Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1967. / "January 1967." Includes bibliographical references.

Thesis (Ph.D.). / Written for the Dept. of Physics. Title from title page of PDF (viewed 2009/06/11). Includes bibliographical references.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1968. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1962. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 169-174).

Theses (M.S.)--Marshall University, 2006. / Title from document title page. Includes abstract. Document formatted into pages: contains xii, 76 pages. Bibliography: p. 71-76.

Motivados por trabalhos anteriores que analisaram diferentes comportamentos entre cristais e filmes policristalinos, relacionados com a cristalinidade e a concentração de impurezas, neste trabalho investigamos métodos de obtenção e processamento de filmes de haletos alcalinos dopados. Durante este trabalho foi montado um sistema de evaporação que disponibilizou a utilização de duas fontes de evaporação para a produção de amostras: resistiva e via feixe de elétrons. Apresentamos uma comparação entre resultados de caracterizações dos filmes produzidos e de monocristais existentes na literatura. A fim de se obter filmes dopados com impurezas mono e divalente e, também, duplamente dopados, alguns métodos alternativos de processamento foram investigados. A partir da comparação entre os sistemas KCl:(In +, Tl+ e Cu+) determinamos a dependência da cristalinidade em função do tamanho do íon dopante. O efeito da temperatura do substrato durante a evaporação foi investigado para o sistema KCl:Tl+, e comparado com resultados obtidos em filmes submetidos a tratamentos térmicos. Para a obtenção de filmes do sistema KCl:Yb2+:CN-, a preparação dos materiais precursores é um aspecto muito importante a ser considerado, a fim de se reproduzir nos filmes propriedades similares às dos monocristais. Nesse sentido, para evaporação foram utilizados o próprio cristal e pastilhas dos sais precursores obtidas a partir de técnicas de processamento cerâmico. A caracterização óptica dos filmes foi feita através de espectroscopia de absorção óptica e luminescência. A morfologia foi observada através de microscopia eletrônica de varredura e de força atômica, e a estrutura determinada por técnica de difração de raios X / The present work has been motivated by previous research on doped alkali halides films, that had been compared with single crystals, yielding different features, wich were related to crystallinity and impurity concentration. Preparation and processing techniques of doped alkali halides polycrystalline films have been investigated in this work. Two different evaporation sources have been used for samples production: resistive and via electron beam gun. Main results presented here are used to compare single crystals and films. In order to prepare single and double doped films, we have also tried several processing methods. From investigation of KCl:Tl+ system we have determined crystallinity dependency with impurity ion size. The KCl:Tl+ system has been used to verify the effect of substract temperature during evaporation. Results have been compared with films submited to thermal annealing. To obtain double doped KCI:Yb2+ :CN- films, we were very careful with preparation of precursor materials, since we intended to reproduce single crystals physical properties. Then, we have used single crystal itself for evaporation, besides pressed power pieces from precursor salts, obtained from ceramics processing technique. Optical absorption and photoluminescence have been carried out to perform optical characterization of evaporated films. Morphology has been observed by atomic force microscopy and scanning electron microscopy, and film structure has been observed by X-ray diffraction technique

Os modos vibracionais localizados dos pares H-H-, D-D- e H-D- em KCl, KBr, KI, RbCl e NaCl foram estudados para diversas configurações. As frequências dos modos infravermelho ativos determinados experimentalmente mostram boa concordância com o modelo de dois osciladores harmônicos acoplados. A largura de linha para os diferentes modos nos cristais examinados é discutida. A dependência com a temperatura da largura de linha para os modos transversais T1 e T2 no sistema KCl+ H- H-, indica que o alargamento das mesmas é devida ao \"mecanismo de decomposição\", no qual dois fônons são criados. Estes fônons são devidos ao decaimento do modo localizado em fase num fônon acústico da rede e num fônon localizado fora de fase. Propriedades gerais, como a lei de Ivey e diversas outras particularidades dos halogenetos alcalinos estudados são apresentadas / The localized vibrational modes of H-H-, D-D- and H-D- in KCl, KBr, KI, RbCl and NaCl were studied for different pair configurations. The measured frequencies of the infrared active modes were found to be in good agreement with a model of two coupled harmonic oscillators. The line width for different modes in the salts studied is discussed. The temperature dependence for the transversal modes T1 and T2 of the line width for the H- H- pairs in KCl indicates that the broadening of these lines is due to the \"decomposition mechanism\", that generates two phonons. The generated phonons due to the decay of the localized phonon that corresponds to the out of phase vibration of the H- H- pair. The general properties, as the Ivey law and several particulars of the properties in the alkali-halides studied are presented

