations were found in residues (up to 40 wt%) and site substrate (up to 30 wt%) at the Blackwater processing sites (background < 0.05 wt%). Here, roasting of the gold ore converted the orginal As mineral, arsenopyrite, into the mineral arsenolite (As[III] trioxide polymorph) and volatilised the sulphur. The resultant sulphur-defficient chemical system is driven by arsenolite dissolution and differs significantly from mine sites where arsenopyrite is the main As source. Arsenolite is significantly more soluble than arsenopyrite. In the surficial environment, arsenolite dissolution is limited by kinetics only, which are slow enough to preserve exposed arsenolite over decades in a temperate, wet climate. This process results in surface waters with up to ca. 50 mg/L dissolved As. In reducing conditions, dissolved As concentrations are also controlled by the solubility of arsenolite producing As concentrations up to 330 mg/L. Field based cathodic stripping voltammetry showed that the As[III]/As[V] redox couple, in particular the oxidation of As[III], has a major control on system pH and Eh. Site acidification is mainly caused by the oxidation of As[III], resulting in a close link between As[V] concentrations and pH. Similarly, a strong correlation between calculated (Nernstian) and measured (electrode) Eh was found in the surface environment, suggesting that the overall Eh of the system is, indeed, defined by the As[III]/As[V] redox couple. Once the metalloid is mobilised from its original source, its mobility is controlled by at least one of the following attenuation processes: (a) precipitation of secondary metalloid minerals, (b) co-precipitation with - or adsorption to - iron oxyhydroxide (HFO), or (c) dilution with background waters. The precipitation of secondary minerals is most favoured in the case of As due to the relatively low solubility of iron arsenates, especially at low pH (~0.1 mg/L). Observations suggest that scorodite can be the precursor phase to more stable iron arsenates, such as kankite, zykaite, bukovskyite or pharmacosiderite and their stability is mainly controlled by pH, sulphur concentrations and moisture prevalence. Empirical evidence indicates that the sulphur-containing minerals zykaite and bukovskyite have a similar pH dependence to scorodite with solubilities slightly lower than scorodite and kankite. If dissolved As concentrations decline, iron arsenates potentially become unstable. Their dissolution maintains a pH between 2.5 and 3.5. This acidification process is pivotal with respect to As mobility, especially in the absence of other acidification processes, because iron arsenates are several orders of magnitude more soluble in circum-neutral pH regimes (~100 mg/L). From this, it becomes apparent that external pH modifications, for example as part of a remediation scheme, can significantly increase iron arsenate solubility and resultant As mobility. In contrast to As, the precipitation of secondary Sb and B minerals is limited by their high solubilities, which are several orders of magnitude higher than for iron arsenates. Thus, secondary Sb and B minerals are restricted to evaporative waters, from which they can easily re-mobilised during rain events. Metalloid adsorption to HFO is mainly controlled or limited by the extent of HFO formation, which in turn is governed by the availability of Fe and prevailing Eh-pH conditions. Thus, mineralisation styles and associated geochemical gradients, in particular pyrite abundance, can control the amount of HFO and consequent metalloid attenuation, and these can vary even within the same goldfleld. Furthermore, it was found that there is a mineralogical gradation between ferrihydrite with varying amounts of adsorbed As, amorphous iron arsenates and crystalline iron arsenates, suggesting that the maturity of mine waste is an important factor in As mineralogy. Once dissolved metalloids enter the hydrosphere, dilution is the main control on metalloid attenuation, which is especially pronounced at the inflow of tributaries. Dilution is, therefore, closely related to the size and frequency of these tributaries, which in turn are controlled by the regional topography and climate. Dilution is a considerably less effective attenuation mechanism and anomalous metalloid concentrations from mining related sites can persist for over 10 km downstream. The complex and often inter-dependent controls on metalloid mobility mean that management decisions should carefully consider the specific site geochemistry to minimize economic, health and environmental risks that can not be afforded. On a regional scale, background metalloid flux determines the downstream impact of an anomalous metalloid source upstream. For example, the Bullendale mine is located in a mountainous region, where rapidly eroding slopes expose fresh rock and limit the extent of soil cover and chemical weathering. Consequently, the background As flux is relatively low and As point sources, such as the Bullendale mine, present a significant contribution to the downstream As flux. In contrast, the bedrock at the Blackwater mine has undergone deep chemical weathering, resulting in an increased background mobilisation of As. Thus, the Prohibition mill site discharge, for example, contributes only about 10% to the downstream As flux. This information is relevant to site management decisions because the amount of natural background metalloid mobilisation determines whether site remediation will influence downstream metalloid chemistry on a regional scale.

