Dissertations / Theses on the topic 'Quantitative X-ray diffraction (QXRD)'

New quantitative methods are developed for analyser-based phase contrast imaging (ABI) with hard X-rays. In the first instance we show that quantitative ABI may be implemented using an extended incoherent source. Next, we outline how complex Green’s functions may be reconstructed from phase contrast images and we apply this method to reconstruct the thick perfect crystal Green’s function associated with an ABI imaging system. The use of quantitative ABI with incoherent X-ray sources is not widespread and the first set of results pertains to the feasibility of quantitative ABI imaging and phase retrieval using a rotating anode X-ray source. The necessary conditions for observation of ABI phase contrast are deduced from elementary coherence considerations and numerical simulations. We then focus on the problem of extracting quantitative information from ABI images recorded using an extended incoherent X-ray source. The results of an experiment performed at Friedrich-Schiller University, Germany using a rotating anode X-ray source demonstrate the validity of our approach. It is shown that quantitative information may be extracted from such images under quite general and practicable conditions. We then develop a new use for phase contrast imaging systems that allows the Green’s function associated with a linear shift-invariant imaging system to be deduced from two phase contrast images of a known weak object. This new approach is applied to X-ray crystallography where the development of efficient methods of inferring the phase of rocking curves is an important open problem. We show how the complex Green’s function describing Bragg reflection of a coherent scalar X-ray wavefield from a crystal may be recovered from a single image over a wide range of reciprocal space simultaneously. The solution we derive is fast, non-iterative and deterministic. When applied to crystalline structures for which the kinematic scattering approximation is valid, such as thin crystalline films, our technique is shown to solve the famous one-dimensional phase retrieval problem which allows us to directly invert the Green’s function to retrieve the depth-dependent interplanar spacing. Finally we implement our Green’s function retrieval method on experimental data collected at the SPring-8 synchrotron in Hyogo, Japan. In the experiment we recorded analyser-based phase contrast images of a known weak object using a thick perfect silicon analyser crystal. It is then demonstrated that these measurements can be inverted to recover the complex Green’s function associated with the analyser crystal Bragg peak. The reconstructed Green’s function is found to be in good agreement with the prediction of dynamical diffraction theory.

COORDENAÇÃO DE APERFEIÇOAMENTO DO PESSOAL DE ENSINO SUPERIOR
UNIVERSIDADE FEDERAL DA BAHIA
A análise de sistemas de medição consiste do exame da adequação do sistema quanto ao operador, ao instrumento e a outras fontes de variação, bem como da comparação da variância do erro de medição com a variância natural do processo. Nesse aspecto, esta pesquisa teve por objetivo a análise das incertezas da quantificação de fase pelo método de Rietveld em análise de pó. Os efeitos de vários fatores na quantificação de fase foram avaliados utilizando técnicas estatísticas de planejamento experimental e de análise multivariada, com a utilização de materiais de alto nível de rastreabilidade na realização dos experimentos, no Laboratório de difração de raios X do Departamento de Ciências de Materiais e Metalurgia da PUC-Rio. Através da determinação do construto de variação do processo, constatou-se que a quantificação das fases analisadas sofre influência das condições de medição de forma diferenciada de material para material, impossibilitando a obtenção de uma fórmula geral para cálculo dos erros de quantificação, embora os erros possam ser determinados por uma análise de repetitividade e reprodutibilidade apropriadamente conduzida.
The analysis of measurement systems is done by the examination of the adequacy of the system according to the operator, the instrument and other sources of variability, as well as by the comparison of the measurement error variance with the natural process variance. This research consisted in the evaluation of the uncertainties of phase quantification in powder analysis by the Rietveld method. The evaluation of the effects of several factors on the phase quantification was performed using statistical techniques of design of experiments and of multivariate analysis, with the use of materials of high level of traceability for the conduction of the experiments, in the Laboratory of X-ray Diffraction of the Pontifícia Universidade Católica do Rio de Janeiro. Through the determination of the variational structure of the process it was verified that the analyzed phases suffer influence of the measurement conditions in a differentiated way, which prevents the obtention of a general formula for calculation of the quantification error, although the errors can be determined by a repeatability and reproducibility analysis properly conducted.

The goal of this work has been to evaluate the different experimental techniques used for quantitative analysis of multi-phase materials systems.

Powder based specimens containing two-phases, austenite and ferrite , were fabricated and quantified. The volume fraction of ferrite varied from 2 Vol% to 50 Vol%.

