X-Ray Absorption Spectroscopy and Computer Modelling Study of Nanocrystalline Binary Alkaline Earth Fluorides

Nanocrystalline samples of Ba1-xCaxF2 prepared by high-energy milling show an unusually high F-ion conductivity, which exhibit a maximum in the magnitude and a minimum in the activation energy at x = 0.5. Here, we report an X-ray absorption spectroscopy (XAS) at the Ca and Sr K edges and the Ba L-3 edge and a molecular dynamics (MD) simulation study of the pure and mixed fluorides. The XAS measurements on the pure binary fluorides, CaF2, SrF2 and BaF2 show that high-energy ball-milling produces very little amorphous material, in contrast to the results for ball milled oxides. XAS measurements of Ba1-xCaxF2 reveal that for 0 < x < 1 there is considerable disorder in the local environments of the cations which is highest for x = 0.5. Hence the maximum in the conductivity corresponds to the composition with the maximum level of local disorder. The MD calculations also show a highly disordered structure consistent with the XAS results and similarly showing maximum disorder at x = 0.5.

Studies on the reactions of thionyl fluoride

Thionyl fluoride undergoes quantitative oxidation with chloramine-T and reduction with lithium aluminium hydride and sodium borohydride. At elevated temperatures, (>150°C) it reacts with metals such as copper, silver, zinc and lead forming the corresponding metal sulphides, fluorides and sulphur dioxide. With the respective metal oxides, the metal fluorides and sulphur dioxide are formed.

Atomic Layer Deposition for optical applications: metal fluoride thin films and novel devices

Thin films of various metal fluorides are suited for optical coatings from infrared (IR) to ultraviolet (UV) range due to their excellent light transmission. In this work, novel metal fluoride processes have been developed for atomic layer deposition (ALD), which is a gas phase thin film deposition method based on alternate saturative surface reactions. Surface controlled self-limiting film growth results in conformal and uniform films. Other strengths of ALD are precise film thickness control, repeatability and dense and pinhole free films. All these make the ALD technique an ideal choice also for depositing metal fluoride thin films. Metal fluoride ALD processes have been largely missing, which is mostly due to a lack of a good fluorine precursor. In this thesis, TiF4 precursor was used for the first time as the fluorine source in ALD for depositing CaF2, MgF2, LaF3 and YF3 thin films. TaF5 was studied as an alternative novel fluorine precursor only for MgF2 thin films. Metal-thd (thd = 2,2,6,6-tetramethyl-3,5-heptanedionato) compounds were applied as the metal precursors. The films were grown at 175 450 °C and they were characterized by various methods. The metal fluoride films grown at higher temperatures had generally lower impurity contents with higher UV light transmittances, but increased roughness caused more scattering losses. The highest transmittances and low refractive indices below 1.4 (at 580 nm) were obtained with MgF2 samples. MgF2 grown from TaF5 precursor showed even better UV light transmittance than MgF2 grown from TiF4. Thus, TaF5 can be considered as a high quality fluorine precursor for depositing metal fluoride thin films. Finally, MgF2 films were applied in fabrication of high reflecting mirrors together with Ta2O5 films for visible region and with LaF3 films for UV region. Another part of the thesis consists of applying already existing ALD processes for novel optical devices. In addition to the high reflecting mirrors, a thin ALD Al2O3 film on top of a silver coating was proven to protect the silver mirror coating from tarnishing. Iridium grid filter prototype for rejecting IR light and Ir-coated micro channel plates for focusing x-rays were successfully fabricated. Finally, Ir-coated Fresnel zone plates were shown to provide the best spatial resolution up to date in scanning x-ray microscopy.