Apresentamos resultados experimentais sobre o comportamento fora de centro do íon de Cu+ em cristais de RbCl, RbBr, RbI, NaI e em cristais mistos de KI +%KCl e KCl +%KI; como também do íon de Ag+ em RbI. Usamos técnicas de absorção ótica no ultra travioleta, corrente termoestimulada (ITC) e dicroísmo induzido por pressão uniaxial. Com estas técnicas, determinamos o comportamento da força do oscilador em dependência com a temperatura, energia de ativação, tempo de relaxação em dependência com a temperatura, momento dos dipolos elétricos, a mudança de configuração do íon de Cu + na reorientação num sistema de multipoço trigonal . puro para um multipoço ortorrómbico no crital misto de KI+1%KCl. Detetamos pela primeira vez a relaxação por ativação térmica de bandas de ITC a temperatura relativamente baixa, como é o caso do íon de Ag+ em RbI que acontece em 24ºK. Ainda, apresentamos alguns resultados sobre o comportamentp do íon de Li + que fica fora de centro no KC1, em cristais de KCl contendo centros U de H- e de D-, usando absorção ótica no infravermelho médio. / Experimental results are given on the off-center behavior of Cu+ ion in RbCl, RbBr, Hbl, NaI and in mixed crystals of KI+%KCl and KCl+%KI, as also on Ag+ in RbI. We use UV optical absorption, ionic thermal current (ITC) and uniaxial stress induced dichroism techniques. It is studied the temperature dependence of the oscillator strength, the relaxation time and the electric dipo1e moment are determined in the above crystals. We observe and discuss the change on the equi1ibrium configuration trigonal of the Cu+ ion in KI to the ortorrhombic in Kl+%KCl mixed crystal. For the first time we detect with the ITC measurements a thermal activated process at low temperature (24ºK), this behaviour occurs in RbI:Ag+. Using mid-infrared absorption measurements, we give several results and discussions on the U centers (either H- or D-) perturbed by Li+ ion in KCl crystals.

Conventional Ag/AgX electrodes, responsive to halide X, cannot be used to monitor the addition of a second halide Y since such additions result in a slow chemical conversion of the macroscopic halide coating AgX to AgY. This is a serious problem in the manufacture of photographic emulsions that frequently contain more than one silver halide. The thesis describes a new electrochemical measurement technique with the ability to make appropriate determinations in solutions of mixed halides. In the new technique (termed "clean/coat/measure"), silver electrodes were prepared "in situ" by applying square wave pulses to the electrode. First the previous halide layer was removed, then the electrode was coated in situ with a new layer of silver halide and this was used to measure the open circuit potential before the cycle was repeated. In this way the halide coating reflected the composition of the measurement solution. Existing commercial instrumentation was inappropriate for the proposed measurement sequence. Thus, a range of instrument hardware and software was designed and built by the author and used to study the influences of a multitude of parameters on the measurement performance. 1. A stable and accurate measurement system was designed and fabricated allowing the potentials of eight electrodes to be measured simultaneously in grounded solutions. Data was collected and stored on a PC using custom written software. Calibration curves for conventional silver/silver chloride, bromide and iodide electrodes were obtained over a range of concentrations and temperatures. Silver/silver halides electrodes with small surface areas (< 9 mm2) and thin halide coatings (< 1 nm thick) were studied to ensure that such electrodes performed as conventional large, thickly coated electrodes. Calibration curves showed no deterioration of response due to small surface areas and, over short time scales (< 2 min), no deterioration due to thin layers. 2. A laboratory instrument was designed and built to apply potential pulses, control a rotating disc electrode (RDE) and collect data. The system allowed both controlled potential pulses to be applied to the electrodes and open circuit potentiometric measurements to be made. Measurements of potential and current were collected at a rate of 10,000 measurements per second. The system used custom software running on a PC to control the instrumentation and to store data on the PC. Using this instrumentation a RDE was used to study the new "clean/coat/measure" pulsed technique. Results from the RDE study indicated that an electrode capable of sensing halide could be produced by this technique if an applied potential pulse with sufficient charge was applied. This minimum charge (11 x w-s C cm-2) produced a coating thickness approximately equivalent to a monolayer. The study also indicated that the technique was independent of the speed of rotation of the silver electrode and was successful over a wide range of conditions of pulse time, applied potential and cycle times for solution of potassium bromide in the range 0.001 to 0.05 M. The technique also successfully measured the addition of potassium iodide to a solution of potassium bromide while conventional thickly coated electrodes did not. 3. Two further instrumentation systems were designed and built to be used in a grounded stainless steel emulsion making vessel , one to apply controlled potential pulses and one to apply constant current pulses. Using these instruments and the conditions found for the RDE, static cylindrical electrodes in stirred solutions were investigated using both controlled potential and constant current square wave pulses of between 50 and 500 ms. Both potential step and current step techniques successfully measured the halide concentration of solutions of potassium chloride and bromide (0.001 to 0.5 M) and potassium iodide (0.0001 to 0.5 M). Both methods were also shown to be able to successfully monitor the addition of iodide to bromide and chloride solutions. With respect to future work, modifications to the instrumentation are proposed, including the replacement of the PC by an on-board microprocessor, the design of a multi-channel system and use of intelligent software to determine the optimum potential or current to apply. Areas of work required to be carried out before the system could be used in a production environment are given.

No description available.