X ray powder diffraction (XRD) measurements were based on two peak analysis. Computer based software Topas was used for quantitative analysis, which is believed to be the most advanced in this field. XRD results were found within the absolute limit of +/- 4% of given ferrite volume fraction. Volume fraction as low as 2 Vol% was successfully detected and quantified using XRD. However, high statistical error was observed in case of low volume fraction, such as 2 Vol% and 5 Vol% ferrite volume fraction.

Magnetic balance (MB) measurements were performed to determine the volume fraction of magnetic phase, ferrite. MB results were found in good agreement with given volume fractions. As low as 2 Vol% volume fraction was detected and quantified with MB. MB results were within the absolute limit of +/- 4% of given ferrite volume fraction.

Image analysis (IA) was performed after proper sample preparation as required by electron backscatter diffraction (EBSD) mode of Scanning electron microscopy (SEM). IM results were found within the absolute limit of +/- 2 % of given ferrite volume fraction. However, high statistical error was observed in case of 2 Vol% volume fraction.

Interpretation problems are commonly associated with calculating water saturation in nonhomogenous shaly sand reservoirs. Redefining petrophysical properties based on well logs in shaly sand reservoirs by using fundamental geologic attributes is an important tool in developing subsurface hydrocarbon resources. Studies of the electrical anisotropy of shaly sands have shown that the level of our understanding and our ability to correctly evaluate low resistivity and low contrast pay can be greatly improved. The model developed in this thesis is similar in form to the shaly sand Dual Water model by Clavier et al. (1984). It is an experiment based model designed to directly assess and quantify the mineralogical and electrical effects of clay minerals in heterogeneous reservoirs. Clay minerals usually have multiple effects on petrophysical properties obtained from geophysical well log measurements. The total expansible clay model evaluates these effects via direct measurement of independent mineralogy and conductivity of clay minerals within reservoir sands. This model integrates the following as an effective basis for characterizing shaly sand reservoirs: ??? Rietveld based Siroquant assay for quantitative X-ray diffraction, used in determining mineral percentages from standard XRD trace patterns, ??? Cation exchange capacity, used to determine the quantity of cations involved in the exchange at the shale-water interface, ??? Porosity, permeability, density and resistivity measurements, ??? Thin section petrography, used in identifying mineral patterns, visible porosity and reservoir quality. Overall, application of correlations drawn from the model yields improved results for water saturation which appeared consistent with those earlier calculated using known water saturation models (Clavier et al Dual Water model, 1984, Juhasz, 1981). A total of twenty three samples from two wells in the Cliff Head fIeld were analyzed for this study.

This thesis is concerned with the evaluation, in-situ, of the elastic strain energy release rate of cracks. This can define the criteria for crack propagation, and it is usually necessary to obtain this via calculation from the geometry and applied load. A new method is proposed, based on the conjoint use of digital image correlation to measure full-field displacements and finite element to extract the strain energy release rate of surface cracks. It has been extended to 3-D datasets with the use of digital volume correlation and tomographic imaging. A finite element model with imported full-field displacements measured by DIC/DVC acting as boundary conditions is solved and the J-integral is calculated. For linear elastic materials, modal contributions can be separated via the interaction integral. The method has been benchmarked using synthetic datasets to assess its sensitivity to noise and experimental uncertainties. It is very robust to experimental noise and can be used without knowledge of the specimen geometry and applied loads. The application of the method in 2-D is demonstrated in an analysis of experimental data for a mode I fatigue crack, introduced to an aluminium alloy compact tension specimen. Analysis of mixed-mode cracks in 2-D is shown on a PMMA sample with the Arcan geometry. In 3-D, static loading of a fatigue crack in nodular graphite cast iron is studied and the results from the method are compared with those obtained via a field-fitting approach. Diffraction analysis of polycrystalline materials can determine the full tensor of the elastic strains within them. Maps of elastic strains can thus be obtained typically using synchrotron X-rays or neutrons. A method is presented to calculate the elastic strain energy release rate of a crack from 2-D diffraction strain maps. The diffraction data is processed via a finite element approach to obtain the parameters required to calculate the $J$-integral. A validation is presented using a synthetic dataset from a finite element model. Its experimental application is demonstrated in an analysis of synchrotron X-ray diffraction strain maps of a propagating fatigue crack in a bainitic steel, before and after an overload. Finally, a complex case study of stable fracture propagation in polygranular isotropic nuclear graphite is presented. Synchrotron X-ray tomography and strain mapping by diffraction were combined with DVC and image analysis to extract the full-field displacements and elastic crystal strains. The displacement fields have been analysed using the developed methods to extract the critical strain energy release rate for crack propagation. Non-linear properties described the effect of microcracking on the elastic modulus in the fracture process zone. The analysis was verified by comparison of the predicted and measured elastic strain fields.

