Estudo de monocromadores assimétricos de raios-X

Orientador: Stephenson Caticha-EllisDissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb WataghinResumo: Neste trabalho são estudados monocromadores assimétricos, isto é, formado por cristais com a superfície cortada segundo um ângulo f0 com os planos refletores. O estudo experimental baseado no método de Evans, Hirsch & Kellar( 11 ) , é feito medindo a intensidade de raios-X espalhada pela reflexão Ge( 111 ), com o cristal montado de forma a poder ser girado ao redor da normal ao plano correspondente. No decorrer do trabalho mostramos que o metodo de Evans, Hirsch & Kellar, que experimentalmente é muito atraente, necessitando-se cortar o cristal com o ângulo f0 e simular diferentes ângulos de corte por meio do giro ao redor da normal aos planos refletores, implica em complicações teóricas bastante difíceis de serem superadas muitas das quais foram resolvidas neste trabalho. Na parte teórica deste trabalho, deduzimos em forma geral as expressões da potência e da intensidade refletidas em reflexão assimétrica por um cristal cortado sob um ângulo f0 em relação aos planos de ref1exão, baseando-nos exclusivamente na teoria da interacão dos feixes multiplamente difratados em cristal mosaico ( Caticha-Ellis S., 1969 ( 9 ) ). Foram encontrados efeitos novos, tal como a rotação do feixe difratado numa reflexão assimétrica, efeito que não tinha sido encontrado pelos demais autores que já trabalharam em problemas de reflexão assimétrica. O acordo entre os resultados teóricos e experimentais é analisado no texto. Experimentalmente, fizemos medidas da potência e intensidade do feixe difratado e do ângulo de rotação da seção transversal deste feixe, assim como medidas da intensidade refletida pelas superfícies paralela e inclinada, em função do tratamento aplicado a elas. As equações desenvolvidas para a potência e intensidade relativas do feixe refletido em função da assimetria, permite afirmar que a máxima relação possivel a ser esperada na intensidade do feixe concentrado com relação a reflexão simetrica, é sempre menor do que 2,0. A variação da potência total concorda bem com os valores previsto pela teoria as máximas discrepâncias ocorrendo para as posições de máxima assimétria. onde os valores experimentais devem ser possivelmente mais influenciados pelos fatores instrumentais e pelo defeitos de regularidade e planaridade da superfície. Dos resultados experimentais concluimos. que para obtermos máxima intensidade com um monocromador assimetrico, o ângulo f0 entre planos refletores e superficie deve ser aproximadamente igual a 4,8° para a Ge( 111 ) e de 5,3 para a Si( 111 ), dando origem a aumento de intensidade da ordem de 41% e 31% respectivamente em relação à superfície paralela aos planos. A posição desses máximos depende do tratamento superficial o que faz então impossível dar uma solução válida para todos os casos. Além do mais o valor correto a ser usado deverá ser obtido após as correções da curva pelos fatores instrumentais, sendo estes muito complicados e atingem grande importância para maiores graus de assimetria, isto é b = +-1. O perfil w obtido apresenta irregularidades ( vários picos com forma esquisitas ), segundo o tratamento superficial da amostra. Os polimentos mecânicos mesmo feitos de forma extremamente cuidado com grãos de até 0,05 mm de diâmetro, não foram capazes de eliminar essas irregularidades. O tratamento químico puro ( etching ) também foi imcapaz de resolver o problema. Somente o tratamento mecânico-químico desenvolvido neste trabalho conseguiu obter pontos de varredura de forma correta, reproduzivel e quase sem variações de um siti o do cristal a outro. Nos tratamentos teóricos feitos até agora, pelos diferentes autores, a partir de Evans, Hirsch & Kellar em diante, faziam depender a intensidade e a potência de um só parâmetro geometri co de assimetria. Neste trabalho mostramos que é necessário introduzir mais um parâmetro que depende da relação entre o ângulo de corte f0 e do angulo, de Brag qB. Foi assim definido o fator de corte do cristal k = tgf0 / tgqB,em função do qual diversas expressões adotam formas convenientes. Finalmente são discutidas prováveis extensões deste trabalhoAbstract: Asymmetric X-ray monochromators, firsts introduced by I. Fankuchen ( 1937 ) with the purpose of concentrating an X-ray beam have been the subject of numerous investigations. Evans, Hirsch and Kellar as early as 1948, based ther well known and hitherto unchallenged study on the hypothetic existence of a non-ref1ecting surface layer with an absorption coefficient different from that of the bulk crystal which they used to fit a "theoretical" curve to their experimental data. In this Thesis it is shown that the physical behavior of asymmetric monochromators can be explained without recourse to any kind of artificial hypothesis, by means of the theory of multiple scattering of X-rays ( Caticha-Ellis, 1969 ). The differential equations governing the interchange of power among the incident and the diffracted waves were solved in the two-beam asymmetric case and the solutions expressed in terms of the asymmetry parameters: R = sen( qB - f ) / Sen( qB + f ) or B = 1 - R / 1 + R, where qB is the Bragg angle and f0 the angle between the reflecting plane and the reflecting surface measured on the plane of incidence. f0 is the dihedral angle between the o plane surface and the reflecting planes. The solutions were found to depend not just on one but on two parameters, one of assimmetry and k = tgf0 / tgqB which was called a "cutting parameter". The experimental method used here is based in that of Evans et al. A crystal cut with f0 > qB, turns around the normal to the reflecting planes thus generating different asymmetry f angles. The experimental advantage is th at only one crystal has to be cut. The theoretical complications involved, most of which are discussed here in detail, are the price for that simplifications. A new effect, the rotation of the asymmetrically diffracted beam was predicted and confirmed experimentally. The theory also demonstrates that the intensity in the concentrated beam can not be move than twice the intensity of the symmetrically reflected beam, a fact already known to previous authors. The measured diffracted power agrees well with the maximum discrepancies occur when approaching of maximum asymmetry b = +-1, where the experimental values are largely affected by surface irregularities as well instrumental factors, which how ever have not yet been studied. w - profiles taken on different regions of the crystal showed pronounced differences according to the suface treatment; even after extremely careful polishing with corrudum powder of 0.05 mm grain size. Etching worsened the situation by splitting the w - peak in several smaller anes. Only a hybrid mechanical - chemical treatment, developped for this purpose was able to produce surfaces whose w - profiles possess a reasonable peak shape and are practically invariant for the differente regions of the crystal. In conclusion the theory used irl this thesis explains well the power and intensity diffracted asymmetrically by a crystal cut with an angle f0 with respect to the reflecting planes except under extreme conditions of asymmetri where the instrumental and surface effects are dominantMestradoFísicaMestre em Físic

