This document describes a thesis submitted by Joel N. O'Dwyer to the University of Wollongong in fulfillment of the requirements for a Doctor of Philosophy degree. The thesis develops a new technique called energy-dispersive X-ray diffraction (EDXRD) for monitoring mineralogy in industrial process streams in real-time. Monte Carlo modeling was used to simulate X-ray diffraction and optimize the design of a prototype EDXRD analyzer. Quantitative mineral analysis experiments demonstrated that the technique can determine mineral components in samples with accuracies of better than 1 wt%. The results validate EDXRD as a viable tool for online mineral analysis of process streams.
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A label free and enzyme-free aptasensor for visual cd2+ detection based on sp...Vincent Paul Schmitz
The document describes a label-free and enzyme-free aptasensor for visual detection of Cd2+ based on split G-quadruplex DNAzyme fragments. The sensing system utilizes a three-way junction structure constructed from three hairpin molecules. In the presence of Cd2+, the aptamer binds Cd2+ and initiates branch migration of the hairpins, forming the junction. This brings the split G-quadruplex fragments into proximity to form an intact G-quadruplex upon addition of hemin. The formed G-quadruplex DNAzymes catalyze a color change reaction, providing naked-eye visual detection of Cd2+ with high sensitivity down to 10 pM concentration. The biosensor
Pratik Motwani is a PhD candidate in electrical engineering at the University of Houston. His research focuses on developing novel metallic nano-sensors for biosensing applications. He has over 4 years of experience developing nanoscale materials and devices through cleanroom fabrication. Motwani has authored 5 publications and holds a patent related to his sensor research. He maintains a 3.78 GPA and received his bachelor's degree in electronics engineering from India with high honors.
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This document discusses the application of luminescence techniques to national security issues. Specifically:
1. Luminescence can be used to detect radiation exposure in materials like bricks and salt, even after radiation sources have been removed. This allows reconstruction of "dirty bomb" sites and forensic analysis of cleaned facilities.
2. The Defence Science and Technology Organisation is working with the University of Adelaide to develop expertise in luminescence techniques. They are studying how different common materials like ceramics, glass and salt can reveal prior radiation exposure through luminescence signals.
3. Precise luminescence measurements of the absorbed radiation dose in opportunistic materials like those found at homes or carried by people may help with
This document provides an overview of the application of lasers in medicine. It begins with an introduction to lasers and electromagnetic waves. It then discusses several important medical lasers including the Neodymium: YAG laser, Argon laser, Carbon Dioxide laser, and Dye laser. These lasers are used for applications such as laparoscopic surgery, gynecologic surgery, ophthalmology, and cancer treatment. The document explains that lasers allow surgeons to perform more complex operations and obtain better results. Safety measures must be taken when using medical lasers.
This is a brief corporate presentation of the GeoMark Research & Engineering LLC, an industrial safety solutions provision company. GeoMark comprises vast experience and deep academic knowledge of the subject reinforced by the research and innovation skills of its stuff of scientists and engineers.
This document provides a summary of Abdel-Aleam H Mohamed's qualifications including his education, experience, skills, honors and projects. It outlines his PhD in plasma physics from Old Dominion University and over 10 years experience teaching physics courses. It also details his experience in plasma physics research and developing cold plasma systems, as well as several research projects and patents in this area.
IRJET- A Novel Detection Technique for Nuclear Radiations: Solid State Nuclea...IRJET Journal
This document reviews the use of solid state nuclear track detector CR-39 for detecting nuclear radiations. CR-39 is a plastic that is highly sensitive to charged particles like alpha particles and protons. When these particles pass through the plastic, they leave latent damage tracks that can be chemically etched to become visible. The document discusses how CR-39 has been used to detect products of nuclear fusion reactions and measure radon concentrations. It also examines different etching methods and conditions that allow tracks to be enlarged and counted more easily. CR-39 provides a simple, robust, and inexpensive way to detect ionizing radiation and has various applications in fields like health physics and fusion research.
A label free and enzyme-free aptasensor for visual cd2+ detection based on sp...Vincent Paul Schmitz
The document describes a label-free and enzyme-free aptasensor for visual detection of Cd2+ based on split G-quadruplex DNAzyme fragments. The sensing system utilizes a three-way junction structure constructed from three hairpin molecules. In the presence of Cd2+, the aptamer binds Cd2+ and initiates branch migration of the hairpins, forming the junction. This brings the split G-quadruplex fragments into proximity to form an intact G-quadruplex upon addition of hemin. The formed G-quadruplex DNAzymes catalyze a color change reaction, providing naked-eye visual detection of Cd2+ with high sensitivity down to 10 pM concentration. The biosensor
Pratik Motwani is a PhD candidate in electrical engineering at the University of Houston. His research focuses on developing novel metallic nano-sensors for biosensing applications. He has over 4 years of experience developing nanoscale materials and devices through cleanroom fabrication. Motwani has authored 5 publications and holds a patent related to his sensor research. He maintains a 3.78 GPA and received his bachelor's degree in electronics engineering from India with high honors.
Luminescence of common materials application to national security spoonerLeishman Associates
This document discusses the application of luminescence techniques to national security issues. Specifically:
1. Luminescence can be used to detect radiation exposure in materials like bricks and salt, even after radiation sources have been removed. This allows reconstruction of "dirty bomb" sites and forensic analysis of cleaned facilities.
2. The Defence Science and Technology Organisation is working with the University of Adelaide to develop expertise in luminescence techniques. They are studying how different common materials like ceramics, glass and salt can reveal prior radiation exposure through luminescence signals.
3. Precise luminescence measurements of the absorbed radiation dose in opportunistic materials like those found at homes or carried by people may help with
This document provides an overview of the application of lasers in medicine. It begins with an introduction to lasers and electromagnetic waves. It then discusses several important medical lasers including the Neodymium: YAG laser, Argon laser, Carbon Dioxide laser, and Dye laser. These lasers are used for applications such as laparoscopic surgery, gynecologic surgery, ophthalmology, and cancer treatment. The document explains that lasers allow surgeons to perform more complex operations and obtain better results. Safety measures must be taken when using medical lasers.
This is a brief corporate presentation of the GeoMark Research & Engineering LLC, an industrial safety solutions provision company. GeoMark comprises vast experience and deep academic knowledge of the subject reinforced by the research and innovation skills of its stuff of scientists and engineers.
This document provides a summary of Abdel-Aleam H Mohamed's qualifications including his education, experience, skills, honors and projects. It outlines his PhD in plasma physics from Old Dominion University and over 10 years experience teaching physics courses. It also details his experience in plasma physics research and developing cold plasma systems, as well as several research projects and patents in this area.
The document discusses website design ideas for a band that does not currently have its own site. It considers having the band be the prominent face of the site, but notes that may not fit with the organic feel of the rest of the campaign. It suggests the site should conform to the organic nature of the other materials and not focus heavily on images of the band. Examples are provided of both organic and synthetic homepage designs that could serve as starting points.
Este documento presenta un curso para formar visitadores médicos. El curso pretende formar especialistas capaces de prestar apoyo al servicio de salud en áreas sanitarias, administrativas y de gestión. El curso enseña habilidades sociales, técnicas de venta para visitadores médicos y conceptos de calidad total. Al completar el curso con éxito, los estudiantes reciben un diploma y certificado que acredita su especialización.
Power point relativo al principio de la hospitalidad. Aristóteles y Nietzsche. Casos y dilemas para pensar. Cada uno lleva una cuestión que no obliga a tomar decisiones con sustento en diferentes aspectos.
Решение для учебной аудитории / конференц-зала для тренингов на базе Cisco SX...Cisco Russia
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Tim Totin has over 15 years of experience in BIM and Revit modeling with an emphasis on electrical and fire protection drafting. He currently works as a BIM Manager where he is responsible for BIM management, model creation and management, family creation and management, and maintaining company standards. Previously he has held positions as a BIM Technician, Drafter, and Designer where he gained experience in Revit, AutoCAD, Navisworks, Dynamo and other Autodesk programs. He has an Associate's degree in Drafting and Design and a Bachelor's degree in Audio Arts and Acoustics.
Double the profits through digital transformation - digital insurance in AfricaThe Digital Insurer
Tawanda Chatikobo, Digital Manager for Nedbank Insurance presented at the Digutial Insurance Conference in Johannesburg in 2015 on how digital transformation can increase profits in the context of bancassurance
Este documento resume quiénes son sujetos de derecho mercantil de acuerdo con el Código de Comercio mexicano. Los sujetos de derecho mercantil son los comerciantes, definidos como personas que realizan actos de comercio de forma habitual con el fin de obtener ganancias, y aquellos que accidentalmente realizan actos de comercio. El Código de Comercio estipula que son sujetos del derecho mercantil las personas con capacidad legal para ejercer el comercio, las sociedades constituidas de acuerdo con las le
nurago zählt zu den weltweit innovativsten Experten für die digitale Marken-, Media- und Usability-Forschung. Auf Basis flexibler technologischer Plattformen kombiniert nurago neuartige Messverfahren und klassische Forschungsmethoden. nurago setzt damit Marktstandards und ermöglicht besonders effiziente und valide Erfolgskontrollen zur Optimierung der Touchpoints in digitalen Medien.
Als Teil der GfK-Unternehmensgruppe arbeiten an den Standorten Hannover, Hamburg, München, Berlin, London und Los Angeles mehr als 70 Mitarbeiter für internationale Werbetreibende unterschiedlicher Branchen sowie Media-Agenturen und Forschungsinstitute (u.a. Google, YouTube, eBay, Yahoo, SpiegelQC, pilot, G+J|ems, aevolve, die Advertising Research Foundation und das IAB).
This document is a thesis submitted by Theodore E. Burye to Michigan State University for the degree of Doctor of Philosophy in Chemical Engineering in 2015. The thesis investigates techniques to control the particle size of infiltrated mixed ionic and electronic conducting materials used in solid oxide fuel cell cathodes and determines oxygen surface exchange resistance values for these infiltrated particles through finite element modeling. Specifically, the thesis develops two processing techniques, precursor nitrate solution desiccation and ceria oxide pre-infiltration, that are shown to systematically reduce the average particle size of infiltrated La0.6Sr0.4Co0.8Fe0.2O3-δ from 50 nm to 22 nm. This particle size
This thesis presents a generalized Monte Carlo tool for investigating the properties of materials using a non-parabolic band structure model. The tool allows users to define new material parameters and properties by making every parameter a variable. It incorporates various scattering mechanisms and uses an analytic band structure model, making it fast. The tool has been integrated with the Rappture interface and deployed on nanoHUB.org for broad accessibility. Results from the tool closely match experimental data for common semiconductors like silicon, germanium, and gallium arsenide, demonstrating its versatility. The user-friendly interface allows defining materials and obtaining accurate results without coding.
This document provides an overview and motivation for the research conducted in the author's PhD thesis on high-speed optical fibre transmission using advanced modulation formats. The rapid growth of bandwidth-hungry internet services is driving demand for ever higher network capacities. While WDM and OTDM have increased capacities, advanced modulation formats that use phase and amplitude have the potential to further improve spectral efficiency and transmission reach. The author's research focuses on experimental implementation and transmission of QPSK and QAM16 modulation schemes with coherent detection and digital signal processing. The goals are to maximize bit rates and transmission distances achievable over standard single-mode fibre. Return-to-zero pulse shaping and nonlinearity compensation are also investigated to increase transmission reach.
An Efficient Approach for Ultrasonic Characterization of Biomaterials using N...inventionjournals
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This thesis examines quantum decoherence in self-assembled quantum dots, which are promising candidates for quantum computing. Three studies are conducted to better understand decoherence mechanisms and how they can be controlled. The first study bypasses spectral diffusion in neutral quantum dots through resonant excitation. The second study observes spontaneous nuclear spin self-polarization in a charged quantum dot for the first time. The third study reveals factors limiting hole spin lifetime by measuring polarization correlations in a positively charged quantum dot.
The document is a dissertation submitted by Mahato Lipika for the degree of Master of Science in Computer Control and Automation in 2016. It discusses leak location detection in gas pipeline networks. Chapter 1 introduces the background of gas pipeline networks in Singapore and the motivation for leak detection. The objective is to analyze pressure profile data using different methods to locate leaks in the network. Chapter 2 reviews literature on gas pipeline networks, leak detection techniques, and computational fluid dynamics modeling. Chapter 3 describes initial calculations, experiments conducted to collect pressure profile data from a test network setup under different leak conditions. Chapter 4 presents results of analyzing the data using various methods to locate leaks. Chapter 5 provides conclusions and suggestions for future work.
This document describes a thesis that evaluates the concept of using a remotely controlled robot for inspections of offshore wind turbines. The thesis includes:
1) Development of a prototype remote inspection robot and laboratory for evaluating the concept through usability testing with participants.
2) Simulations that indicate the concept could improve availability and lower the cost of energy for offshore wind farms.
3) A method called Software Module Real-time Target for simplifying development of control systems that include code generated from Simulink.
4) Four experiments were conducted with the prototype to evaluate usability and effectiveness of remote inspection compared to manned inspection. Results showed remote inspection was almost as effective with room for improvement.