Reaction of sulphuryl chlorofluoride with a few metals and metal oxides

Sulphuryl chlorofluoride has no observable reaction with metals and metal oxides at room temperature. Metals like copper, silver, iron, and zinc react with the chlorofluoride in the temperature range 200–400°C. Metal chlorides, metal fluorides and sulphur dioxide are the main products of these reactions. With the corresponding metal oxides, on the other hand, the respective metal sulphates are formed in addition to the metal chlorides and fluorides. In the case of lead and lead oxide, lead chlorofluoride is formed instead of lead chloride and lead fluoride. Sulphuryl fluoride is formed in small quantities in all these reactions by the decomposition of the chlorofluoride. Glass is not attacked by sulphuryl chlorofluoride below 500°C.

An investigation of the PrBa2Cu3O7-δ system

Members of the PrBa2Cu3O7–delta system possessing the orthorhombic structure over a wide range of oxygen stoichiometry (delta=–0.5 to +0.5) have been prepared and characterized. Similar compositions with a tetragonal structure have also been prepared. None of the oxides is superconducting, independent of the structure or stoichiometry. Praseodymium seems to be present to a small extent in the 4+ state in oxygen-excess (negative delta) samples. Orthorhombic PrBa2Cu3O7–delta samples show the presence of twins suggesting that twins arise from orthorhombicity and have no relation to the superconductivity. A neutron diffraction study of a near-stoichiometric sample has shown a disordered orthorhombic structure with 72% occupancy of the 01 (chain) sites and with no interchange between Pr and Ba sites.

Use of metastable equilibria for determination of Gibbs energy of solids

Attempts are made to measure activities of both components of a binary alloy (A�B) at 650 K using a solid-state galvanic cell incorporating a new composite solid electrolyte. Since the ionic conductivity of the composite solid electrolyte is three orders of magnitude higher than that of pure CaF2, the cell can be operated at lower temperatures. The alloy phase is equilibrated in separate experiments with flourides of each component and fluorine potential is measured. The mixture of the alloy (A�B) and the fluoride of the more reactive component (BF2) is stable, while (A�B) + AF2 mixture is metastable, Factors governing the possible use of metastable equilibria have been elucidated in this study. In the Co�Ni system, where the difference in Gibbs energies of formation of the fluorides is 21.4 kJ/mol, emf of the cell with metastable phases at the electrode is constant for periods ranging from 90 to 160 ks depending on alloy composition. Subsequently, the emf decreases because of the onset of the displacement reaction. In the Ni�Mn system, measurement of the activity of Ni using metastable equilibria is not fully successful at 650 K because of the large driving force for the displacement reaction (208.8 kJ/mol). Critical factors in the application of metastable equilibria are the driving force for displacement reaction and diffusion coefficients in both the alloy and fluoride solid solution.

A study of the reaction of divalent transition metal chlorides with pyridinium poly(hydrogen fluoride), ppht, and the effect of potassium hydrogen fluoride on fluorination and complexation

Studies of the reaction of metal chlorides, MCl2 (M = Mn, Co, Ni, Cu, Zn) with PPHF at room temperature have shown that Mn, Co and Zn form the corresponding metal fluorides, MF2, while Ni and Cu form their dipyridine metal(II) dichloride complexes. Nickel and copper complexes further undergo fluorination and complexation by potassium hydrogen fluoride in PPHF to form KNiF3 and KCuF3.

Combustion synthesis and properties of Ce1-xPrxO2-delta red ceramic pigments

Praseodymium-doped ceria red pigments, Ce1−xPrxO2−δ, x=0–0.5 have been prepared by the thermal decomposition of the redox compound Ce1−xPrx(N2H3COO)3·3H2O as well as by the combustion of aqueous solutions containing cerous nitrate, praseodymium nitrate and oxalyl dihydrazide (ODH)/ammonium acetate. Formation of the pigment has been confirmed by its characteristic red colour and reflectance spectra which shows the reflection edge not, vert, similar690 nm corresponding to charge transfer from the ligand orbitals to the localised 4f1 of Pr4+. The particulate properties of praseodymium-doped ceria pigments obtained from the combustion of redox compounds and redox mixtures are compared.