Thermal Degradation of Polypropylene Pine Sawdust Composite Filaments through Successive Heating and Reprocessing

Considering the use of the new molding thermoplastic technique, where viscous filaments can be artistically or technically manipulated to create three-dimensional pieces using an extruder, this paper discusses the optimal PP/wood fiber filament preparation conditions especially the thermal degradation. Not only is it essential to know the best processing conditions of the composites but also gain durability and/or advantageous color change when the final products made with viscous filaments are subjected to thermal treatments. Very few papers have been published on polypropylene-pine wood filament composites and the thermal degradation of such filaments. This paper presents the preparation and characterization of filament composites using 5, 10, and 20wt.% pine sawdust with a compatibilizer obtained by hot molding through the use of an extruder, and discusses the effect of both drying time and temperature on the prepared filament composites to understand thermal degradation when subjected to 60°C and/or 120°C. Prepared filament composites are characterized for physical (density, water absorption, and crystallinity), thermal and tensile properties besides their morphology along with fractography. X-ray diffraction results confirmed the data obtained in thermal studies indicating that increased fiber content decreased both the crystallinity and the thermal resistance while decreasing the melting temperature of the filament composites. Fractographic studies revealed low adhesion between the sawdust and the matrix, evidenced by the presence of loose and some unattached sawdust particles in some composites, thus, supporting the observed low strength in these composites, besides the influence of drying time and temperature on the mechanical properties of the composites

Diamond Thermal Expansion Measurement Using Transmitted X-ray Back-diffraction.