This document provides an introduction to nondestructive evaluation (NDE) techniques. It defines NDE as testing without destroying an object to detect flaws, measure properties, or determine structure/composition. The main NDE methods discussed are radiography, magnetic particle, ultrasonics, liquid penetrant, eddy current, and visual testing. It notes that NDE is widely used across many industries and that certification of NDE personnel is important for safety and qualifications.
The document discusses website design ideas for a band that does not currently have its own site. It considers having the band be the prominent face of the site, but notes that may not fit with the organic feel of the rest of the campaign. It suggests the site should conform to the organic nature of the other materials and not focus heavily on images of the band. Examples are provided of both organic and synthetic homepage designs that could serve as starting points.
Este documento presenta un curso para formar visitadores médicos. El curso pretende formar especialistas capaces de prestar apoyo al servicio de salud en áreas sanitarias, administrativas y de gestión. El curso enseña habilidades sociales, técnicas de venta para visitadores médicos y conceptos de calidad total. Al completar el curso con éxito, los estudiantes reciben un diploma y certificado que acredita su especialización.
Power point relativo al principio de la hospitalidad. Aristóteles y Nietzsche. Casos y dilemas para pensar. Cada uno lleva una cuestión que no obliga a tomar decisiones con sustento en diferentes aspectos.
Решение для учебной аудитории / конференц-зала для тренингов на базе Cisco SX...Cisco Russia
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Tim Totin has over 15 years of experience in BIM and Revit modeling with an emphasis on electrical and fire protection drafting. He currently works as a BIM Manager where he is responsible for BIM management, model creation and management, family creation and management, and maintaining company standards. Previously he has held positions as a BIM Technician, Drafter, and Designer where he gained experience in Revit, AutoCAD, Navisworks, Dynamo and other Autodesk programs. He has an Associate's degree in Drafting and Design and a Bachelor's degree in Audio Arts and Acoustics.
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Este documento resume quiénes son sujetos de derecho mercantil de acuerdo con el Código de Comercio mexicano. Los sujetos de derecho mercantil son los comerciantes, definidos como personas que realizan actos de comercio de forma habitual con el fin de obtener ganancias, y aquellos que accidentalmente realizan actos de comercio. El Código de Comercio estipula que son sujetos del derecho mercantil las personas con capacidad legal para ejercer el comercio, las sociedades constituidas de acuerdo con las le
nurago zählt zu den weltweit innovativsten Experten für die digitale Marken-, Media- und Usability-Forschung. Auf Basis flexibler technologischer Plattformen kombiniert nurago neuartige Messverfahren und klassische Forschungsmethoden. nurago setzt damit Marktstandards und ermöglicht besonders effiziente und valide Erfolgskontrollen zur Optimierung der Touchpoints in digitalen Medien.
Als Teil der GfK-Unternehmensgruppe arbeiten an den Standorten Hannover, Hamburg, München, Berlin, London und Los Angeles mehr als 70 Mitarbeiter für internationale Werbetreibende unterschiedlicher Branchen sowie Media-Agenturen und Forschungsinstitute (u.a. Google, YouTube, eBay, Yahoo, SpiegelQC, pilot, G+J|ems, aevolve, die Advertising Research Foundation und das IAB).
This document is a thesis submitted by Theodore E. Burye to Michigan State University for the degree of Doctor of Philosophy in Chemical Engineering in 2015. The thesis investigates techniques to control the particle size of infiltrated mixed ionic and electronic conducting materials used in solid oxide fuel cell cathodes and determines oxygen surface exchange resistance values for these infiltrated particles through finite element modeling. Specifically, the thesis develops two processing techniques, precursor nitrate solution desiccation and ceria oxide pre-infiltration, that are shown to systematically reduce the average particle size of infiltrated La0.6Sr0.4Co0.8Fe0.2O3-δ from 50 nm to 22 nm. This particle size
This thesis presents a generalized Monte Carlo tool for investigating the properties of materials using a non-parabolic band structure model. The tool allows users to define new material parameters and properties by making every parameter a variable. It incorporates various scattering mechanisms and uses an analytic band structure model, making it fast. The tool has been integrated with the Rappture interface and deployed on nanoHUB.org for broad accessibility. Results from the tool closely match experimental data for common semiconductors like silicon, germanium, and gallium arsenide, demonstrating its versatility. The user-friendly interface allows defining materials and obtaining accurate results without coding.
This document provides an overview and motivation for the research conducted in the author's PhD thesis on high-speed optical fibre transmission using advanced modulation formats. The rapid growth of bandwidth-hungry internet services is driving demand for ever higher network capacities. While WDM and OTDM have increased capacities, advanced modulation formats that use phase and amplitude have the potential to further improve spectral efficiency and transmission reach. The author's research focuses on experimental implementation and transmission of QPSK and QAM16 modulation schemes with coherent detection and digital signal processing. The goals are to maximize bit rates and transmission distances achievable over standard single-mode fibre. Return-to-zero pulse shaping and nonlinearity compensation are also investigated to increase transmission reach.
An Efficient Approach for Ultrasonic Characterization of Biomaterials using N...inventionjournals
The methodology for characterization of biomaterial is the source of signal, Biomaterial and the response detector. The high frequency ultrasonic signal generator generates signals of high frequency suitable for biomaterial characterization. In this system, Ultrasonic signals are made to fall on the biomaterial to be characterized. While passing through the biomaterial, the ultrasonic signals are absorbed, reflected and scattered along different directions. The transmitted and reflected received signals are sense and detect by receiving transducer. The sensor produces proportional current in microamperes. This current will be applied to sensing circuit, which converts current into proportional amplified voltage with the help of Op-Amp. An Analog to Digital Converter (ADC) converts analog signal into digital signal. This digital signal provides data to a computer. Data acquisition circuit interconnects the PC and driver software to which the data is input. Driver software makes NI LabVIEW to interact with hardware. The PC with LabVIEW platform is used to study characteristics of the biomaterials.
This thesis examines quantum decoherence in self-assembled quantum dots, which are promising candidates for quantum computing. Three studies are conducted to better understand decoherence mechanisms and how they can be controlled. The first study bypasses spectral diffusion in neutral quantum dots through resonant excitation. The second study observes spontaneous nuclear spin self-polarization in a charged quantum dot for the first time. The third study reveals factors limiting hole spin lifetime by measuring polarization correlations in a positively charged quantum dot.
The document is a dissertation submitted by Mahato Lipika for the degree of Master of Science in Computer Control and Automation in 2016. It discusses leak location detection in gas pipeline networks. Chapter 1 introduces the background of gas pipeline networks in Singapore and the motivation for leak detection. The objective is to analyze pressure profile data using different methods to locate leaks in the network. Chapter 2 reviews literature on gas pipeline networks, leak detection techniques, and computational fluid dynamics modeling. Chapter 3 describes initial calculations, experiments conducted to collect pressure profile data from a test network setup under different leak conditions. Chapter 4 presents results of analyzing the data using various methods to locate leaks. Chapter 5 provides conclusions and suggestions for future work.
This document describes a thesis that evaluates the concept of using a remotely controlled robot for inspections of offshore wind turbines. The thesis includes:
1) Development of a prototype remote inspection robot and laboratory for evaluating the concept through usability testing with participants.
2) Simulations that indicate the concept could improve availability and lower the cost of energy for offshore wind farms.
3) A method called Software Module Real-time Target for simplifying development of control systems that include code generated from Simulink.
4) Four experiments were conducted with the prototype to evaluate usability and effectiveness of remote inspection compared to manned inspection. Results showed remote inspection was almost as effective with room for improvement.
This document provides an introduction to nondestructive evaluation (NDE) techniques. It defines NDE as testing without destroying an object to detect flaws, measure properties, or determine structure/composition. The main NDE methods discussed are radiography, magnetic particle, ultrasonics, liquid penetrant, eddy current, and visual testing. It notes that NDE is widely used across many industries and that certification of NDE personnel is important for safety and qualifications.
This thesis presents new techniques to diagnose process variability in industrial plasma etching systems. Optical emission spectroscopy and electrical sensors are used to measure plasma parameters during etching. Statistical analysis methods like principal component analysis and gradient boosting trees are applied to sensor data to correlate variability in etch rate with measurements. A case study of an etching process is presented where time series OES data is analyzed across process steps. Variability due to the "first wafer effect" is investigated. Process excursions are also examined by studying shifts in principal components. The combination of in-situ sensors and statistical analysis provides a powerful tool for process engineers to diagnose sources of variability.
Bioceramics, process ceramics and advanced ceramics and ceramic-based composites are the main focus on the journal. It accepts all types of original research articles and review papers that are concerned with the scope and focus of the topic.
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2) Laboratory and field tests evaluated the sensor's data acquisition performance and immunity to interference in high voltage environments.
3) Test results demonstrated the sensor could perform continuous wireless data acquisition of insulator pollution levels and earth impedance measurements in substations.
This document reviews the application of electrical resistance tomography (ERT) for conducting vessel walls. ERT is a non-invasive tomography technique that has advantages for industrial process monitoring applications. The document discusses the evolution of ERT techniques for conducting vessels over decades of research. It presents different ERT measurement strategies and challenges for conducting boundaries. It also addresses electrode fabrication and designs for effective ERT systems on conducting vessel walls.
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The facility is a multi-instrument laboratory costing £4.5 million housing instruments for structure determination, spectroscopy, mass spectrometry, and calorimetry. It is free for university staff, students, and postdocs to use and aims to provide a centralized location for analytical chemistry run by academic experts. Key instruments include NMR spectrometers, X-ray diffractometers, mass spectrometers, thermal analyzers, and spectroscopy equipment for applications like protein structure analysis, materials characterization, and metabolic profiling. Limited technical support is currently provided for the NMR and mass spec instruments.
Dissertation BE 1180 Gagandeep Singh 10038702 April 15, 2012 Project ManagementGagandeep Singh
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Final year project: To Design and Test a low cost Gamma Ray detectorChristopher Mitchell
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This document discusses fusion power and the DIII-D fusion reactor located in La Jolla, California. The DIII-D employs magnetic confinement fusion using deuterium and tritium fuels to produce hot plasma and induce fusion. A diagnostic tool called DiMES is used at DIII-D to monitor neutron flux from the fusion reactions by activating samples with neutrons. The author's work computationally applies the DiMES design to DIII-D to accurately infer fusion power and neutron flux in near real-time by using a circulating fluid activated by neutrons and monitored with a detector. Simulations were used to determine activation yields and optimize detector geometry.
This document discusses the effects of different source and streamer datum correction techniques on seismic image quality and resolution. It focuses on analyzing the advantages and disadvantages of three techniques - bulk static shift, intermediate static shift, and dynamic correction using NMO - on both real and synthetic deep tow seismic datasets. Statistical and spectral analysis is used to assess the differences between the techniques and determine the optimum method. While the dynamic correction yields superior results, the improvement is not significant enough to warrant changing from the currently used bulk static correction. However, as acquisitional advances continue to be made, it will be important to keep investigating optimum datuming methods to ensure high quality final images.
Similar to Energy-dispersive x-ray diffraction for on-stream monitoring of m (20)
Energy-dispersive x-ray diffraction for on-stream monitoring of m
1. University of Wollongong
Research Online
University of Wollongong Thesis Collection University of Wollongong Thesis Collections
2009
Energy-dispersive x-ray diffraction for on-stream
monitoring of mineralogy
Joel N. O'Dwyer
University of Wollongong
Research Online is the open access institutional repository for the
University of Wollongong. For further information contact the UOW
Library: research-pubs@uow.edu.au
Recommended Citation
O'Dwyer, Joel N., Energy-dispersive x-ray diffraction for on-stream monitoring of mineralogy, Doctor of Philosophy thesis, School of
Engineering Physics, Faculty of Engineering, University of Wollongong, 2009. http://ro.uow.edu.au/theses/3193
2.
3. Energy-Dispersive X-ray Diffraction for
On-stream Monitoring of Mineralogy
A thesis submitted in fulfillment of the
requirements for the award of the degree
Doctor of Philosophy
from
UNIVERSITY OF WOLLONGONG
by
Joel N. O’Dwyer
B. MedRadPhys (Hons)
School of Engineering Physics
2008
4. CERTIFICATION
I, Joel N. O’Dwyer, declare that this thesis, submitted in fulfillment of the
requirements for the award of Doctor of Philosophy, in the School of Engineering
Physics, University of Wollongong, is wholly my own work unless otherwise
referenced or acknowledged. The document has not been submitted for
qualifications at any other academic institution.
Joel O’Dwyer
May, 2009
5. i
Abstract
Mineral processing and metal production techniques depend on the
mineralogy of the feedstock fed into the processing plant. The ability to perform
on-stream mineralogical characterisation of feedstock materials, or to monitor
intermediate, product and waste streams would allow better process control and
increased efficiency. On-line elemental analysers based on X-ray fluorescence
and prompt gamma-ray neutron activation analysis are widely used, but existing
mineralogical analysis methods rely on extracting and measuring small samples.
This can introduce sampling errors and is time consuming, particularly if the
sample must be removed to a laboratory for analysis. These methods are therefore
ill-suited to process control applications.