Rocks of the South Island of New Zealand are locally enriched in metalloids, namely arsenic (As), antimony (Sb) and boron (B). Elevated levels of As and Sb can be found in sulphide minerals mostly in association with mesothermal gold deposits, whereas B enrichment occurs in marine influenced coal deposits. The mobility of these metalloids is important because they can be toxic at relatively low levels (e.g. for humans >0.01 mg/L of As). Their mobilisation occurs naturally from background weathering of the bedrock. However, mining and processing of coal and gold deposits, New Zealand's most economically important commodities, can significantly increase metalloid mobility. In particular, historic mines and associated industrial sites are known to generate elevated metalloid levels because of the lack of site remediation upon closure. This work defines and quantifies geological, mining, post-mining and regional processes with respect to metalloid, especially As, mobility. At the studied historic gold mines, the Blackwater and Bullendale mines, Sb levels in mineralised rocks were generally negligible (<14 ppm) compared to As (up to 10,000 ppm). Thus, Sb concentrations in solids and in water were too low to yield any meaningful information on Sb mobility. In contrast, dissolved As concentrations downstream from mine sites were found to be very high (up to 59 mg/L) (background = 10⁻� mg/L). In addition, very high As concentrations were found in residues (up to 40 wt%) and site substrate (up to 30 wt%) at the Blackwater processing sites (background < 0.05 wt%). Here, roasting of the gold ore converted the orginal As mineral, arsenopyrite, into the mineral arsenolite (As[III] trioxide polymorph) and volatilised the sulphur. The resultant sulphur-defficient chemical system is driven by arsenolite dissolution and differs significantly from mine sites where arsenopyrite is the main As source. Arsenolite is significantly more soluble than arsenopyrite. In the surficial environment, arsenolite dissolution is limited by kinetics only, which are slow enough to preserve exposed arsenolite over decades in a temperate, wet climate. This process results in surface waters with up to ca. 50 mg/L dissolved As. In reducing conditions, dissolved As concentrations are also controlled by the solubility of arsenolite producing As concentrations up to 330 mg/L. Field based cathodic stripping voltammetry showed that the As[III]/As[V] redox couple, in particular the oxidation of As[III], has a major control on system pH and Eh. Site acidification is mainly caused by the oxidation of As[III], resulting in a close link between As[V] concentrations and pH. Similarly, a strong correlation between calculated (Nernstian) and measured (electrode) Eh was found in the surface environment, suggesting that the overall Eh of the system is, indeed, defined by the As[III]/As[V] redox couple. Once the metalloid is mobilised from its original source, its mobility is controlled by at least one of the following attenuation processes: (a) precipitation of secondary metalloid minerals, (b) co-precipitation with - or adsorption to - iron oxyhydroxide (HFO), or (c) dilution with background waters. The precipitation of secondary minerals is most favoured in the case of As due to the relatively low solubility of iron arsenates, especially at low pH (~0.1 mg/L). Observations suggest that scorodite can be the precursor phase to more stable iron arsenates, such as kankite, zykaite, bukovskyite or pharmacosiderite and their stability is mainly controlled by pH, sulphur concentrations and moisture prevalence. Empirical evidence indicates that the sulphur-containing minerals zykaite and bukovskyite have a similar pH dependence to scorodite with solubilities slightly lower than scorodite and kankite. If dissolved As concentrations decline, iron arsenates potentially become unstable. Their dissolution maintains a pH between 2.5 and 3.5. This acidification process is pivotal with respect to As mobility, especially in the absence of other acidification processes, because iron arsenates are several orders of magnitude more soluble in circum-neutral pH regimes (~100 mg/L). From this, it becomes apparent that external pH modifications, for example as part of a remediation scheme, can significantly increase iron arsenate solubility and resultant As mobility. In contrast to As, the precipitation of secondary Sb and B minerals is limited by their high solubilities, which are several orders of magnitude higher than for iron