A travers l’étude par fluorescence X et diffraction de rayons X de trois grottes ornées Paléolithiques en rapport avec les questionnements des archéologues, c’est un travail de recherche physico-chimique autant que méthodologique qui est présenté au lecteur. La complexité analytique qu’il y a derrière l’étude in situ et non-invasive d’un art rupestre, a guidé notre réflexion sur le développement de procédures de traitement quantitatif des données, adaptées au site étudié (nature des pigments analysés, condition de conservation des œuvres). Cette complexité vient du fait qu’une couche picturale, tracée sur un support rocheux, est discontinue et ne recouvre pas uniformément la roche. Elle est de plus généralement peu épaisse. Pour ces raisons, une forte contribution de la paroi se retrouve dans l’information physico-chimique propre au pigment.Trois approches différentes ont ainsi été proposées pour approcher la matière picturale des grottes de Rouffignac et de Font-de-Gaume, situées en Périgord dans le sud-ouest de la France, et de la grotte de La Garma, localisée dans la région Cantabrique dans le nord de l’Espagne. L’une consiste en la semi-quantification d’oxydes discriminant le pigment de la paroi, bouclés à cent pourcent, permettant de s’affranchir de paramètres propres aux conditions expériences ; une deuxième est une semi-quantification par rapport à l’élément calcium, de sorte que la contribution de la paroi à travers la couche picturale reste la même d’un point de mesure à l’autre ; la dernière adopte une approche par simulation Monte Carlo afin de séparer clairement les informations de la paroi de celles du pigment. L’application de ces approches quantitatives a permis d’enrichir la connaissance stylistique que les archéologues en avaient, en apportant une vision physico-chimique à l’organisation des œuvres au sein de la grotte et des relations qu’elles entretiennent les unes avec les autres. Ce travail s’ouvre également au milieu karstique lui-même en intégrant à l’étude de l’art pariétal, un travail sur la genèse des faciès des parois. Le but étant d’acquérir le recul nécessaire pour mieux évaluer les interactions entre support et œuvres, et l’évolution des supports ornés, resituées dans leur contexte karstique général
The present study is a physicochemical research as well as a methodological work, carried out through the study of three Palaeolithic caves by X-ray fluorescence and X-ray diffraction. The analytical complexity behind in situ and non-invasive study of rock art, has guided our reflexion about the development of quantitative procedures of data processing, in order to adjust them appropriately to the specificity of the site and its rock art (specific constitution of the analysed pigment and conservation condition of the ornamented wall). This complexity is due to the fact that pigment layers don’t cover uniformly the rock surface. Also, the layers are generally very thin. For this reason, in the pigment signal, the proportion of the physicochemical information specific to the substrate is very high.Three approaches have been tested in the caves of Rouffignac, Font-de-Gaume and La Garma to characterise their Palaeolithic rock art. The two first are located in the Périgord region in the south-west of France, the last one in the Cantabrian region of Spain. One is related to the semi-quantification of oxides which discriminate the pigment from the substrate, allowing to not taking account experimental condition parameters; the second is a semi-quantification related to Ca, in order that the contribution in the concentration of the substrate detected through the paint layer remains the same for each measurement point; the last one is based on a Monte Carlo simulations method to separate distinctly the pigment information to those from the wall. These quantitative approaches enhanced the stylistic knowledge of archaeologists, bringing new physicochemical insights into the organisation of the representations and their relationship with the others inside the cave. Also, this work is concerned by the karstic environment; incorporating a research on wall taphonomy to the pigment study. The aim is to access to a better appreciation of the pigment-wall interactions and their evolution during time, given their global environmental context