This thesis develops a new technique for monitoring the mineralogy of
industrial process streams in real-time. The technique, called energy-dispersive
X-ray diffraction (EDXRD), is well-suited to the application of on-stream
mineralogical analysis of mineral slurries. An EDXRD analyser measures the
energy spectrum of X-rays diffracted by a sample material at a fixed angle. This
method uses much higher X-ray energies than the conventional X-ray diffraction
technique, therefore greater depth penetration and is obtained with less reliance on
sample preparation. This results in it being better suited to the application of
on-line diffraction measurement.
An extension to the EGSnrc Monte Carlo code was developed that enables
X-ray diffraction to be modelled. Diffractive scattering from both crystalline and
amorphous materials can be modelled, as well as materials containing both
crystalline and amorphous components. It was shown that this method can be
used to simulate the diffraction spectra of samples containing mixtures of
different materials. The purpose for developing this extended code was to use it
to aid in the design and development of EDXRD analysers.
A laboratory prototype EDXRD analyser was designed and developed.
The instrument was designed to measure a wide range of commercially important
minerals in both dry powder and slurry form. Monte Carlo modelling was used
extensively to optimise the design of the instrument and predict its performance.
6. ii
Comparisons between Monte Carlo modelled and experimental spectra obtained
with the instrument showed good agreement, validating the method developed to
simulate diffractive scattering.
Quantitative mineral phase analysis was performed on two suites of
materials in order to investigate the accuracy with which the mineral components
could be determined with the EDXRD analyser. The first suite consisted of
twenty samples, each containing six commercially important minerals.
Regression analysis performed on the spectra showed that all six components
could be quantified with accuracies of better that 1 wt%. The second suite
contained seven minerals found in potash slurry. Good measurement accuracies
were obtained for most of the components. The spectra of the samples in both
suites were also modelling using Monte Carlo simulation in order to determine if
simulated spectra can be used to predict the measurement accuracy of an EDXRD
analyser. It was found that the analysis accuracies obtained from the modelled
spectra agreed well with the experimental results. This showed that the
measurement accuracy of an EDXRD analyser can be predicted using Monte
Carlo simulation.
A system for optimising the design of an EDXRD analyser was developed.
The system uses performance data derived from Monte Carlo modelling for
1.7 million instrument designs and a computer code to find the optimal analyser
design to measure a material of interest. The advantage of the system was
demonstrated by redesigning the prototype analyser using the optimisation code.
It was shown that the optimised instrument delivers significantly better
performance than the prototype analyser.
Finally, the methods and knowledge developed in the thesis were put to
use in the design of a potash slurry analyser. The analyser was designed to
measure potash slurry on-line for the purpose of process control. The design of
the analyser was optimised using the optimisation code. The analysis accuracy of
the analyser was predicted using Monte Carlo modelling, which showed that all
mineral components of the slurry could be quantified with accuracies of better
than 0.7 wt%. This result demonstrated that EDXRD has the potential to be a
viable tool for the on-line analysis mineral slurries.
7. iii
Acknowledgements
I would like to thank my supervisor Dr James Tickner of the
Commonwealth Scientific and Industrial Research Organisation (CSIRO) for his
support and guidance throughout this project. His experience and enthusiasm for
physics has been an inspiration and has made my experience as a PhD student all
the more enjoyable. I have learned an enormous amount from James in many
aspects of radiation physics and I am greatly appreciative to him. I also thank
James for coding the Monte Carlo techniques developed in this thesis into
EGSnrc.
I would also like to thank my co-supervisor Professor Anatoly Rosenfeld
for his support. Professor Rosenfeld has guided my development as a physicist
since I was an undergraduate student and I thank him for the time and effort he
has dedicated to help me get to this stage of my career.
My thanks also go to Greg Roach of CSIRO, who has helped to guide me
through this project from its conception. Greg’s hands-on knowledge of X-ray
detectors and experimental techniques were particularly invaluable. I am also
greatly thankful for the work of Ivan Kekic, formerly of CSIRO, who developed
the mechanical design of the X-ray diffraction rig produced in this project. Ivan’s
skills and attention to detail contributed to the successful results obtained with the
instrument.
This project was conducted with the CSIRO Minerals Division and I am
thankful for the opportunity and support I have received from the organisation. I
also extend my thanks to the members of the CSIRO Minerals On-line Analysis
and Control group, with whom this project was conducted. In particular I thank
Dr Nick Cutmore, Michael Millen and Janet Warder. I am also grateful for the
financial support of the Australian government through an Australian
Postgraduate Award and CSIRO in the form of a stipend.
I would particularly like to thank my friends Diana Sargent, Rachel
Bradley and Mirjana Zimonjic for providing fun and conversation on our daily
commute to and from Lucas Heights. The “De-stress Car” was the perfect place
to unwind after a day of frustration in the lab! I especially thank Diana and
8. iv
Rachel for providing me with VIP service at the Australian Nuclear Science and
Technology Organisation library.
Most importantly I would like to thank my family for their support. My
brother Mark, who has been through the rigors of a PhD himself, was my most
valuable source of information on thesis writing and general PhD matters. And of
course, my parents for their unwavering support.
9. v
Table of Contents
Abstract ……………………………………………………………..…….. i
Acknowledgements ……………………………………………………….. iii
Table of Contents ………………………………………………………..... v
List of Figures …………………………………………………………….. xii
List of Tables ……………………………………………………………… xxvii
List of Patents, Publications and Conferences ………………………..... xxx
General Note ………………………………………………………………xxxii
Chapter 1 Introduction …………………………………………………. 1
1.1 Mineral Processing …………………………………………………. 1
1.2 Process Control ………………………………………………….…. 5
1.3 EDXRD for On-line Mineral Analysis …………………………...... 9
1.4 Thesis Overview ……………………………………………………. 10
Chapter 2 Photon Interactions with Matter and X-ray Diffraction .… 13
2.1 Interactions of X-rays with Matter …………………………………. 13
2.1.1 Photoelectric Effect .…………………………………………… 13
2.1.2 Rayleigh Scattering .…………………………………………… 14
2.1.3 Compton Scattering .…………………………………………… 16
2.2 Diffractive (Bragg) Scattering .……………………………………... 17
2.3 Methods for X-ray Diffraction Measurement ……………………... 19
2.3.1 Angular-Dispersive X-ray Diffraction .………………………… 20
2.3.2 Energy-Dispersive X-ray Diffraction .…………………………. 24
2.4 Existing On-line XRD Mineralogical Analysers ..…………………. 27
2.4.1 The Midfox On-stream XRD Analyser .……………………….. 27
2.4.2 The FCT-ACTech Continuous XRD Analyser ..……………….. 34
2.5 Advantages of EDXRD for On-line Mineralogical Analysis ...…….. 39
10. vi
Chapter 3 EDXRD Analyser Design Issues ..………………………….. 41
3.1 Introduction to Design Issues .……………………………………… 41
3.2 Geometrical Setup ..……………………..………………………….. 42
3.2.1 The Pencil-Pencil Geometry .………………………….……….. 42
3.2.2 The Pencil-Cone Geometry ..…………………………….……... 45
3.3 Geometry and Design Optimisation ..……………………………… 47
3.3.1 The Diffraction Angle .………………….……………………… 48
3.3.2 Incident X-ray Energy Distribution .…………………………… 50
3.3.3 X-ray Detector ..………………………………………………… 54
3.3.4 Beam Divergence ..…………………………………………….. 57
3.3.5 Acquisition Time .……………….……………………………... 59
3.3.6 Shielding .…………………….………………………………… 60
3.4 Summary ..……………………….…………………………………. 61
Chapter 4 The Simulation of X-ray Diffraction Using Monte
Carlo Modelling ..…………………………………………… 63
4.1 Introduction ..………………………………………………………. 63
4.2 Simulation of Coherent Scattering in the Standard EGS Code .….… 64
4.3 Modelling Diffractive Scattering from Amorphous Materials .……. 65
4.4 Modelling Diffractive Scattering from Crystalline Powders ……….. 69
4.5 Computer Code for Calculating the Scattering Cross Sections and
Form Factors of Mixed Crystalline and Amorphous Materials ..…… 73
4.5.1 Brief Overview of the EDXRD Crystallography Package ..……. 74
4.5.1.1 Materials in EDXRD Crystallography Package ...………….. 75
4.5.1.2 Samples in EDXRD Crystallography Package ..…………… 76
4.5.2 Calculation of the Cross Sections and Form Factors of a
Mixture ..………………………………………………………... 78
4.5.2.1 Calculation of the Rayleigh Cross Section and Form Factor
of a Mixture ..……………………………………………….. 78
4.5.2.2 Calculation of the Bragg Cross Section and Form Factor
of a Mixture ..……………………………………………….. 79
11. vii
4.5.3 Examples of Cross Section and Form Factor Calculations for
a Mixture .………………………………………………………. 80
4.6 Modification of the EGSnrc Code .…………………………………. 81
4.6.1 Specification of Cross Section and Form Factor Data for a
Material ………………………………………………………… 82
4.6.2 Modification to Coherent Scatter Modelling in the EGSnrc Code . 83
4.6.3 Variance Reduction .…………………………………………… 84
4.7 Example Simulated EDXRD Spectra ..…………………………….. 86
4.8 Summary ..………………………………………………………….. 88
Chapter 5 Design of an EDXRD Instrument for Mineral Analysis … 90
5.1 Introduction ..………………………………………………………. 90
5.2 Geometrical Setup ..………………………………………………… 90
5.2.1 The Cone-Cone Design ..………………………………………. 91
5.2.2 Advantages of the Cone-Cone Design ..……………………….. 92
5.3 The Diffraction angle …………………………………………….. 97
5.3.1 Definition of the Diffraction Angle .…………………………… 98
5.3.2 Identification of Test Materials ..………………………………. 99
5.3.3 X-ray Energy Distribution ..…………………………….……… 102
5.3.4 Detector Efficiency .…………………………………………… 104
5.3.5 Coherent and Compton Scattering Cross Sections …………… 106
5.3.6 Resolution ..…………………………………………………….. 108
5.3.7 Selection of the Diffraction Angle ..……………………………. 109
5.4 Collimator Design …..……………………………………………... 111
5.4.1 Collimator Arrangement .……………………………………… 111
5.4.1.1 The Source Collimator .……………………………………. 112
5.4.1.2 The Primary Beam Collimator ..…………………………… 113
5.4.1.3 The Scatter Collimator …..…………………………………. 115
5.3.1.4 The Detector Collimator …..………………………………. 117
5.4.2 Cone Beam Diameter …….…………………………………… 118
5.4.3 Collimator Opening Widths …...………………………………. 119
12. viii
5.4.3.1 Source Collimator Opening Width ………..……………….. 119
5.4.3.2 Primary Beam, Scatter and Detector Collimator Opening
Widths ……………………..……………………………….. 120
5.4.4 Collimator Construction ..……………………………………... 123
5.4.4.1 Collimator Material …..……………………………………. 123
5.4.4.2 Collimator Dimensions …..…………………………….….. 123
5.5 Tolerances …………..……………………………………………… 126
5.5.1 Horizontal Tolerances ...………………………………………... 127
5.5.2 Vertical Tolerances ……...…………………………………….. 130
5.5.3 Angular Tolerances …..….…………………………………….. 132
5.6 Spatial Sensitivity ……….………………………………………… 133
5.6.1 Vertical Spatial Sensitivity …..………………………………… 134
5.6.2 Horizontal Spatial Sensitivity ……..…………………………… 137
5.7 Summary …………………………..………………………………. 139
Chapter 6 EDXRD Analyser Construction and Performance …….... 141
6.1 Introduction …...…………………………………………………… 141
6.2 The Complete Analyser ……….…………………………………… 141
6.3 Collimators ………….……………………….……………………. 144
6.3.1 Source Collimator ………..…………….……………………… 144
6.3.2 Primary Beam and Scatter Collimators ………...……………… 145
6.3.3 Detector Collimator ………………..………………………….. 146
6.3.4 Alignment of the Collimators ………..………………………… 147
6.4 Analyser Performance ……………..………………………………. 148
6.4.1 EDXRD Spectra ……………..………………………………… 149
6.4.2 Validation of the Monte Carlo Model and Performance
Analysis …………………..……………………………………. 155
6.4.2.1 Comparison of Experimental and Monte Carlo Diffraction
Spectra ……………….……………………………………. 156
6.4.2.2 Comparison of Experimental and Monte Carlo Resolution ... 164
13. ix
6.4.2.3 Comparison of Experimental and Monte Carlo Spatial
Sensitivities ….……………………..………………………. 166
6.5 Conclusions ………...……………………………………………… 168
Chapter 7 Analysis of Dry Mineral Powders and Potash Slurry …..... 169
7.1 Introduction …………………………..…………………………… 169
7.2 Dry Mineral Powder Analysis …………..………………………… 169
7.2.1 Experimental Method ………………………………………….. 170
7.2.2 Analysis Results and Discussion ……..……………………….. 171
7.3 Potash Analysis ………………………...………………………….. 175
7.3.1 Potash Slurry Analysis ……………..…………………………. 177
7.3.1.1 Potash Slurry Diffraction Spectra ………...………………... 177
7.3.1.2 Reproducibility of the Potash Diffraction Spectra …..……. 179
7.3.1.3 Particle Size Effects ……………………………..………… 181
7.3.1.4 Solids Loading Effects …………………..………………… 184
7.3.2 Synthetic Potash Analysis …………………..…………………. 188
7.3.2.1 Experimental Method …………………..…………………. 189
7.3.2.2 Analysis Results and Discussion …………..……………… 189
7.4 Conclusions …………………………..…………………………… 194
Chapter 8 Predicting Analysis Accuracies Using Monte Carlo
Modelling …………………..……………………………….. 196
8.1 Introduction ……………………………………………………….. 196
8.2 Monte Carlo Analysis of a Dry Powder Suite ………..…………… 197
8.2.1 Simulation of the Spectra Using Monte Carlo Modelling …..… 197
8.2.2 Analysis Results and Discussion ……………………..………. 198
8.3 Monte Carlo Analysis of Synthetic Potash ………………..………. 201
8.3.1 Simulation of the Spectra Using Monte Carlo Modelling …...… 202
8.3.2 Analysis Results and Discussion ………………………..….…. 203
8.4 Conclusions ……………………………………………..………… 205
14. x
Chapter 9 Optimisation of an EDXRD Analyser ……….…………… 206
9.1 Introduction ………………………………………..……………… 206
9.2 EDXRD Design Facilitator ……………………….………………. 212
9.2.1 Creation of a Library of Monte Carlo Derived Performance
Data …………………………………………..….…………….. 213
9.2.1.1 Design Variations ……………………….………………… 213
9.2.1.2 Sample Material and X-ray Source …….….………………. 216
9.2.1.3 Monte Carlo Simulation Method ………..………………… 217