arsenates. Thus, secondary Sb and B minerals are restricted to evaporative waters, from which they can easily re-mobilised during rain events. Metalloid adsorption to HFO is mainly controlled or limited by the extent of HFO formation, which in turn is governed by the availability of Fe and prevailing Eh-pH conditions. Thus, mineralisation styles and associated geochemical gradients, in particular pyrite abundance, can control the amount of HFO and consequent metalloid attenuation, and these can vary even within the same goldfleld. Furthermore, it was found that there is a mineralogical gradation between ferrihydrite with varying amounts of adsorbed As, amorphous iron arsenates and crystalline iron arsenates, suggesting that the maturity of mine waste is an important factor in As mineralogy. Once dissolved metalloids enter the hydrosphere, dilution is the main control on metalloid attenuation, which is especially pronounced at the inflow of tributaries. Dilution is, therefore, closely related to the size and frequency of these tributaries, which in turn are controlled by the regional topography and climate. Dilution is a considerably less effective attenuation mechanism and anomalous metalloid concentrations from mining related sites can persist for over 10 km downstream. The complex and often inter-dependent controls on metalloid mobility mean that management decisions should carefully consider the specific site geochemistry to minimize economic, health and environmental risks that can not be afforded. On a regional scale, background metalloid flux determines the downstream impact of an anomalous metalloid source upstream. For example, the Bullendale mine is located in a mountainous region, where rapidly eroding slopes expose fresh rock and limit the extent of soil cover and chemical weathering. Consequently, the background As flux is relatively low and As point sources, such as the Bullendale mine, present a significant contribution to the downstream As flux. In contrast, the bedrock at the Blackwater mine has undergone deep chemical weathering, resulting in an increased background mobilisation of As. Thus, the Prohibition mill site discharge, for example, contributes only about 10% to the downstream As flux. This information is relevant to site management decisions because the amount of natural background metalloid mobilisation determines whether site remediation will influence downstream metalloid chemistry on a regional scale.

The coordination chemistry of compounds featuring P-P and P—Sb bonds has been investigated to define the fundamental features of bonding in these systems. New reaction methodologies to form P—P bonds have been evolved based on careful consideration of bond strengths in the gas and condensed phase. Insights revealed from systematic studies of molecular structures have been used to augment and expand the scope of existing models for structural prediction (e.g. VSEPR theory). Unique classes of catena-antimony compounds have been discovered, illustrating a remarkable structural and electronic diversity for this heavy p-block metal. Detailed mechanistic examinations have revealed a previously unrecognized mode of ligand activation for phosphine complexes of very electrophilic acceptors. Stable sources of the hitherto unisolated and highly reactive tris-triflate reagents, E(OTf)3 (E = P, As, Sb, Bi), have been prepared and their coordination chemistry as Lewis acids and oxidizing agents has been mapped. Collectively, the findings described here span a range of coordination chemistry paradigms for p-block elements that may be broadly applicable across the periodic table. A robust plan has been proposed for applying these insights towards the preparation of fundamentally interesting molecular frameworks and towards new strategies for small molecule activation. / Graduate / 0488 / 0485

Made available in DSpace on 2014-10-09T12:23:32Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:55Z (GMT). No. of bitstreams: 1 01128.pdf: 3948265 bytes, checksum: 3a9bcbd37aaa9370f50785853df87539 (MD5) / Dissertacao (Mestrado) / IEA/D / Instituto de Quimica, Universidade de Sao Paulo - IQ/USP