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Tese (Doutoramento)
IPEN/T
Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Le but de la thèse est de déterminer l’historique de chargement d’une pièce rompue ou fissurée en service, par analyse des surfaces de fissuration. Pour les analyses de défaillances, les enjeux sont de définir le rôle du chargement dans la défaillance et de déterminer la fraction de durée de vie atteinte lors de la détection de la fissure. Un enjeu complémentaire est d’enrichir la base de données de chargements en service. L’organe choisi pour cette étude est l’essieu-axe ferroviaire. Ainsi, la sollicitation étudiée est en flexion rotative et les matériaux considérés sont les aciers A4T (25CrMo4) et A1N (C40). Suite à une revue bibliographique, quatre méthodes d’analyse quantitative des surfaces de fissuration ont été ciblées et testées, deux ont été retenues et développées. La première est basée sur la quantification des faciès de rupture (stries de fatigue, cupules, fissures secondaires…). La seconde s’appuie sur l’analyse des contraintes résiduelles (fractographie X) en profondeur pour déterminer l’épaisseur de matériau plastifié sous la surface de rupture. Cette profondeur correspond au sillage plastique induit par la propagation de la fissure et est fonction du chargement recherché
The aim of the thesis is to determine the loading history of a broken or cracked piece in service, by analysing the cracking surfaces. For failure analyses, the issues are to define the role of the loading in the failure and to determine the fraction of lifespan reached when the crack is detected. An additional issue is to expand the in-service loadings database. The component chosen for this study is the railway axle. Thus, the studied stress is in alternate bending and the considered materials are the steels A4T (25CrMo4) and A1N (C40). Following a bibliographic review, four methods for quantitative analysis of cracking surfaces were targeted and tested, two of which were selected and developed. The first one is based on the quantification of fractographic features (fatigue striations, dimples, secondary cracks...). The second is based on the in-depth analysis of the residual stresses (X-ray fractography) to determine the thickness of plasticized material below the fracture surface. This depth corresponds to the plastic wake induced by the crack propagation and is a function of the sought loading

O projeto enfocou a aplicação da difração de raios-X (DRX) na caracterização e quantificação dos compostos cristalinos do clínquer de cimento Portland, através do método de Rietveld, constituindo-se em contribuição pioneira sobre o tema em âmbito nacional. Foram utilizadas 40 amostras de clínquer provenientes de cinco diferentes unidades fabris, visando ampla representatividade do material de estudo. O clínquer de cimento Portland é o material sinterizado e peletizado, resultante da calcinação de uma mistura adequada de calcário e argila e, eventualmente, de componentes corretivos. Os compostos metaestáveis do clínquer Portland podem ser subdivididos em três grupos distintos: os silicatos cálcicos (C3S e C2S), a fase intersticial (C4AF, C3A, C12A7), e o grupo dos componentes menos freqüentes como o periclásio, a cal livre e os sulfatos. As proporções destes compostos são parâmetros importantes no controle de processo industrial de clinquerização. O método de Rietveld tem por base a simulação de todo o perfil difratométrico a partir de parâmetros estruturais das fases constituintes, permitindo refinar parâmetros de natureza instrumental e cristalográfica. A comparação do difratograma calculado com o observado e redução das diferenças através do método de mínimos quadrados permitem a obtenção de resultados quantitativos. DRX-Rietveld apresentou-se como uma técnica de quantificação de elevada reprodutibilidade com vantagens de cunho técnico e logístico com relação aos dois métodos correntemente utilizados no Brasil (microscopia e cálculo potencial de Bogue). Técnicas analíticas adicionais permitiram comparar resultados quantitativos obtidos por DRX-Rietveld e também correlacionar características dos compostos com o seu perfil difratométrico. A microscopia óptica foi a técnica de maior importância para comparações tanto qualitativas como quantitativas. A microscopia eletrônica (MEV-EDS) permitiu a aferição de fases não identificadas por microscopia óptica, como o C12A7 e sulfatos. A técnica de dissolução seletiva, aplicada para a concentração da fase intersticial, deu suporte para a aferição quantitativa de teores de polimorfos do C3A. A técnica mostrou resultados coerentes com a microscopia e o cálculo potencial de Bogue, sendo que constituintes não quantificados nestes puderam ser introduzidos (C12A7 e sulfatos), bem como possibilitou a distinção entre polimorfos de um mesmo composto (C3A). A redução no tempo de análise e a diminuição da subjetividade das análises, face às metodologias usuais, constituem fatores importantes da técnica visando atender os interesses da indústria do cimento.
The project has focused on the application of X-ray diffraction (XRD) on the characterization and quantification of the Portland cement clinker crystalline compounds using the Rietveld method. The present research represents a pioneer scientific contribution on the theme in Brazil. Overall forty clinker samples from five distinct kiln lines were collected for analysis aiming to get a broad representativeness of various cement process parameters. Portland cement clinker is the sintered and pelletized product from calcination of an adequate mix of limestone and clay and minor corrective materials. The metastable Portland clinker compounds are subdivided into three main groups: calcium silicates (C3S and C2S), matrix (C4AF, C3A, C12A7) and minor components as periclase, free lime and sulfates. The proportioning of these phases are important parameters to the industry clinkering process. The Rietveld XRD method is based on the simulation of the whole diffraction spectrum from the components structural data, allowing for refining instrumental and crystallographic parameters. By comparing the calculated and actual diffractograms and minimizing differences mathematically through a least squares method quantitative values are obtained. The Rietveld XRD has shown to be a high reproducible quantification technique, with technical and logistics advantages in comparison to the more usual microscopy and Bogue potential calculation. Additional analytical techniques have given reference data to compare quantitative results obtained from Rietveld XRD and to correlate characteristics of the compounds with their diffractogram profile. Optical microscopy was the most relevant technique for comparison both qualitative and quantitatively. Scanning electronic microscopy - energy dispersive system has allowed recognition of phases that could not otherwise be identified by optical microscopy, like C12A7 and sulfates. Selective dissolution of silicates carried out in order to concentrate matrix compounds sustained the quantitative results of C3A polimorphs found by Rietveld XRD. Rietveld has shown coherent results with both microscopy and Bogue potential calculation, but additionnally made it possible quantifying other compounds like C12A7 and sulfates, as well as distinguishing C3A polimorphs. The significant time saving and subjectivity minimization it provides makes up key-factors for the cement industry needs.