Thermodynamic properties of Ln-O (Ln = La, Pr, Nd) solid solutions and their deoxidation by molten salt electrolysis

The lanthanide metals lanthanum, praseodymium and neodymium containing 2,200, 2,600, 1,850 mass ppm oxygen, respectively, were deoxidized to 20-30 ppm level at 1,073 K by an electrochemical method. The metal to be deoxidized was used as the cathode in an electrolysis cell which consisted of a graphite anode and molten CaCl2 electrolyte. The calcium metal produced at the cathode by electrolysis effectively deoxidized the lanthanide metal. Calcium oxide produced by deoxidation, dissolved in the melt. The liberation of carbon monoxide/dioxide at the anode was found to prevent accumulation of oxygen in the melt. For a quantitative discussion of the limits of deoxidation achievable by this technique, a thermodynamic investigation of the lanthanide-oxygen (Ln-O ; Ln = La, Pr, Nd) solid solutions was conducted. The lanthanide metal, yttrium and titanium samples were immersed in calcium-saturated CaCl2 melt, containing a small quantity of dissolved CaO, at 1,093 K. The oxygen potential of the melt and the Ln-O solid solutions were obtained from the oxygen content of yttrium samples at equilibrium, and the known thermodynamic properties of yttrium-oxygen solid solution. The results were confirmed by using Y/Y2O3 equilibrium to control the oxygen potential of the molten salt reservoir. The oxygen affinity of the metals was found to decrease in the order : Y > Ti > Nd > Pr > La. The deoxidation results are consistent with the thermodynamic properties of the RE-O solid solutions.

Influence of heat treatment on spectroscopic properties of Er3+ in multicomponent ZrF4-ZnF2-AlF3-YF3-MF2 (M = Ca, Sr, Ba) based glass

Er3+ doped multicomponent fluoride based glass was prepared. These precursor fluoride glass samples were then heated using different schedules. Crystalline phase particles were successfully precipitated in the multicomponent fluoride glass samples after heat treatment. The influence of heat treatment on the spectroscopic properties of Er3+ in multicomponent fluoride based glass samples were discussed. Small changes of the Judd-Ofelt parameters Omega(i) (i = 2,4,6) were found in multicomponent fluoride glass samples before and after heat treatment compared to oxyfluoride telluride glass. Preparation conditions used to produce transparent multicomponent fluoride glass ceramics doped with rare-earth ions are discussed. (c) 2007 Elsevier B.V. All rights reserved.

碱金属氟化物对掺Yb~(3+)氟磷酸盐玻璃析晶稳定性和光谱性质的影响

研究了碱金属氟化物对掺Yb3+氟磷玻璃的光谱性质和析晶稳定性能的影响。运用倒易法计算了Yb3+的发射截面。结果显示,LiF的引入对吸收和发射截面的提高作用较大并出现最佳引入量极值,其次为KF。碱金属氟化物的引入可提高二元体系的析晶稳定性能,使玻璃网络结构得到改善;拉曼光谱显示二元体系中引入YbF3后玻璃网络结构得到增强,而在引入碱金属氟化物的三元体系中掺杂YbF3后破坏了网络完整性,降低系统析晶稳定性能。

Thermal analysis of glasses in TeO2-BaF2-LaF3 systems

Divalent metal fluorides MF2 (M=Sr, Mg, Ca) in oxyfluoride tellurite glasses TeO2-BaF2-LaF3 were synthesized. The densities, refractive indices and characteristic temperatures of synthesized glasses were measured. The influence of divalent metal fluorides MF2 (M=Sr, Mg, Ca) on the thermal stability of oxyfluoride tellurite glasses TeO2-BaF2-LaF3 were studied. Results show that the replacement of BaF2 by SrF2 and MgF2 can enhance the thermal stability against crystallization of the glass. A glass system with good thermal stability was produced, which could be a potential candidate for the host materials of the fiber devices.