xxiv, 203 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / The ever-expanding field of supramolecular chemistry has recently incorporated use of the main group ions. This dissertation presents a supramolecular approach to the coordination chemistry of the Group 15 elements, with a special emphasis on arsenic (As). Arsenic is ubiquitous in our environment, contaminates the drinking water of large human populations, and is a worldwide health concern. Arsenic's legendary toxicity is thought to be due to its thiophilicity and the stability of arsenic-thiolate bonds within proteins. Chapter I is a review of the current literature on the kinetics, thermodynamics, and supramolecular chemistry of the As(III)-thiolate bond and reveals that the stability and lability of the bond make it well-suited for supramolecular chemistry. The remainder of the dissertation explains our supramolecular design strategies for the As(III) ion with thiolate ligands, then expands the approach to the Group 15 elements phosphorus, antimony, and bismuth. Chapter II presents an approach to controlling diastereoselectivity in the self-assembly of supramolecular As 2 L 2 Cl 2 macrocycles using intramolecular steric interactions. Chapter III expands upon this approach by using intermolecular steric interactions to control diastereoselectivity and dimer formation of As 2 L 2 Cl 2 macrocycles. Chapter IV gives insight into the self-assembly of these As 2 L 2 Cl 2 macrocycles by identifying several reaction intermediates and kinetic mistakes that form during the course of the reaction. In Chapter V the application of our design strategy to the heavier Group 15 elements of antimony and bismuth is shown through the presentation of E 2 L 3 cryptands (E = As, Sb, Bi). Additionally, a Group 15 "transmetallation" reaction is explained which allows, for the first time, the preparation of the elusive P 2 L 3 cryptand. Chapter VI further examines the transmetallation reaction, the solution isomerism of the E 2 L 3 cryptands, and presents three heterometallic EE'L 3 cryptands. Finally, Chapter VII briefly concludes this dissertation and provides some potential future directions for the project. This dissertation includes co-authored material and previously published results. / Committee in charge: James Hutchison, Chairperson, Chemistry; Darren Johnson, Member, Chemistry; Catherine Page, Member, Chemistry; Michael Haley, Member, Chemistry; Scott Bridgham, Outside Member, Biology

Made available in DSpace on 2014-06-11T19:26:13Z (GMT). No. of bitstreams: 0 Previous issue date: 2005-05-06Bitstream added on 2014-06-13T19:33:35Z : No. of bitstreams: 1 borges_em_me_rcla.pdf: 583445 bytes, checksum: a94bcee1df858747cf63f7c61d62429e (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / No presente trabalho são descritas as etapas para o desenvolvimento de uma metodologia para determinação de arsênio, antimônio e bismuto em materiais geológicos, utilizando gerador de hidretos acoplado ao ICPOES, proporcionando a determinação dos elementos de interesse em baixas concentrações. O método é sensível, por isso está sujeito a interferências, como as causadas por elementos presentes na matriz. Foram realizadas otimizações nos parâmetros operacionais e analíticos do equipamento, que visaram uma melhor sensibilidade e um método eficiente de solubilização completa de amostra de rocha, que permita a determinação dos elementos de interesse em baixas concentrações. Para a etapa de validação do método foram realizados diversos ataques com adições de padrão e testes com o uso de tiouréia e iodeto de potássio com ácido ascórbico em diferentes concentrações com o objetivo de minimizar possíveis interferências presentes na matriz. Os resultados finais foram obtidos através da solubilização de materiais de referência internacionais geológicos na determinação de arsênio, bismuto e antimônio e se mostraram satisfatórios. / In this study, the steps for the development of a methodology to the determination of arsenic, antimony and bismuth in geological materials, with the use of hydride generation and ICPOES are being described. The methodology is sensitive due to that, subject is bound to suffer interferences from matrix elements. Optimizations in operations and analyticals parameters were done in the equipment. They aimed a better sensitivite and an efficient method of complete dissolution techniques in a sample of rock, which permits the determination of the analyte in low concentrations. For the steps of methodology validation, many dissolutions were realized with the addition of standard and tests with the use of thiourea and KI and acid ascorbic in different concentrations with the objective of minimizing some interferences from matrix elements. The final results were obtained through dissolutions with international reference materials in the determination of arsenic, antimony and bismuth.