9.2.1.4 Summary ………………………………..…………………. 217
9.2.2 Calculation of the Instrument Performance ….…….………….. 218
9.2.3 Selection of the Optimal Design ……..…………….………….. 223
9.2.3.1 Brief Overview of EDXRD Design Facilitator …...……….. 225
9.2.3.2 Functions in EDXRD Design Facilitator ……………..…… 226
9.2.3.3 Finding the Best Design ………………………….………... 237
9.2.3.4 Calculation of the Diffraction Spectrum of a Sample ……... 242
9.2.4 Illustration of the Advantage of EDXRD Design Facilitator ..… 247
9.3 Summary ……………………………………………………….…. 249
Chapter 10 Design of an On-line Slurry Analyser …………………….. 251
10.1 Introduction ………………………….…………………….……… 251
10.2 Potash Processing ……………….…….………………….……….. 252
10.3 EDXRD Instrument for On-line Potash Analysis …….…..………. 253
10.3.1 Composition of Potash Slurry ………………….……..………. 253
10.3.2 Resolution Required …………………………………..………. 255
10.3.3 Sample Thickness ……………………………………..……… 260
10.3.4 Maximum Cone Beam Radius and Source-to-Sample Distance .. 260
10.3.5 Hardware Selection: X-ray Tube and Detector …………..…… 260
10.3.6 Measurable Diffraction Peaks …………………………..…….. 262
10.3.7 Usable energy Range ……………………………………..…… 263
10.3.8 Beam Geometry ………………………………………..……… 265
10.4 Instrument Construction and Online Configuration ………..……... 269
15. xi
10.4.1 By-line Configuration to Sample a Slurry Stream ……..……... 269
10.4.2 Gravity Fed Arrangement ……………………………..……… 270
10.4.3 Submerged Arrangement ………………………………..…….. 273
10.5 Predicted Analysis Accuracy of the Potash Slurry Analyser ……… 275
10.5.1 Analysis Results and Discussion ……………………………… 276
10.6 Summary ……………………………………………….…………. 279
Chapter 11 Conclusions and Future Direction ….…………...………… 281
11.1 Summary and Conclusions …………………….………….……… 281
11.2 Future Direction ……………………….………..………………… 289
References …………………………….…………..……………………… 292
16. xii
List of Figures
Figure 1.1 General stages involved in mineral processing. Each step
typically involves many sub-steps. ……..………………..… 2
Figure 1.2 Basic schematic of the froth flotation process for
concentration of a mineral slurry. …………..………..……. 3
Figure 1.3 Simple diagram showing the concept of process control. The
mixture of the materials is monitored by an on-line analysers.
The results of the analysis are used to continually control
and optimise the blend. ………………………………..…... 5
Figure 1.4 Off- and on-line analysis of a slurry stream. In off-line
analysis, a sample of slurry is taken from the stream and
analysed by a laboratory instrument. The on-line analyser
measures the stream directly and provides data in (near)
real-time. …………………………………………..…...….. 6
Figure 2.1 The photoelectric effect. The atom absorbs the incident
photon of energy hν and ejects a K shell electron. An L shell
electron fills the vacancy and emits a photon of energy equal
to the difference in the shell binding energies
E2-E1. …………………………………………..……..….… 14
Figure 2.2 Thompson scattering of a photon. The photon is scattered
through an angle Θ and retains the same energy and phase
as the incident photon. …………………………..…………. 15
Figure 2.3 Compton scattering from a free electron. The energy of the
incident photon is shared between the scattered photon and
the recoil electron. ……………………………….………… 16
Figure 2.4 Bragg diffraction from a set of atomic planes with spacing d.
Diffraction can only occur if the incident and scatter
angles are equal. ………………………………..………….. 18
17. xiii
Figure 2.5 Schematic of an ADXRD diffractometer. The beam emitted
by the X-ray tube is monochromated, collimated and passed
onto the sample. A detector is rotated about the sample so
that the diffracted intensity as a function of angle is
measured. ………………………………….……………….. 20
Figure 2.6 Example X-ray tube spectrum for a tungsten target and
operating voltage of 100 kV. The sharp lines are
characteristic lines of the target. …………………………. 21
Figure 2.7 ADXRD spectrum of quartz. ………………….…………… 23
Figure 2.8 Basic setup of an EDXRD analyser. ……………..………… 25
Figure 2.9 EDXRD spectrum of quartz. ……………………………… 26
Figure 2.10 Diagram of the Midfox on-line XRD system. The selected
slurry stream is de-aerated, split into two and passed through
two joint analysers. One analyser monitors the quartz
concentration of the slurry and the other monitors the apatite
concentration. ………………………………….…………... 29
Figure 2.11 The diffraction spectra of the amine feeds, final concentrates,
rougher tails and pure water. The angles at which the
Midfox analyser measures diffraction from the stream are
shown. ………………………………………………..……. 30
Figure 2.12 Midfox calibration curve for quartz in the final
concentrates. ………………………………..……………… 31
Figure 2.13 Midfox calibration curve for apatite in the final
concentrates. ………………………………..……………… 31
Figure 2.14 Midfox versus laboratory analysis of the concentration of
quartz in all three slurries. …………………..…………..… 32
Figure 2.15 Midfox versus laboratory analysis of the concentration of
apatite in all three slurries. …………………..…………….. 32
Figure 2.16 Photograph of the FCT-ACTech analyser. ………...………. 36
Figure 2.17 Added versus analysed lime content determined using a
laboratory diffractometer and Rietveld analysis. ……..…… 38
18. xiv
Figure 2.18 Comparison of the reduced oxide values determined with
XRD and XRF. The plot B is an expansion of the low
abundance region of plot A. ………………………..……… 38
Figure 3.1 The pencil-pencil EDXRD geometry. ………………..……. 43
Figure 3.2 Pencil-pencil geometry with variable diffraction angle and
collimator opening widths. …………………………………. 44
Figure 3.3 Illustration of the loss of diffraction counts with the pencil-
pencil geometry. The detector only samples a small section
of the diffracted cone. ……………………………...………. 45
Figure 3.4 Pencil-cone EDXRD geometry. ……………………………. 46
Figure 3.5 Diffraction spectra of PE4 taken over an angular range of 2°
to 8° with the instrument in Figure 3.2. ………...………….. 48
Figure 3.6 Effect on the diffraction spectrum of changing the X-ray tube
potential. ……………………………………………………. 51
Figure 3.7 X-ray spectra of tungsten and molybdenum target X-ray
tubes with voltage and current settings of 100 kV and 1 mA
respectively. …………………………………...…………… 53
Figure 3.8 Response of an ideal and real detector to monochromatic
photons. …………………………………………………….. 54
Figure 3.9 The effect of beam divergence on the resolution, count-rate
and sample volume measured. The resolution of the
instrument ΔΘ/Θ is poorer with larger collimator openings
since ΔΘ2>ΔΘ1. ……………………………..…………….. 58
Figure 3.10 Effect of changing the acquisition time on the spectrum
noise. ……………………………………………………….. 60
Figure 3.11 Shielding required to protect the detector from background
scattered X-rays. ……………………………..…………….. 61
Figure 4.1 Form factor of liquid water calculated with and without the
assumption of independent atoms. The oscillatory structure
function was taken from [74]. ………………...……………. 68
19. xv
Figure 4.2 Coherent cross section of liquid water calculated with and
without the assumption of independent atoms. ……...…….. 68
Figure 4.3 Form factor of wüstite calculated with and without the
assumption of independent atoms. In reality, the Bragg form
factor peaks are delta functions with infinite magnitude. For
illustrative purposes, the area under the delta peaks are
represented by the peak heights. …………………..………. 71
Figure 4.4 The face-centred cubic unit cell of wüstite. ………………. 71
Figure 4.5 Bragg cross section of wüstite. ………..…………………… 72
Figure 4.6 Screenshot of the main GUI of EDXRD Crystallography
Package. …….………………………………….…………... 75
Figure 4.7 Creating materials in EDXRD Crystallography Package – (a)
an amorphous material (water) and (b) a crystal (wüstite). ... 76
Figure 4.8 Sample creator in EDXRD Crystallography Package. …….. 76
Figure 4.9 Information displayed by EDXRD Crystallography Package
upon completion of a calculation. ………………………….. 77
Figure 4.10 Bragg form factor of a sample containing 50 wt% rutile and
50 wt% anatase. …………………………..…….………….. 80
Figure 4.11 Bragg cross section of a sample containing 50 wt% rutile and
50 wt% anatase. …………………………...….……………. 81
Figure 4.12 Data format for cross section and form factor data for
importation of data into XPERT. ……..…….……………… 82
Figure 4.13 Material editor in XPERT. Data can be imported from
EDXRD Crystallography Package using the options under
‘Coherent scattering’. ………………...……………………. 83
Figure 4.14 Flow diagram describing how each scattering process is
selected in the modified EGSnrc code. …..…….…….…….. 84
Figure 4.15 Simulated EDXRD spectrum of rutile. …………….……….. 87
Figure 4.16 Simulated EDXRD spectrum of anatase. ….…..…………… 87
Figure 4.17 Simulated EDXRD spectrum of a sample containing 50 wt%
rutile and 50 wt% anatase. ………………………………….. 88
20. xvi
Figure 5.1 The cone-cone geometrical setup. The incident and scattered
beams are conical, producing a circular-shaped beam at the
sample. ……………………………………………………… 92
Figure 5.2 Resolution performance vs. efficiency for the pencil-pencil,
pencil-cone and cone-cone geometies. For high-resolution
setups the cone-cone design delivers the best performance. .. 94
Figure 5.3 Spectrum of 241
Am measured with a CdTe detector. Notice
the significant exponential tail on the low-energy side of the
photopeak. ………………………………..………………… 95
Figure 5.4 Comparison of the photopeaks of 241
Am and 57
Co measured
with a CdTe detector. Note that the effect of hole-tailing
becomes worse with increasing energy. ………...…………. 97
Figure 5.5 The diffraction angle Θ is defined as the path through the
centre of the collimator openings after scattering at the centre
of the sample. ……………...……………………………….. 99
Figure 5.6 X-ray tube spectrum incident on and transmitted through a
15-mm thick bauxite slurry. The transmitted spectrum is the
most important to consider when designing an EDXRD
instrument. …………………..…………………………….. 103
Figure 5.7 Detection efficiency of the Amptek XR-100T-CdTe detector
used in the EDXRD analyser. …………..………………….. 105
Figure 5.8 Bragg and Compton for wüstite as a function of angle at (a)
30 keV and (b) 60 keV. The magnitude of the Bragg cross
section has been normalised for viewing purposes. …..…… 107
Figure 5.9 Rayleigh cross section of water as a function of angle at
30 keV and 60 keV. ……………………………..…………. 108
Figure 5.10 The prototype instrument contains four collimators: the (i)
source collimator, (ii) primary beam collimator, (iii) scatter
collimator and (iv) detector collimator. The collimators are
arranged as shown. …………………………………………. 112
Figure 5.11 The source collimator is a metal block with a cylindrical hole
at its centre. …….…………………………..………………. 113
21. xvii
Figure 5.12 The primary beam collimator is a metal plate with two
openings. An annular opening creates a conical incident
X-ray beam for diffraction measurements while a pinhole at
the centre provides a means to measure the transmitted
beam. ……………………………………………………..... 114
Figure 5.13 The primary beam collimator plate must be large enough so
that it blocks the direct line of sight of the scatter and
detector collimators. This eliminates the possibility that
X-rays emanating from above the collimator reaching the
detector. …………………………………...……………….. 115
Figure 5.14 If the collimators are not designed properly diffraction from
the inner surfaces of the openings may be observed. On the
left, diffracted X-rays from the primary beam (red) and
scatter (blue) collimators are able to reach the detector. On
the right, the collimator diffracted X-rays are blocked. This
must be the case otherwise unwanted diffraction peaks will
appear in the diffraction spectrum of the sample. ………….. 116
Figure 5.15 The detector collimator is a metal plate with a conical hole at
its centre. ………………………………………..…………. 117
Figure 5.16 The opening width of the source collimator must be large
enough so that the cone beam produced just covers the
primary beam collimator opening. …..………….…………. 119
Figure 5.17 Resolution vs. count-rate performance for various
combinations of primary beam/scatter and detector
collimator opening widths. …………...……………………. 121
Figure 5.18 Monte Carlo EDXRD spectrum of wüstite and water
collected with instruments with collimator thicknesses
ranging from 5 mm to 30 mm. …………………………….. 124
Figure 5.19 Primary beam collimator with lead shield. The scatter and
detector collimators also have similar lead shields. Note that
the openings in the shield are much wider than the collimator
opening as the shield is not intended. ……...………………. 125
22. xviii
Figure 5.20 Monte Carlo modelled effect on the diffraction peak when
the primary beam collimator is misaligned in the horizontal
direction whilst all other collimators remain perfectly
aligned. A misalignment of just 200 µm is sufficient to
significantly reduce the peak intensity. ……………………. 128
Figure 5.21 Monte Carlo modelled effect on the diffraction peak when
the scatter collimator is misaligned in the horizontal direction
whilst all other collimators remain perfectly aligned. The
effect of misalignment of this collimator is much the same as
the primary beam collimator. ……………………………… 128
Figure 5.22 Monte Carlo modelled effect on the diffraction peak when
the primary beam and scatter collimators are misaligned in
the horizontal direction simultaneously whilst all other
collimators remain perfectly aligned. The effect is much
more severe than for misalignment of collimators
individually. The results indicate that these collimators must
be aligned to within 100 µm. ……..…...………………….. 129
Figure 5.23 Monte Carlo modelled effect on the diffraction peak when
the detector collimator is misaligned in the horizontal
direction whilst all other collimators remain perfectly
aligned. This collimator must be aligned to within 100 µm
of the central axis. …………………………….………...… 130
Figure 5.24 Monte Carlo modelled effect on the diffraction peak when
the primary beam collimator is misaligned in the vertical
direction whilst all other collimators remain perfectly
aligned. Vertical alignment is less critical than horizontal
alignment. ……………………………………………….… 131
23. xix
Figure 5.25 Monte Carlo modelled effect on the diffraction peak when
the primary beam and scatter collimator is misaligned
simultaneously in the vertical direction whilst all other
collimators remain perfectly aligned. The loss of counts is
much more severe when both collimators are misaligned.