Efetividade da aplicação semestral de verniz fluoretado na redução da incidência de cárie dentária em pré-escolares: resultados após 18 meses

O objetivo deste trabalho foi avaliar se, após 18 meses de acompanhamento, a aplicação semestral de verniz fluoretado em pré-escolares reduz a incidência de cárie na dentição decídua. Os possíveis efeitos adversos e a aceitabilidade da intervenção também foram investigados. Desenho do estudo: ensaio clínico controlado, randomizado, duplo-cego, com uso de placebo. Ingressaram no estudo 200 crianças na faixa etária de 12 a 48 meses, recrutadas em uma unidade da rede pública de saúde. Cem crianças foram alocadas no grupo teste (verniz fluoretado Duraphat, Colgate Oral Pharmaceuticals, New York, NY, USA) e 100 no grupo controle (verniz placebo, Colgate Oral Pharmaceuticals, New York, NY, USA). Os exames clínicos, seguidos das aplicações semestrais de verniz nos grupos teste e controle, foram realizados por duas odontopediatras treinadas (Kappa=0,85) que utilizaram o International Caries Detection and Assessment System II (ICDAS II) para registrar o índice ceo-s nos níveis c1 (lesão ativa em esmalte não cavitado, lesão em esmalte cavitada e lesão em dentina) e c3 (lesão em dentina) de detecção de doença. Verificou-se também a ocorrência de efeitos adversos e outras queixas por entrevistas telefônicas com os responsáveis 7 a 10 dias após a primeira aplicação de verniz. Como resultado aos 18 meses de acompanhamento, 85 crianças do grupo teste e 92 do grupo controle foram examinadas. As diferenças nos incrementos médios de cárie, entre os grupos teste e controle, foram -0,9 (IC95%: -2,4;0,4) no nível c1 e -0,8 (IC95%:-1,9;0,2) no nível c3. O risco de desenvolvimento de novas lesões de cárie em dentina foi 30% (RR=0,70; IC 95%:0,49;0,99) menor nas crianças do grupo teste em relação às do grupo controle. Foram feitas entrevistas com 183 responsáveis sobre os efeitos adversos e a aceitabilidade da intervenção. Um relatou que a sua criança sentiu ardência na cavidade bucal após a aplicação do placebo e outro ficou incomodado com a coloração amarelada dos dentes da criança imediatamente após a aplicação do verniz fluoretado. A aplicação semestral de verniz fluoretado na dentição decídua de pré-escolares reduz o risco de desenvolver lesão de cárie dentária em dentina. Além disso, essa intervenção é segura e bem aceita pelos pais e pelas crianças.

Effect of alkali and alkaline earth fluoride introduction on thermal stability and structure of fluorophosphate glasses

The thermal stability and structure of RF-RF2-AIF(3)-Al(PO3)(3) fluorophosphate glasses were investigated. Analyses of infrared absorbance spectra and Raman spectra reveal that with increasing number of alkali and alkaline earth fluoride components, the sum of P-O-P bond and O-P-O bond increases and glass network is strengthened. Consequently, the inhibition to nucleation and crystallization processes is improved, which is proved by the increment of thermal stability factors AT and S determined by differential scanning calorimetry. In addition, it was found that LiF has poor ability to form glass in univalent alkali fluorides and MgF2 has comparative strong ability to form glass in bivalent alkaline earth fluorides. (c) 2006 Published by Elsevier B.V.

Growth, characterization and optical quality of CaF2 single crystals grown by the temperature gradient technique

The CaF2 single crystals with diameters up to 200 mm were successfully grown by modified temperature gradient technique (TGT), which are suitable for application as optical elements in the ultraviolet range. The optimizations of various growth parameters were systematically studied. Properties of as-grown CaF2 crystals were characterized by the nature of inclusions, dislocations, crystallinity, and impurities contents. The results showed that the dislocations and multinucleation were mostly constrained in the conical part of the crystals with the cylindrical parts having the best crystalline quality and lowest impurity contents. The high optical quality of TGT-grown CaF2 single crystals was also confirmed to have excellent optical transmission in 190-2500 nm and refractive index homogeneity. (c) 2005 Elsevier Ltd. All rights reserved.