The linear thermal expansion coefficient of diamond has been measured using forward-diffracted profiles in X-ray backscattering. This experimental technique is presented as an alternative way of measuring thermal expansion coefficients of solids in the high-resolution Bragg backscattering geometry without the intrinsic difficulty of detecting the reflected beam. The temperature dependence of the lattice parameter is obtained from the high sensitivity of the transmitted profiles to the Bragg angle variation with temperature. The large angular width of the backscattering profiles allows the application of this technique to mosaic crystals with high resolution. As an application of this technique the thermal expansion coefficient of a synthetic type-Ib diamond (110) single crystal was measured from 10 to 300 K. Extremely low values (of the order of 1 x 10(-7) +/- 5 x 10(-7)) for the linear thermal expansion coefficient in the temperature range from 30 to 90 K are in good agreement with other reported measurements.12349-5

X-rays anomalous dispersion measurement.

Com a crescente disponibilidade de luz síncrotron tem-se utilizado cada vez mais a dispersão anômala (f´) no estudo de materiais. Apesar dos vários métodos já empregados na medida do fator de espalhamento atômico, ainda é pequeno o número de elementos abrangidos. Este trabalho apresenta uma contribuição à ampliação da gama de elementos mensuráveis através de um método interferométrico diferencial para a determinação experimental de f´. A sua demonstração é feita através de medidas em Selênio obtendo-se o mesmo nível de precisão do método &#933-&#933/2 usado em trabalhos anteriores. Esses dois métodos são criticados quanto ao limite de erro atingível devido à sua natureza não-absoluta. Uma técnica de preparação de amostras para materiais de baixo ponto de fusão é explorada, permitindo determinar f´absolutamente, com erro de 0,03 elétron. A medida do fator de espalhamento atômico através do desvio angular entre as reflexões de Bragg e Laue é proposta e testada com resultados de qualidade bastante inferior às técnicas interferométricas. A construção de interferômetros de raios X estáveis e de alto contraste é estudada quanto à seleção dos monocristais de silício e tratamento após o corte do dispositivo, atingindo-se contraste de 80% com estabilidade de uma milifranja por hora.The use of anomalous dispersion (f\') in the study of materials has been increasing with the availability of synchrotron radiation. Although many methods have been designed for the measurement of the atomic scattering factor, the number of elements the cover is still small. This work presents a contribution to the widening of the range of measurable elements through a Differential interferometric method for the determination of f´. Its demonstration is achieved by measurements on Selenium, reaching the same level of accuracy obtained by the &#933-&#933/2 method used in previous work. These two methods are criticized in terms of the achievable errors due to its non-absolute nature. A technique for the preparation of samples with low melting point materials is developed, allowing the determination of f´ absolutely, with an error of 0,03 electron. The measurement of atomic scattering factor through the angular offset between Bragg and Laue reflections is proposed and tested, with low quality results compared to interferometric methods. The construction of high stability and good contrast X-ray interferometers is studied in terms of silicon single crystal selection and its treatment after device cutting. 80% contrast was achieved with a stability of one milifringe per hour

X-rays anomalous dispersion measurement.

Com a crescente disponibilidade de luz síncrotron tem-se utilizado cada vez mais a dispersão anômala (f´) no estudo de materiais. Apesar dos vários métodos já empregados na medida do fator de espalhamento atômico, ainda é pequeno o número de elementos abrangidos. Este trabalho apresenta uma contribuição à ampliação da gama de elementos mensuráveis através de um método interferométrico diferencial para a determinação experimental de f´. A sua demonstração é feita através de medidas em Selênio obtendo-se o mesmo nível de precisão do método &#933-&#933/2 usado em trabalhos anteriores. Esses dois métodos são criticados quanto ao limite de erro atingível devido à sua natureza não-absoluta. Uma técnica de preparação de amostras para materiais de baixo ponto de fusão é explorada, permitindo determinar f´absolutamente, com erro de 0,03 elétron. A medida do fator de espalhamento atômico através do desvio angular entre as reflexões de Bragg e Laue é proposta e testada com resultados de qualidade bastante inferior às técnicas interferométricas. A construção de interferômetros de raios X estáveis e de alto contraste é estudada quanto à seleção dos monocristais de silício e tratamento após o corte do dispositivo, atingindo-se contraste de 80% com estabilidade de uma milifranja por hora.The use of anomalous dispersion (f\') in the study of materials has been increasing with the availability of synchrotron radiation. Although many methods have been designed for the measurement of the atomic scattering factor, the number of elements the cover is still small. This work presents a contribution to the widening of the range of measurable elements through a Differential interferometric method for the determination of f´. Its demonstration is achieved by measurements on Selenium, reaching the same level of accuracy obtained by the &#933-&#933/2 method used in previous work. These two methods are criticized in terms of the achievable errors due to its non-absolute nature. A technique for the preparation of samples with low melting point materials is developed, allowing the determination of f´ absolutely, with an error of 0,03 electron. The measurement of atomic scattering factor through the angular offset between Bragg and Laue reflections is proposed and tested, with low quality results compared to interferometric methods. The construction of high stability and good contrast X-ray interferometers is studied in terms of silicon single crystal selection and its treatment after device cutting. 80% contrast was achieved with a stability of one milifringe per hour