The results indicate that these collimators must be placed in
the vertical direction to within 1 mm of their ideal
positions. ……………………………………………..……. 132
Figure 5.26 Monte Carlo modelled effect on the diffraction peak when
the primary beam and scatter collimator opening angles are
misaligned with the direction of the X-ray beam. A
misalignment of less than 1° is enough to effectively block
the passage of X-rays. Note that both the inner and outer
surfaces are misaligned by the same amount, not just the
outer surfaces as depicted in the figure. …………………… 133
Figure 5.27 Sample positioning for vertical sensitivity measurements.
The sample was moved over a 20 mm range in 0.2 mm
increments. ………………………………………………… 134
Figure 5.28 Vertical sensitivity of the prototype instrument determined
by Monte Carlo modelling. The total sensitive region spans
approximately 13 mm with a FWHM of about 6 mm. ……. 135
Figure 5.29 The sensitive region of the instrument is the region enclosed
by the blue lines, which represent the boundaries of the
incident and scatter beams. The total height of the sensitive
region is approximately 13 mm. …………………………… 136
Figure 5.30 Sample positioning for vertical sensitivity measurements.
The sample was oriented parallel (left) and perpendicular
(right) to the aperture joins. For both orientations the sample
was moved over a 40 mm range in 1 mm increments. …….. 138
Figure 5.31 Horizontal spatial sensitivity of the prototype instrument as
determined by Monte Carlo. The instrument is most
sensitive to the outer edges of the sample. ………………… 138
24. xx
Figure 6.1 Photograph of the prototype analyser showing the X-ray tube
(A), source collimator (B), primary beam collimator (C),
scatter collimator (D), translation stage for the primary
beam/scatter collimator assembly (E) and the sample stage
(F). The detector collimator and CdTe detector are located
inside the shielding below the lower shelf. ………………... 142
Figure 6.2 The detector and detector collimator attached to the
instrument. …………………………………………………. 143
Figure 6.3 The source collimator attached to the X-ray tube. ………… 144
Figure 6.4 The primary beam and scatter collimator assembly. ……… 145
Figure 6.5 Close up of the primary beam collimator with the lead
shielding removed to show the annular opening. …………. 146
Figure 6.6 Photograph of the detector collimator and detector. ……… 147
Figure 6.7 EDXRD spectrum of rutile collected with the prototype
analyser. …………………………………………………… 149
Figure 6.8 EDXRD spectrum of anatase collected with the prototype
analyser. ……………………………………………………. 150
Figure 6.9 EDXRD spectrum of quartz collected with the prototype
analyser. …………………………………………………… 150
Figure 6.10 Photograph of a loose powder sample used for
measurements. The above material is quartz. ……………… 151
Figure 6.11 EDXRD spectrum of the polypropylene Petri dishes used to
contain the loose powder samples. ………………………... 152
Figure 6.12 Number of counts registered in the 241
Am peak by the
XR-100T-CdTe detector during 30 s acquisitions over tens of
hours. Intermittently the cover of the PX2 box was either
removed or replaced in order to change the temperature of
the RTD circuit. When RTD is on the counts vary according
to the change in temperature. However no change is
observed when RTD is off. ………………………………... 154
25. xxi
Figure 6.13 59.54 keV 241
Am photopeak with the PX2 covered (warm)
and uncovered (cool). The warm peak shows fewer counts
and slightly reduced tailing. ……………………………….. 155
Figure 6.14 Comparison of the Monte Carlo modelled and experimental
spectra of a sample containing 50 wt% halite and 50 wt%
sylvite. ……………………………………………………… 157
Figure 6.15 Comparison of the Monte Carlo modelled and experimental
spectra of a sample containing 30 wt% halite and 70 wt%
sylvite. …………………………………………………….. 157
Figure 6.16 The diffraction spectrum of the 50/50 wt% halite/sylvite
sample with increasing collimator opening widths. The
opening of each collimator was oversized by the value given
in the legend. ………………………………………………. 159
Figure 6.17 Increase in the sample volume measured by rotating the
sample during measurement. ………………………………. 160
Figure 6.18 Comparison of the Monte Carlo modelled and experimental
spectra of a sample containing 70 wt% halite and 30 wt%
quartz. ……………………………………………………… 162
Figure 6.19 Comparison of the Monte Carlo modelled and experimental
spectra of a sample containing 80 wt% halite and 20 wt%
quartz. ……………………………………………………… 163
Figure 6.20 Vertical spatial sensitivity of the prototype instrument plotted
with the Monte Carlo data determined in Chapter 5. The
spatial sensitivity curve of the instrument is slightly broader
than the Monte Carlo data. ………………………………… 167
Figure 7.1 EDXRD spectra of the six reference samples. The spectra
are offset in the vertical axis for clarity. …………………… 172
Figure 7.2 EDXRD spectrum of mixed sample 1. The spectrum shows
features of the individual mineral component spectra shown
in Figure 7.1. ……………………………………………….. 172
Figure 7.3 Comparison of the inferred and true masses of each mineral
contained in the suite of twenty samples. ………………….. 174
26. xxii
Figure 7.4 Coarse (left) and fine (right) slurries. The coarse feed
material is relatively dry with large particles whereas the fine
feed particles are suspended in saturated brine. …………… 177
Figure 7.5 EDXRD spectra of the coarse and fine feed potash slurries
obtained from Mosaic potash. ……………………………… 178
Figure 7.6 Repeated acquisitions of the coarse feed potash sample. The
sample was thoroughly stirred between collections. ………. 180
Figure 7.7 Repeated acquisitions of the fine feed potash sample. The
sample was thoroughly stirred between collections. ………. 180
Figure 7.8 Sampling errors of the halite and sylvite peaks from course
and fine feed potash as a function of the total solids mass of
material measured. ………………………………………… 183
Figure 7.9 Fine feed potash slurry with various solids loadings. ……… 185
Figure 7.10 Signal-to-background ratio of fine feed potash slurry with a
range of solids loadings. …………………………………… 186
Figure 7.11 Estimated sampling errors for fine feed potash as a function
of solids loading. The errors are shown for three measured
slurry volumes: 10 L, 100 L and 300 L. …………………… 188
Figure 7.12 EDXRD spectrum of sample 1 of the synthetic potash
suite. ………………………………………………………... 190
Figure 7.13 Synthetic potash analysis results. …………………………. 191
Figure 7.14 Repeated measurements of synthetic potash sample 2. The
sample was stirred before each collection to redistribute the
particles. …………………………………………………… 192
Figure 8.1 Inferred and true masses of each mineral contained in the
suite determined by Monte Carlo modelling for comparison
against the equivalent experimental data presented in
Chapter 7. ………………………………………………….. 199
Figure 8.2 Inferred and true masses of each mineral contained in the
synthetic potash samples determined by Monte Carlo
modelling for comparison against the equivalent
experimental data presented in Chapter 7. ………………… 203
27. xxiii
Figure 9.1 Diagram of the pencil cone instrument used in optimisation
process developed by Bomsdorf et al [92]. ……………….. 207
Figure 9.2 Projection of a scatter event in the xy-plane for the
instrument in Figure 9.1. …………………………………... 208
Figure 9.3 (a) Measured and simulated iron diffraction peak with
collection times of 500 s and 10 s. (b) Measured and
simulated iron diffraction peaks with various primary
collimator opening widths. ………………………………… 209
Figure 9.4 (a) Measured (upper trace) and non-normalised simulated
(lower trace) diffraction spectrum of SiC before
optimisation. The counting time was 1000 s. (b) Optimised
diffraction spectra collected for 25 s. ……………………… 211
Figure 9.5 Example EDXRD spectrum from on e of the library designs.
Peaks appear at energies of 40 and 70 keV with heights IP1
and IP2 respectively. The spectrum terminates at 95 keV in
accordance with the X-ray spectrum used in the
simulations. ………………………………………………… 219
Figure 9.6 Resolution of setups with variable detector collimation
determined using Monte Carlo Modelling. This data can be
used to estimate the resolution of similar designs, as shown
by the blue circles. ………………………………………… 220
Figure 9.7 Peak heights of the 40 keV line of setups with variable
detector collimation determined using Monte Carlo
Modelling. This data can be used to estimate the resolution
of similar designs, as shown by the blue circles. …………. 220
Figure 9.8 Resolution values as a function of the detector collimator
opening. Intermediate values are calculated from the
interpolation line. The data determined using Monte Carlo
modelling (black dots) agrees well with the interpolation
line. ………………………………………………………… 222
28. xxiv
Figure 9.9 Peak height values of the 40 keV line as a function of the
detector collimator opening. Intermediate values are
calculated from the interpolation line. The data determined
using Monte Carlo modelling agrees well with the
interpolation line. ………………………………………….. 222
Figure 9.10 Screenshot of the main page of the EDXRD Design
Facilitator GUI. ……………………………………………. 227
Figure 9.11 Material and sample creators in EDXRD Design
Facilitator. …………………………………………………. 228
Figure 9.12 Test transmission function in EDXRD Design Facilitator.