Made available in DSpace on 2015-05-14T13:21:07Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2772098 bytes, checksum: 3c1518599ff53c3339b74cffefd4da7a (MD5) Previous issue date: 2010-09-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In this work were synthesized, characterized and studied experimentally and theoretically, the compounds of general formula [MX3 (L)], where M = Sb or Bi, X = Cl, Br, L = 2,2'-bipyridine (Bpy), 1,10-phenanthroline (Phen). The synthesized compounds were characterized by elemental analysis (C, H, N, Cl and Br), thermal analysis (TG / DTA) and absorption spectroscopy in the infrared region. The results of elemental analysis suggest a stoichiometry of 1:1 salt / ligand in agreement with the stoichiometry suggested by thermogravimetric analysis. The infrared data of the ligands when compared with those of the adducts indicate a strengthening of the CC bonds, CN the aromatic ring with the coordination.The Thermochemical parameters were obtained experimentally by solution calorimetry. The enthalpy of reaction, acid-Lewis base, determined by calorimetry indicate the strongest basic character of Phen compared to metals. Enthalpies of metal-nitrogen bond follows the order of bonding strength: [BiBr3(Phen)] > [SbCl3(Phen)] > [BiBr3(Bpy)] > [SbCl3(Bpy)]. The theoretical studies were aimed to the structural properties and thermochemistry in the gas phase, through the semi-empirical PM3 method. The results of the calculations predict a geometry type distorted square pyramidal for all the adducts studied, indicating the strong influence of the lone pair of electrons of metals over distance of bond metal-nitrogen. Dipole moments are calculated in the range 10-14D, suggesting a large polar character of the compounds studied. / Nesse trabalho foram sintetizados, caracterizados e estudados experimentalmente e teoricamente, os compostos de formula geral [MX3(L)], onde M = Sb ou Bi; X= Cl, Br; L= 2,2 -bipiridina (Bpy) , 1,10-fenantrolina (Phen). Os compostos sintetizados foram caracterizados por análise elementar (C,H,N,Cl e Br), análise térmica (TG/DTA) e espectroscopia de absorção na região do infravermelho. Os resultados da analise elementar sugerem uma estequiometria de 1:1 sal/ligante em concordância com a estequiometria sugerida pela análise termogravimétrica. Os dados de infravermelho dos ligantes quando comparados com os do adutos indicam um fortalecimento das ligações CC,CN do anel aromático com a coordenação. Os parâmetros termoquímicos foram obtidos experimentalmente por calorimetria em solução. As entalpias de reação, ácido-base de Lewis, determinadas por calorimetria indicam o maior caráter básico da Phen frente aos metais estudados. Das entalpias de ligação metal-nitrogênio segue a ordem de força de ligação: [BiBr3(Phen)] > [SbCl3(Phen)] > [BiBr3(Bpy)] ] > [SbCl3(Bpy)]. Os estudos teóricos foram realizados visando as propriedades estruturais e termoquímicas em fase gasosa, através do método sem-empírico PM3. Os resultados dos cálculos predizem uma geometria do tipo pirâmide de base quadrada distorcida para todos os adutos estudados, indicando a forte influência do par de elétrons isolado dos metais sobre as distâncias de ligação metal-nitrogênio. Os momentos de dipolo calculados estão na faixa 10-14D, sugerindo um elevado caráter polar dos compostos estudados.