The epitaxial growth of evaporated cu/caf2 bilayers on si(111)

Successful and unexpected epitaxial growth of Cu/CaF2, bilayers on hydrogen terminated Si(111) wafers by thermal evaporation is reported. The bilayers were characterized with conventional x-ray diffraction experiments, grazing angle incidence x-ray diffraction experiments, rocking curves, and x scans. The growth mode of Cu films on CaF2 epitaxially grown on Si(111) is completely different from that of the Cu film grown directly on Si(111)

Structural change and heteroepitaxy induced by rapid thermal annealing of CaF/sub 2/ films on Si(111)

In this article we show that heteroepitaxial CaF2 films can be induced on Si~111! with a rapid thermal anneal. The change from preferentially oriented polycrystals to a single crystal with type- B epitaxy is visible by different structural techniques. The x-ray photoelectron spectroscopy results indicate the presence of a reacted layer at the CaF2 /Si interface with a pronounced increase of fluorine atoms at this interface. Transmission electron microscopy results show that big structural changes occur due to the thermal pulse

Structural change and heteroepitaxy induced by rapid thermal annealing of CaF/sub 2/ films on Si(111)

In this article we show that heteroepitaxial CaF2 films can be induced on Si~111! with a rapid thermal anneal. The change from preferentially oriented polycrystals to a single crystal with type- B epitaxy is visible by different structural techniques. The x-ray photoelectron spectroscopy results indicate the presence of a reacted layer at the CaF2 /Si interface with a pronounced increase of fluorine atoms at this interface. Transmission electron microscopy results show that big structural changes occur due to the thermal pulse

Improvement Of Tetracaine Antinociceptive Effect By Inclusion In Cyclodextrins.

Local anesthetics (LA) are among the most important pharmacological compounds used to attenuate or eliminate pain. However, systemic toxicity is still a limitation for LA application, especially for ester-type drugs, such as tetracaine (TTC) that presents poor chemical stability (due to hydrolysis by plasma esterases). Several approaches have been used to improve LA pharmaceutical properties, including the employment of drug-delivery systems. Here we used beta-cyclodextrin (β-CD) or hydroxypropyl-beta-cyclodextrin (HP-β-CD) to develop two new TTC formulations (TTC:β-CD and TTC:HP-β-CD). The inclusion complexes formation, in a 1:1 stoichiometry, was confirmed by differential scanning calorimetry, X-ray diffraction, UV-VIS absorption and fluorescence. Nuclear magnetic resonance (DOSY experiments) revealed that TTC association with HP-β-CD is stronger (Ka=1200 mol/L(-1)) than with β-CD (Ka=845 mol/L(-1)). Moreover, nuclear Overhauser effect (NOE) experiments provided information on the topology of the complexes, where TTC aromatic ring is buried inside the CD hydrophobic cavity. In vitro tests with 3T3 fibroblast cells culture revealed that complexation decreased TTC cytotoxicity. In addition, the total analgesic effect of TTC, tested in rats through the infraorbital nerve test, was improved in 36% with TTC:β-CD and TTC:HP-β-CD. In conclusion, these formulations presented potential for future clinical use, by reducing the toxicity and increasing the antinociceptive effect of tetracaine.2085-9