The plot shows the spectrum incident on the sample and the
transmitted spectrum. The energy region within which the
diffraction peaks should reside is the ‘Usable energy region’
marked in red. ……………………………………………… 230
Figure 9.13 Advanced x-ray tube settings. The target angle and various
filtrations can be set with this menu. ……………………… 230
Figure 9.14 Resolution viewer in EDXRD Design Facilitator enables the
peak overlap to be investigated as a function of resolution. .. 232
Figure 9.15 Perferences GUI in EDXRD Design Facilitator. ………….. 233
Figure 9.16 Specify Lines GUI in EDXRD Design Facilitator. ………... 234
Figure 9.17 Options menu in EDXRD Design Facilitator. …………….. 236
Figure 9.18 Peak positions at 5 in relation to the transmission through a
10 mm thick halitesylvite sample. This information can be
used to fine-tune the usable energy region. ………………... 239
Figure 9.19 Example of the output given by EDXRD Design Facilitator
after the search for the best design. In this case the material
being measured contains equal proportions of the minerals
wüstite, hematite, magnetite, anatase and quartz. …………. 240
Figure 9.20 In order to calculate the count-rate for the sample of interest,
the Monte Carlo spectrum must be converted to the spectrum
of the sample to be measured. …………………………….. 242
29. xxv
Figure 9.21 The line spectrum of a sample containing wüstite, hematite,
magnetite, anatase and quartz in equal proportions. The
spectrum is calculated from the cross sections of the Monte
Carlo and measured samples. The spectrum is uncorrected
for the X-ray tube output, resolution and detector physics of
the real instrument. ………………………………………… 245
Figure 9.22 Comparison of the spectra of a sample obtained with Monte
Carlo and calculated by EDXRD Design Facilitator. The
sample contains equal proportions of wüstite, hematite,
magnetite, anatase and quartz. …………………………….. 246
Figure 9.23 Comparison of the spectra (Monte Carlo) obtained with the
prototype and optimised instruments. …………………….. 249
Figure 10.1 Steps in the conventional processing of potash. …………… 253
Figure 10.2 Simulated spectra of the potash slurry showing the peak
overlap obtained with various resolutions between 30 and 45
keV. The spectra were created using the Check Resolution
function in EDXRD Design Facilitator. …………………… 256
Figure 10.3 Simulated spectra of the potash slurry showing the peak
overlap obtained with various resolutions between 15 and 25
keV. The spectra were created using the Check Resolution
function in EDXRD Design Facilitator. …………………… 257
Figure 10.4 Positions of the Sylvite (200) escape peaks relative to the
kaolinite (001) line. For diffraction angles between Θ = 4°
to Θ = 5.5° the kaolinite line occupies the same energy
region as the escape peaks. ………………………………… 258
Figure 10.5 At Θ = 4° the kaolinite (001) and gypsum (020) lines are
resolved from the escape peaks. …………………………… 259
Figure 10.6 Usable energy region for 10-mm thick potash slurry. …….. 264
Figure 10.7 Selection of the best instrument geometry for potash slurry
analysis by EDXRD Design Facilitator. ………………….. 265
30. xxvi
Figure 10.8 The positions of the gypsum (020) and kaolinite (001) lines
with respect to the Te Kβ1 escapes of the W Kα fluorescent
lines of the X-ray target. …………………………………… 267
Figure 10.9 Modelled EDXRD spectrum of the simulated potash slurry
acquired with the optimised instrument geometry. ………… 268
Figure 10.10 Basic configuration of a system setup to measure material
flowing through a byline. Slurry is diverted to the byline by a
sampler, passed through the instrument and returned to the
main process stream. ……………………………………… 270
Figure 10.11 A gravity fed system. The slurry is fed through the analyser
under the force of gravity. ………………………………… 271
Figure 10.12 Setup of an on-line instrument. Separate detectors are used
to measure the diffracted and transmitted beams so they can
be collected simultaneously. Also, the X-ray tube and
detector collimator are each attached to translation stage.
This allows then to be aligned with the fixed primary beam
and scatter collimators. ……………………………………. 272
Figure 10.13 A possible slurry presenter design for an on-line analyer.
The region where the beam irradiates the sample has a
rectangular cross section. ………………………………….. 273
Figure 10.14 Schematic diagram of an on-line EDXRD configuration in
which the analyser is submerged in a tank of slurry. ……… 274
Figure 10.15 Inferred vs. true masses of each mineral contained in the
simulated potash slurry. …………………………………… 277
Figure 11.1 Arrangement for measuring circulated slurries with the
prototype analyser. The slurry loop consists of two stirring
tanks, a pump and several pipelines. The flow rate is
controlled using the three valves. …………………………. 290
31. xxvii
List of Tables
Table 2.1 Summary of how ADXRD and EDXRD satisfy Bragg's law. …. 24
Table 2.2 Statistical uncertainties in quantifying the concentrations of
quartz and apatite in the feeds, tails and concentrates. .……. 33
Table 2.3 Mineral phases contained in Portland cement. ……………. 35
Table 5.1 List of important test material for the analyser to measure. .. 101
Table 5.2 Composition of the bauxite slurry (solids loading 50% by
weight) used for the calculation of the transmitted X-ray
spectrum in Figure 5.6. ……………………………………. 103
Table 5.3 List of energy ranges/cut-offs due to diffraction angle
considerations. ……………………………………………. 109
Table 5.4 The effect of varying the diffraction angle on a number of
instrument performance properties. The diffraction angle is
assumed to be at a very forward angle. Desirable effects are
labelled in green. ………………………………………….. 109
Table 5.5 Solutions to Bragg's law for X-ray energy (in keV).
Energies labelled in red are outside the usable energy range
25 < E < 90 keV. ………………………………………….. 110
Table 5.6 Collimator opening widths investigated to determine the best
combination for the prototype analyser. The primary beam
and scatter collimator opening were always equal. All
combinations were investigated. ………………………….. 120
Table 5.7 Collimator opening widths. ……………………………….. 122
Table 6.1 Composition of salt samples for Monte Carlo vs. experiment
comparison. ……………………………………………….. 156
Table 6.2 Monte Carlo and experimental peak intensities calculated
from the two brightest peaks of each mineral. The peak
intensities were calculated by summing the total counts in the
peaks and subtracting the background. ……………………. 158
32. xxviii
Table 6.3 Ratio of the Monte Carlo to experimental peak intensities
obtained with oversized collimator opening widths for a
50/50 wt% halite/sylvite sample. …………………………. 159
Table 6.4 The mean diffraction angle as calculated from the Monte
Carlo (MC) and experimental (Exp) spectra. ……………… 161
Table 6.5 Composition of halite/quartz samples. ……………………. 162
Table 6.6 Monte Carlo and experimental peak intensities calculated
from the two brightest peaks of each mineral. ……………. 164
Table 6.7 Comparisons of the resolution of the diffraction peaks
obtained by Monte Carlo and experiment. ………………… 164
Table 6.8 Diffraction peak resolution calculated from the spectra in
Figure 6.16. Also given is the average experimental
resolution. ………………………………………………….. 165
Table 7.1 Compositions of the twenty dry mineral samples use in the
quantitative analysis investigation. All compositions are
given in wt%. ……………………………………………… 171
Table 7.2 Total and statistical standard (root-mean-square) errors,
correlation coefficients and mass ranges for the six mineral
components. ……………………………………………….. 174
Table 7.3 Composition of the coarse and fine feed potash slurry. …… 176
Table 7.4 Compositions of the 15 synthetic potash samples. ………… 189
Table 7.5 Total and statistical standard errors, correlation coefficients
and mass ranges for the mineral components of the synthetic
potash samples. Gypsum and Kaolinite could not be
measured accurately. ……………………………………… 192
Table 8.1 Composition of the simulated dry mineral powder samples
for comparison between Monte Carlo and Experiment.
Sampling errors were included: 0.2 wt% for corundum and
0.1 wt% for all other minerals. ……………………………. 198
Table 8.2 Total errors in the analysis of the six mineral components
compared against the experimental results. ……………….. 199
33. xxix
Table 8.3 Composition of the simulated potash samples for comparison
between Monte Carlo and Experiment. Sampling errors of
0.35 wt% and 0.40 wt% were included for halite and sylvite
respectively. The sampling errors for the minor components
were 0.02 wt%. ……………………………………………. 202
Table 8.4 Inferred and true masses of each mineral contained in the
synthetic potash samples determined by Monte Carlo
modelling for comparison against the equivalent
experimental data presented in Chapter 7. ………………… 203
Table 9.1 Design parameters used to produce a library containing the
performance data of 28 125. ………………………………. 214
Table 9.2 Design parameters common to all designs in the library. …. 215
Table 9.3 Properties of the Monte Carlo sample used to create the
library of performance data. ………………………………. 217
Table 9.4 Design parameters in the library after interpolation. The total
number of combinations is 1 723 392. ……………………. 223
Table 9.5 Optimal design parameters for the prototype analyser
compared against the actual values used in the
instrument. ………………………………………………… 248
Table 10.1 Potash sample composition used to optimise the
instrument. ………………………………………………… 254
Table 10.2 Specification of a Comet MXR-160HP/11 X-ray tube. …… 262
Table 10.3 Materials and lines that the potash analyser will measure. ... 263
Table 10.4 Energy limits for the region in which the diffraction peaks in
Table 10.2 reside at various diffraction angles. …………… 265
Table 10.5 Design parameters of the potash analyser. ………………… 268
Table 10.6 Composition of the 20 simulated potash slurry samples. The
brine was assumed to be homogeneous; hence fractions of
water, NaCl and KCl were equal for all samples. ………… 276
Table 10.7 Total and statistical standard errors for the mineral
components of the simulated potash slurry samples. ……… 277
34. xxx
List of Patents, Publications and Conferences
Patent
J.N. O’Dwyer, J.R. Tickner, An Online Energy Dispersive X-ray Diffraction
Analyser, International Publication No. WO 2009/043095.
Publications
J.N. O’Dwyer and J.R. Tickner, Modelling Diffractive X-ray Scattering Using the
EGS Monte Carlo Code, Nucl. Instrum. Meth. A, Proceedings of the 10th
International Symposium on Radiation Physics, 580(1) (2007) 127-129.
J.N. O’Dwyer, J.R. Tickner, Quantitative Mineral Phase Analysis of Dry Powders
Using Energy-Dispersive X-ray Diffraction, Appl. Radiat. Isot., 66 (2008)
1359-1362.
J.N. O’Dwyer, J.R. Tickner, Monte Carlo Modelling of X-ray Diffraction From
Crystalline and Amorphous Materials, Nucl. Instrum. Meth. B, in press.
Conferences
J.N. O’Dwyer and J.R. Tickner, Implementation of Amorphous and Crystalline
Powder X-ray Diffractive Scattering in the EGS code, presented at The American
Nuclear Society’s 14th
Biennial Topical Meeting of the Radiation Protection and
Shielding Division, Carlsbad New Mexico, USA, April 3-6, 2006.
J.N. O’Dwyer and J.R. Tickner, Calculation of the Cross Sections and Form
Factors of Mixed Crystalline and Amorphous Materials for the Simulation of
Diffractive Scattering Using the EGS Code, presented at Radiation 2006, Sydney
NSW, Australia, April 20-21, 2006.
35. xxxi
J.N. O’Dwyer and J.R. Tickner, A Prototype Energy-Dispersive X-ray Diffraction
Instrument for Online Mineralogical Analysis, poster presentation at the 10th
International Symposium on Radiation Physics, Coimbra, Portugal, September
17-22, 2006.
J.N. O’Dwyer and J.R. Tickner, Modelling Diffractive X-ray Scattering Using the
EGS Monte Carlo Code, presented at the 10th
International Symposium on
Radiation Physics, Coimbra, Portugal, September 17-22, 2006.
J.N. O’Dwyer, On-line Mineralogical Analysis Using Energy-dispersive X-ray
Diffraction Spectrometry, poster presentation at The Australian Institute of
Physics – Physics in Industry Day, Sydney NSW, Australia, 27 September 2006.
R. Bencardino, J. O’Dwyer, G. Roach, J. Tickner, J. Uher, Nuclear and X-ray
Instrument Design and Optimisation using Condor: High Performance Computing
on a Cycle-Harvesting Network, poster presentation at the Transformational
Computational and Simulation Science Workshop, Sydney NSW, Australia, 12-13
December 2007.
36. xxxii
General Note
In X-ray diffraction and crystallography, 2θ is used to denote the total
angle through which an X-ray is scattered during the process of diffraction.
However, in Monte Carlo Modelling, general convention dictates that simply θ be
used to denote the total scatter angle. This thesis investigates both X-ray
diffraction and Monte Carlo modelling. Therefore, in order to resolve the conflict
between the two conventions Θ is used throughout the thesis to denote the total
scatter angle. An exception to this rule is used in Chapter 2, where the convention
of crystallography, 2θ, is used in the description of existing angle-dispersive
X-ray diffractometers.
37. 1
Chapter 1
Introduction
1.1 – Mineral Processing
Mineral processing is the method of beneficiating valuable minerals and
producing metals from ores mined from the Earth’s crust. A mineral ore can
generally be thought of as consisting of two categories of material, valuable
minerals and gangue. The gangue is any material within the ore that is not
economically important. The aim of mineral processing is therefore to separate
the valuable minerals (the values) from the gangue in order to produce an enriched
material. The processes by which minerals are separated from the gangue
materials are many and varied since different methods are required to process
different minerals. For example, the method known as the Bayer process for
extracting alumina from its ore, bauxite, is different to the technique used to
process copper ores [1]. There are also differences between how ores of the same
type are treated, due to differences in the ore mineralogy between mine sites.
However, most mineral processing techniques typically utilise the four general
steps shown in the flowchart displayed in Figure 1.1 [2]. Each of these steps is
broken down into many sub-steps, which can be quite different for the processing
of particular ores.
The first step is called size reduction, or comminution. The primary goal
of comminution is to break the ore into individual particles of valuable mineral
and gangue. This process is commonly called liberation since the valuable
minerals are liberated from the gangue material. Liberation is achieved by
crushing and grinding the ore down to a particle size such that the valuable
minerals are released from the gangue. The output of the liberation process
typically produces three classes of particles: those that contain the values, those
that only contain only gangue materials and particles that contain both values and
gangue (middlings). Crushing and grinding consume significant amounts of
energy, so the particle size at the output should be optimised according to the cost
of comminution and recovery of the values.