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Tese (Doutoramento)
IPEN/T
Intituto de Pesquisas Energeticas e Nucleares, IPEN/CNEN-SP

Expansive clay mineral contamination of road aggregate materials in Texas is a persistent problem. Hydrous layer silicate minerals - particularly smectites - in concretes are associated with decreased strength and durability in Portland cement and asphalt concretes. The Texas Department of Transportation (TXDOT) and Texas A&M Transportation Institute (TTI) evaluated the methylene blue adsorption test for its potential to identify and estimate quantities of expansive clays in aggregate stockpiles. Clay mineral quantification was completed for 27 geologically-diverse aggregate materials from Texas, Oklahoma, and Arkansas. X-ray diffraction analysis (XRD) of separated clays on glass was conducted, and NEWMOD was utilized to model the resulting diffraction patterns. Methylene blue adsorption (MBA) and cation exchange capacity (CEC) of clay fractions (< 2µm) and -40 mesh screenings (< 400 µm) were determined for most aggregates. Many of the aggregates exhibited significant quantities of expansive clay minerals such as smectite, which are linked to deleterious performance properties in concretes. While the majority of aggregates were derived from crushed limestone or calcareous river gravel parent materials, severalexhibited uncommon origins and unusual clay mineralogy. Due to the relatively low number of aggregates tested and diverse geological origins of the different aggregates,it proved difficult to formalize any conclusions abouttrendsbetweenthedifferent aggregate performance properties.

碩士
國立臺北科技大學
有機高分子研究所
101
Calcium phosphates have been extensively used for dental and orthopedic surgical applications due to the biodegradability in human being. It was found that a suitable mixing ratio between β–TCP (β-tricalcium phosphate, Ca3(PO4)3) and HA (hydroxyapatite, Ca5(PO4)3(OH)) is important for the biodegradable bone replacement. In general, β–TCP is synthesized by the decomposition of other calcium phosphate phases such as HA at temperature higher than 800 ℃. Consequently, how to determine the ratio between β–TCP and HA is an important issue on characterization methods. Recently, reference intensity ratio (RIR) method is used for quantification under the comparison with standard reference, but it ignores the peak broadening effect. Rietveld refinement has been widely used in multiphase quantification for many years due to less susceptible on primary extinction effects and minor amounts of preferred orientation. In addition, the advantages of this technique over traditional quantitative analysis methods include the determination of precise cell constants, the approximation of chemical compositions, the potential for the correction of preferred orientation, and microabsorption effects. Therefore, the characterizations of these structures and their quantities by x-ray diffraction (XRD), Raman spectroscopy, Infrared spectroscopy (IR), and Rietveld refinement in such biphasic calcium phosphate (BCP) system are the major work in this study. In the single phase study of HA, β–TCP(sintered), and β–TCP’(unsintered), the Raman spectroscopy can be used to distinguished between β–TCP and β–TCP’ based on the symmetric stretching frequency (?1) of PO4 around 968 cm-1, and XRD can be used to differentiate between HA and β–TCP. However, there are no significant differences on the vibrational frequency of PO4 around 1026 cm-1 in IR spectra. In the quantification of mixing ratio between HA and β–TCP, the best strategy is to apply Rietveld refinement on high resolution powder XRD data. However, for the convenience on the application of industry, the area ratio between reflection (2 0 -10) of β–TCP and reflection (1 2 1) of HA could be used to get the rough results.