O presente trabalho tem como objetivo estudar propriedades ópticas e estruturais de vidros e filmes de fosfato de antimônio dopados. Os vidros foram produzidos pela fusão a 900 °C, em cadinhos de carbono vítreo, dos precursores [Sb(PO3)3]n + Sb2O3 utilizando como dopantes o PbO e Cr2O3, sendo em seguida vertidos e resfriados rapidamente em moldes de aço inox. As composições vítreas em questão são: 20% [Sb(PO3)3]n 77% Sb2O3 3%PbO, 20 %[Sb(PO3)3]n 77% Sb2O3 3%Cr2O3 e 20 %[Sb(PO3)3]n 74% Sb2O3 6%Cr2O3 (mol%). A caracterização das amostras teve início com medidas de EDX para micro - análise composicional. Em seguida para os vidros na forma de bulk foram medidos os espectros de absorção e luminescência. As medidas de luminescência foram realizadas utilizando-se o laser de Kr+ nas linhas MLUV (350 nm) e MLVI (41 5nm). Medidas de EPR foram realizadas para os vidros dopados com Cr por estes possuírem elétrons desemparelhados. Os filmes finos foram depositados em substratos de soda lime pela técnica de evaporação de feixe de elétrons. A partir do espectro de absorção, o valor do bandgap (por volta de 3 eV) foi calculado, verificando que a melhor fonte para irradiação das amostras era o laser de Kr+ em MLUV. Apenas filmes de [Sb(PO3)3]n: 3% Pb2+ apresentaram efeito fotoestrutural. Com isso um estudo variando parâmetros, como tempo de irradiação, densidade de potência e espessura dos filmes, foi realizado a fim de observar a otimização do efeito. Acompanhado das variações fotoestruturais, ocorreram variações fotocrômicas, no caso fotoclareamento, as quais se caracterizaram por um deslocamento da borda de absorção para maiores energias, observado nos espectros de absorção das áreas irradiadas. Com os resultados observados do estudo e caracterização das amostras, algumas aplicações tecnológicas foram discutidas, como no caso dos efeitos observados nos filmes que podem ser utilizados para gravação de redes de difração. / The present work is about the study of the optical and structure properties of doped antimony phosphate glasses and thin films. The glasses were produced by the melting of precursors [Sb(PO3)3]n + Sb2O3 using PbO and Cr2O3 as dopant at 900 °C in vitreous carbon crucibles, then poured and quickly cooled into steel molds. The vitreous composition are: 20% [Sb(PO3)3]n 77% Sb2O3 3%PbO, 20 %[Sb(PO3)3]n 77% Sb2O3 3%Cr2O3 e 20 %[Sb(PO3)3]n 74% Sb2O3 6%Cr2O3 (mol%). The samples characterization started with EDX measurements for compositional micro-analysis. Then for the glasses in bulks form the absorption and luminescence spectra were measured. The luminescence measurements were done using MLUV (350 nm) and MLVI (415 nm) of a Kr+ laser. EPR measurements were taken for the Cr doped glasses because they present unpaired electrons. The thin films were deposited on soda lime substrates by the electron beam evaporation technique. From absorption spectra, the bandgap value around 3 eV was evaluated, noting that the best irradiation source of the samples was using a MLUV of a Kr+ laser. Only [Sb(PO3)3]n: 3% Pb2+ films presented photostructural effects. Therefore a systematic study varying several parameters, like irradiation time, power density and film thickness was conducted to observe the effect optimization. Following the photostructural variation, occurred photocchromic effects, in this case, photobleaching effects, which were characterized by a displacement of absorption edge to lower energies, observed in the absorption spectra of the irradiated areas. With the observed results from the study and characterization of the samples, some technologies applications were discussed, like in the case of the observed films effects that can be used for recording diffraction gratings.

Orientador: Marco Aurelio Zezzi Arruda / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-04T22:53:39Z (GMT). No. of bitstreams: 1 Figueiredo_EduardoCostade_M.pdf: 5877197 bytes, checksum: d13ecbeef095d45a61dd1d47fe72de84 (MD5) Previous issue date: 2005 / Mestrado / Quimica Analitica / Mestre em Química