38. 2
Figure 1.1 - General stages involved in mineral processing.
Each step typically involves many sub-steps [2].
The second step is concentration, where the ore is separated into
concentrates, tailings and middlings. The concentrate is an enriched product
containing the valuable minerals. The tailings are the waste products (gangue),
but can also contain an amount of valuable minerals that are not recovered in the
concentration process. The middlings are generally returned to the comminution
step for further grinding in order to unlock the valuable minerals.
There are several methods used to concentrate ores. The most widely used
method is the froth flotation technique [2-5]. In this technique, the process stream
is fed into large flotation tanks in which air bubbles are introduced. Under the
correct conditions, the particles of the valuable minerals adhere to the air bubbles
and consequently rise to the top of the tank, hence separating them from the rest
of the material. The bubbles and minerals that arrive at the surface of the tank
produce a froth from which the minerals can be recovered. For this method to
work, the valuable minerals must be hydrophobic, that is, they must be repel water
on their surfaces so that they can attach to an air bubble. Many minerals are not
naturally hydrophobic, therefore chemical reagents are added to the pulp in order
to promote floatation. Reagents are also used to aid the production of a stable
froth and to make the gangue minerals hydrophilic so they do not float. Floatation
39. 3
can only be used to concentrate materials of small particle size, since for large
particles the adhesive force between the mineral and the bubble can be insufficient
to float the particle. A basic schematic diagram of the floatation process is shown
in Figure 1.2. Some mineral processing plants also use the reverse floatation
method, in which the gangue is floated rather than the valuable minerals.
Gravity methods are also used to concentrate mineral ores. These methods
rely on differences between the specific gravities of the values and the gangue.
The minerals contained in the ore are separated based on their movements in
response to the force of gravity in conjunction with one or more other forces.
There are a number of different gravity concentration techniques utilised,
including jigs, spirals and shaking tables [2,4]. Other concentration techniques
include magnetic separation and electrostatic separation. Magnetic separation is
used to separate paramagnetic and ferromagnetic minerals from non-magnetic
gangue materials. Minerals that can be separated by their magnetic properties
include ilmenite (FeTiO3), pyrrhotite (FeS), chromite (FeCr2O4) and hematite
(Fe2O3) [2]. Electrostatic separation (also called high-tension separation) exploits
Figure 1.2 - Basic schematic of the froth flotation process for
concentration of a mineral slurry [2]. The valuable minerals are
separated from the gangue by attaching to air bubbles. The
bubbles rise to the top to form a froth. Reagents are added to the
pulp in order to promote flotation.
40. 4
differences in electrical conductivity between minerals and is used extensively in
the separation of rutile (TiO2), zircon (ZrSiO4), tin and various other minerals [5].
The third step in Figure 1.1, product handling, deals with the disposal of
the tailings from the beneficiation process. In some processing plants, the tailings
are retreated in secondary circuits in order to recover further amounts of the
valuable minerals. The final tailings discharged from most plants are usually
dumped into purpose built dams near the processing plant. Other disposal
methods include back-filling, which is the practice of filling mined-out sections of
underground mines with the coarse solid wastes, and dry stacking, where the
tailings are dewatered and deposited on the land.
Upon the completion of the beneficiation process, the concentrated
products can either be used directly or further processed to extract metals from the
concentrated ore. The production of metals from mineral ores is the subject of
extractive metallurgy [6,7]. There are three general processes used to reduce an
ore into metallic form, which are classified as: pyrometallurgy, hydrometallurgy
and electrometallurgy. Pyrometallurgical processes are the most commonly used
techniques and involve treating the ore at high temperatures to extract metals of
interest. Examples include roasting, which is the method of heating, for example,
sulphide minerals in the presence of oxygen, and smelting, in which the ore is
heated in the presence of a reducing agent. An example of the use of smelting is
the extraction of iron from iron ore in a blast furnace [7].
Hydrometallurgical processes involve the extraction of metals through the
use of aqueous solutions. Leaching is a common hydrometallurgical technique in
which the metals are dissolved in an acidic or alkaline solution while the gangue
remains as an insoluble product. The metals of interest are recovered from the
leached solution. Electrometallugical techniques are often used to recover or
purify metals. These methods involve submersion of electrodes connected to an
external circuit in an aqueous solution. The solution may contain the metals,
which are removed from the solution and deposited on the cathode. This is a
common method used to separate metals in leached solutions produced by
hydrometallurgical operations. Another electrometallugical technique is
electrorefining, in which the metal to be purified is the anode. The anode is
41. 5
dissolved in the solution and the pure metal deposited on the cathode surface,
from which it can be removed.
1.2 – Process Control
The physical and chemical processes used to prepare an ore for processing
and to extract the minerals and metals of value tend to be sensitive to the physical
parameters and composition of the ore being processed. Examples may include
the specific mixture of reagents required during froth flotation to achieve
maximum recovery or the optimal particle size to obtain the best level of
separation. Knowledge about parameters such as the particle size, elemental
composition, mineralogical composition, mineral texture, density and pH of a
process stream is therefore extremely important if the optimal recovery of the
valuable minerals is to be obtained. For this reason, modern mineral processing
plants are fitted with sophisticated systems for automated control of processing
operations. These systems use dedicated instruments to measure the important
properties of the material at many points along the process chain. The
information gained is used to adjust the operating parameters in response to
changes in processing conditions, such as the composition of the feed ore, for
Figure 1.3 - Simple diagram showing the concept
of process control. The mixture of the materials
is analysed after mixing. The results of the
analysis are used to control and optimise the
blend.
42. 6
example. The goal of such a system is to compensate for changes and make
adjustment to the process in order to continually operate the plant at its optimal
level. The concept of process control is shown in Figure 1.3.
There are two general classes of analysis techniques used for process
control in mineral processing: off-line and on-line analysis. In off-line analysis, a
small amount of material, or assay, is sampled from the processes stream at an
appropriate location. The sample is then taken to an on- or off-site laboratory for
analysis, as depicted in Figure 1.4. On-line methods on the other hand measure
the material directly on-stream using probes or other devices that enable the
process stream to be measured without the need to remove a sample.
Off-line methods have both advantages and disadvantages (however
generally the disadvantages tend to outweigh the advantages). The advantage of
off-line measurement is that generally a more precise analysis of the material can
be made, since the measurements are carried out in a laboratory under controlled
conditions. However, the lag time between when the assay is taken and the results
Figure 1.4 – Off- and on-line analysis of a slurry stream. In off-line analysis, a sample
of slurry is taken from the stream and analysed by a laboratory instrument. The on-
line analyser measures the stream directly and provides data in (near) real-time.
43. 7
become available can be as large as hours or days. As a consequence, the
operating conditions of the plant can be quite different when the results are
obtained compared to what they were when the sample was taken. In extreme
cases the analysis results may not even be relevant at the time they become
available. The other main issue with off-line techniques is, due to the typically
small sample volumes used for analysis, the composition of the sample itself
many not be entirely representative of the process stream from which it was taken.
Also, the sampling equipment required can be expensive to purchase and operate.
For these reasons, many off-line techniques are ill-suited to process control.
On-line analysers are capable of providing results in near real-time and can
be linked to plant control units. With such systems, automatic adjustments to the
operating parameters can be made rapidly and hence the efficiency of the plant
can be maintained at the optimal level. On-line analysers arranged to measure
material on-stream can also be capable of performing bulk analysis, i.e. the
analysis is performed on large quantities of material rather than small samples.
For example, a slurry analyser may be placed on a pipeline such that it measures
the stream as it flows past the instrument (see Figure 1.4). In this case the total
effective mass of material measured in the course of a single measurement may be
tens or even hundreds of kilograms. Thus, the issues surrounding the obtainment
a representative sample are somewhat alleviated. However, care must still be take
to ensure that the instrument ‘sees’ a representative stream.
The mineral processor would ideally like to have the ability to fully
characterise the properties of the process stream on-line at every point along the
processing chain. This way all processes in the plant could be monitored for
efficiency and hence the plant would always be operated at its optimal level.
While in general this is not practical or possible, there are a number of key
parameters that, if measured, can greatly increase plant efficiency. An example is
particle size analysis of the ground ore during the comminution stage. This
enables the degree of liberation of the valuable minerals to be estimated.
Mineralogical analysis of the feed into the crushers is also beneficial, since the
hardness of a mineral and therefore the grindability of an ore is heavily dependent
on crystal structures of the minerals contained within the material. Hence the
residence time an ore spends within a crusher depends on the mineralogy of the
44. 8
ore. Mineralogy is also extremely important in froth flotation, as flotation
properties are determined by structural characteristics and not solely on chemistry.
Mineralogical and elemental analysis of the tailings can provide information on
the level of mineral and metal recovery and hence indicate the efficiency of the
process.
It can be seen from the above examples that the mineralogy of a process
stream is an important property in controlling the processing of ores. Although
instruments exist for on-line and quasi on-line mineral analysis [8,9], currently
there is no standard method for monitoring the mineralogy of process streams on-
line in mineral processing. This is a significant issue for the mineral processor,
since direct, real-time monitoring of stream mineralogy could greatly increase
plant efficiency. Direct mineralogical analysis of process streams is primarily
limited to off-line techniques. Widely used techniques include scanning electron
microscopy (SEM) [10] and X-ray diffraction (XRD) [11]. Assay sampling is
typically used for these methods and therefore they suffer from the issues listed
above. On-line monitoring of process streams, on the other hand, is largely
restricted to elemental analysers, which measure the chemical composition of the
process stream. Widely used on-line elemental analysis techniques for process
monitoring and control include X-ray fluorescence (XRF) [12] and prompt
gamma-ray neutron activation analysis (PGNAA) [13]. The mineralogical content
of the stream is determined using prior knowledge of the relationship between the
chemical and mineralogical composition of the material in question (normative
mineralogy) [14,15]. The problem with this approach of course is that the
mineralogy is not measured directly, but rather estimated based on the elemental
composition. XRF analysis for the inference of mineralogical composition is a
well-developed technology, however unexpected or unaccounted changes in the
chemical composition of the ore can lead to errors in the estimation of the
mineralogical composition. For example, in reality many minerals do not have a
fixed chemical composition. Substitution of atoms within the crystal lattice is
common (e.g. a solid solution) and hence the chemical composition of minerals
can vary depending on location. This phenomenon and others where the chemical
composition of an ore changes from that which is assumed in the normative
45. 9
calculations can hence produce erroneous results. Measurement of the mineralogy
directly is therefore preferable.
1.3 – EDXRD for On-line Mineralogical Analysis
This thesis attempts to address the challenge of performing on-line
mineralogical analysis by exploring a new method for analysing the mineralogical
composition of slurries. This method, known an energy-dispersive X-ray
Diffraction (EDXRD), is a technique that is well-suited to measuring the
mineralogy of process streams on-stream and in real-time [16]. The EDXRD
technique measures the energy spectrum of polychromatic X-rays diffracted
through a fixed angle. The energy spectrum, called a diffraction spectrum, plots
the number of X-rays detected as a function of energy. For a certain set of
energies, strong scattering is observed due to constructive interference between
waves scattered by successive crystalline planes. This process is called Bragg
diffraction [17] and is described in more detail in Chapter 2. The peaks in the
spectrum produced by this intense scattering are called diffraction peaks. The
positions of the diffraction peaks in the spectrum depend on the crystal structure
of the material under investigation. Since all crystals have a unique structure,
each also diffracts a unique set of X-ray energies. Hence, by detecting these
energies, a crystal or mineral species may be identified and quantified.
The EDXRD method for X-ray diffraction measurement differs from the
more widely used conventional, or angle-dispersive X-ray diffraction (ADXRD)
method. An ADXRD instrument measures the angles through which X-rays of a
single energy are diffracted and therefore a diffraction spectrum of diffraction
angle versus intensity is produced.
The difference in the way that diffraction is measured has important
consequences for the applications to which the techniques are best suited.
EDXRD is rarely used in laboratory analysis of crystal structures, since ADXRD
is capable of providing much better diffraction peak resolution. The higher
resolution of the ADXRD instrument enables much more information to be
derived from the diffraction spectrum than can be obtained from a lower-
resolution EDXRD spectrum. However, in on-line analysis, it is sufficient to
46. 10
measure the key mineral phases contained in the process stream. This does not
necessarily require the extremely high resolution of an ADXRD instrument.
EDXRD also possesses a number of properties that make it better suited to on-line
analysis than ADXRD, with most of its advantages stemming from the use of
much higher X-ray energies. High energies enable the unprepared, coarse
material of an industrial slurry to be analysed with relative ease and at a lower
cost compared to ADXRD. A comprehensive review of both X-ray diffraction
techniques is presented in Chapter 2.
EDXRD has been put to use in a number of practical applications, but until
now it has not been used for on-line mineral analysis. Most of these applications
are those that require the rapid identification of unprepared materials – the area in
which EDXRD excels. Many examples can be found in medical fields such as
bone densitometry [18-20], where EDXRD has been proposed as an alternative to
dual energy X-ray absorptiometry (DEXA) [21], and coherent scatter imaging
[22-24]. Other areas where EDXRD has found use include security and baggage
screening [25-27], non-destructive testing [28,29] and materials investigations
[30-33]. EDXRD has also been used for in situ investigations of materials as they
undergo physical changes during processes in real time. [34,35]. In situ studies
have many commonalities with on-line measurement, such as the need to collect
data rapidly and difficult sample environments.
1.4 – Thesis Outline
The aim of this thesis is to develop the science and methods involved in
designing EDXRD analysers for on-line analysis of mineral slurries. The ultimate
goal is to demonstrate that EDXRD has the potential to be a viable tool for
monitoring the mineralogy of process streams for the purpose of plant control. In
order to pursue this goal, the following research was undertaken:
1. An investigation into the properties of EDXRD analysers with particular
emphasis on the area of on-line analysis.
2. The development of tools and methods for optimising the design of
EDXRD slurry analysers.
47. 11
3. The design and construction of a prototype EDXRD instrument suitable
for measuring both dry powder and slurry samples.
4. The conducting of a variety of experiments to: (i) verify the accuracy of
the optimisation tools in point 2, (ii) investigate the EDXRD properties of
a variety of mineral samples and slurries, and (iii) test the accuracy to
which mineral phases contained in samples can be quantified with the
EDXRD analyser and hence demonstrate the applicability of EDXRD for
mineralogical analysis.
Chapter 2 presents essential background information on the physics of
X-ray interactions with matter and X-ray diffraction. Following this, an
introduction into the methods for measuring X-ray diffraction is presented. Both
the ADXRD and EDXRD methods are explained. Descriptions of two on-line
mineralogical analysers that have been developed using ADXRD are also
presented. This discussion is used to explain why in most cases EDXRD is a
more suitable method for the application of on-line analysis than the ADXRD
technique.
In Chapter 3 a discussion is presented of the main issues that must be
considered when designing an EDXRD analyser. This includes studies that can
be found in the literature and new research.
In Chapter 4 a method for modelling diffractive X-ray scattering from
crystalline and amorphous materials using the EGSnrc Monte Carlo code is
presented. The development of the method is described, including the equations
for calculating the coherent scattering cross sections and form factors for crystals,
amorphous materials and mixtures of the two, and a computer code developed to
calculate this data. Also, modifications to the EGSnrc code to implement the
physics of X-ray scattering from crystalline powders are described.
The design of a prototype laboratory EDXRD analyser is presented in
Chapter 5. The process involved in designing the instrument is described, as well
as predictions of the level of performance obtained with the instrument. The
performance of the analyser is compared against these predictions in Chapter 6.
The validity of the method for modelling diffractive scattering is also studied in
48. 12
Chapter 6 through comparisons between EDXRD spectra obtained with the
prototype analyser and Monte Carlo simulation.
Chapter 7 presents investigations into two types of material with the
prototype analyser. The first is a suite of samples containing six minerals that are
important in a variety of processing industries. The spectra collected with the
EDXRD analyser from each sample are analysed in order to determine how
accurately the mineral components can be quantified. The second material
studied is an industrial potash slurry obtained from a processing plant. The
EDXRD properties of the slurry, such as particle size and solids loading effects,
are investigated. A synthetic version of the slurry is also studied to determine if
the mineral components can be quantified using EDXRD. In Chapter 8, the
spectra of the samples in the six mineral and synthetic potash suites are modelled
using the Monte Carlo simulation code. The aim of this work was to determine
whether the analysis accuracies obtained with the EDXRD analyser could be
predicted using Monte Carlo modelling.
In Chapter 9, a computer code developed for optimising the design of an
EDXRD analyser is explained. The code uses simulated Monte Carlo spectra to
derive performance data for a large number of designs. This data is used to find
the optimal instrument geometry for measurement of a given material. The code
can complete this task in a matter of seconds, saving months of design work.
Finally, in Chapter 10, the code, plus all the other knowledge gained in this
research, is used to design a new EDXRD slurry analyser suitable for on-line
measurement of potash slurries.
49. 13
Chapter 2
Photon Interactions with Matter and X-ray Diffraction
2.1 – Interaction of X-rays with Matter
There are a number of mechanisms through which X-rays interact with
matter. This section provides a discussion of the mechanisms important in the
photon energy region used in EDXRD analysis.
2.1.1 – Photoelectric Effect
The photoelectric effect is a process where the energy of a photon is
transferred to an electron of an atom. The incident photon is completely absorbed
in the interaction and the electron is ejected from the atom with an energy of
ϕν −= hEK , (2.1)
where νh is the photon energy, h being Planck’s constant and ν being the
photon’s frequency, and φ is the energy required to remove the electron from the
atom. The ejected electron usually originates from one of the innermost shells.
This leaves a vacancy in one of the bound shells of the absorber atom, which can
be filled by either a cascade of the electrons moving down from higher energy
shells or less commonly by the capture of an electron from the surrounding
environment. In both cases characteristic X-rays are emitted when electrons move
to lower energy shells; the energy of the X-ray photons created being equal to the
difference in the binding energy of the original and final shells. It is also possible
that some of the excitation energy is carried away from the atom through the
creation of Auger electrons. Photoelectric absorption is generally the most
important interaction process for low energy photons.
50. 14
Figure 2.1 - The photoelectric effect. The atom absorbs the incident photon of energy hν
and ejects a K shell electron. An L shell electron fills the vacancy and emits a photon of
energy equal to the difference in the shell binding energies E2-E1.
2.1.2 – Rayleigh Scattering
Rayleigh scattering is a process in which a photon is scattered by an atom
without losing energy. When an X-ray approaches a free electron, the oscillating
electric field of the X-ray sets the electron into vibration at the same frequency as
the incident X-ray. According to electromagnetic theory, an accelerating electric
charge emits energy in the form of electromagnetic radiation; hence the oscillating
electron emits electromagnetic radiation with the same frequency and phase as the
incident wave. In this process, the incident wave is said to be ‘scattered’ by the
electron. The differential cross section for this scattering process (Thompson
scattering) is given by [36]
( )Θ+=
Θ
22
0 cos1
cos
rπ
d
σd T
(2.2)
where 15
0 108.2 −
×=r m is the classical electron radius and Θ is the scattering
angle.
51. 15
Figure 2.2 - Thompson scattering of a photon. The photon is scattered through an angle
Θ and retains the same energy and phase as the incident photon.
For electrons bound to an atom, the scattering process is more complicated
due to interference effects between the waves scattered by each electron in the
atom. The amplitude of the resulting scattered wave is a function of a quantity
known as the momentum transfer x, which is defined as
⎟
⎠
⎞
⎜
⎝
⎛ Θ
=
2
sin
1
λ
x (2.3)
where λ is the wavelength of the incident photon. The scattering amplitude is a
maximum in the direction parallel to that of the incident X-ray (Θ = 0°) and a
minimum in the antiparallel direction (Θ = 180°). The interference effect is
expressed in terms of the so-called atomic form factor F(x), which is formally
defined as the Fourier transform of the electron charge distribution. The atomic
form factors of the elements Z = 1 to Z = 100 have been tabulated by Hubbell and
Øverbø [37]. The application of the atomic form factor to the Thompson
scattering cross section for scattering from a free electron gives the cross section
for coherent (or Rayleigh) scattering from an atom
( ) ( ) 222
0 cos1
cos
xFrπ
d
σd R
Θ+=
Θ
. (2.4)
Rayleigh scattering is generally only important for photons with energy less than
about 100 keV.
52. 16
2.1.3 – Compton Scattering
Compton scattering [38] occurs when a photon interacts with a loosely
bound or free electron. During the interaction some of the photon’s energy is
transferred to the electron and the photon is deflected at an angle Θ with respect to
its original direction. The phases and frequencies of the incident and scattered
photons are not necessarily the same and therefore Compton scattering is a form
of incoherent scattering.
Figure 2.3 - Compton scattering from a free electron. The energy of the incident photon
is shared between the scattered photon and the recoil electron.
The differential cross section for Compton scattering from a free (loosely
bound) electron in an atom of atomic number Z is given approximately by the
Klein-Nishina [38] formula
KN
KN
ZXrπ
d
σd 2
0
cos
=
Θ
, ⎥
⎦
⎤
⎢
⎣
⎡
Θ−+⎟
⎠
⎞
⎜
⎝
⎛
= 2
2
sin
c
cc
KN
k
k
k
k
k
k
X (2.5)
where k is the energy of the incident photon in units of electron rest energy and kc
is scattered photon energy given by,
)cos1(1 Θ−+
=
k
k
kc . (2.6)
53. 17
The assumption that the electron is free is valid for high-energy photons
where the binding energy of the electron is negligibly small compared to the
photon energy. This assumption breaks down for low energy photons and small
scattering angles because, for Compton scattering to occur, the amount of energy
transferred to the electron must be sufficient to remove it from the atom.
Therefore, Compton scattering tends to be suppressed in the forward direction.
For Compton scattering between a photon and a bound electron, the scattering
cross section is approximated by
)cos,(
cos
2
0 Θ= kSXrπ
θd
σd
KN
comp
. (2.7)
where S(k,cosΘ) is the incoherent scatter function [38]. The values of S(k,cosΘ)
can be found in the tables of reference [37].
2.2 – Diffractive (Bragg) Scattering
The phenomenon of X-ray diffraction was discovered by German physicist
Max von Laue in 1912 after finding that when a beam of X-rays was passed
though a crystal of copper sulphate, a pattern of spots developed on a
photographic plate positioned behind the crystal [17]. X-ray diffraction is a
phenomenon that occurs when photons undergo coherent scattering from
materials in which there is a degree of molecular ordering. This leads to varying
degrees of constructive and destructive interference to occur between scattered
photons, resulting in intense scattering at specific angles. X-ray diffraction is
observed most strongly from crystalline materials in which the atoms are arranged
in a highly ordered structure. In a crystal regularly spaced atomic planes can be
identified, where the distance between adjacent planes is in the order of a few
angstroms. In 1913, William L. Bragg showed that X-rays scattered from
successive planes will be in phase and hence constructively interfere if the
difference in the path length travelled by two waves is an integral multiple of the
wavelength and the scatter angle equals the angle of incidence [17] (see Figure
54. 18
2.4). This phenomenon can be expressed mathematically through the well-known
Bragg law
θλ sin2dn = (2.8)
where λ is the X-ray wavelength, d is the atomic plane spacing, θ is the angle of
incidence and reflection and n is an integer denoting the order of diffraction. For
a given X-ray wavelength, constructive interference hence occurs at angles that
satisfy the Bragg law for each spacing d. Since all crystal types have a unique set
of d-spacings, different crystals diffract X-rays at a unique set of angles for a
given incident X-ray wavelength, or equivalently crystals diffract a unique set of
wavelengths at a given angle. This fact is exploited in X-ray diffraction and
crystallography analysis where either the angles or wavelengths of diffraction are
measured to calculate the d-spacings of the crystal(s) under investigation. The
diffraction information can be used to identify the crystal and investigate many of
its other properties.
Figure 2.4 - Bragg diffraction from a set of atomic planes with spacing d. Diffraction can
only occur if the incident and scatter angles are equal.
The cross section for Bragg scattering from a powdered crystalline
material (a crystal that has been crushed into small grains) is given by [40]
55. 19
( )∑
⎥
⎥
⎦
⎤
⎢
⎢
⎣
⎡
⎟
⎟
⎠
⎞
⎜
⎜
⎝
⎛ Θ+
⎟
⎟
⎠
⎞
⎜
⎜
⎝
⎛
=
hkl
hkl
hkl
c
B xFmd
NV
λr
σ
2
222
0
2
cos1
2
(2.9)
where N is the number of atoms contained in the unit cell of volume Vc and m, d
and Fhkl are the multiplicity, d-spacing and structure factor of the plane hkl
respectively. The multiplicity m adjusts the magnitude of the cross section
according to the number of planes that contribute to a particular hkl reflection. It
should be noted that Equation 2.9 is only valid if λ, θ and d satisfy the Bragg Law.
The structure factor of a plane hkl accounts for the interference between waves
scattered by different planes and is calculated as
( ) ( ) ( )
∑=
++−−
j
jlwjkvjhuiπjM
jhkl eexFxF
2
(2.10)
where j is the number of atoms in the unit cell, ( )xFj is the atomic form factor of
the jth atom, jM
e
−
is the Debye temperature factor and uj, vj, and wj are the
fractional coordinates of the atoms in the unit cell. The structure factor describes
both the amplitude of the diffracted wave (proportional to ( ) 2
xFhkl ) and its
phase.
2.3 – Methods for X-ray Diffraction Measurement
Various experimental methods exist for measuring the diffraction of
X-rays from materials. These methods can be broadly categorised into two
classes: (i) angle-dispersive X-ray diffraction (ADXRD) and (ii) energy-
dispersive X-ray diffraction (EDXRD). The follow sections provide an overview
of the instruments and methods involved in measuring X-ray diffraction using the
angle- and energy-dispersive techniques.
56. 20
2.3.1 – Angle-Dispersive X-ray Diffraction
There are a number of different experimental setups in use that measure
X-ray diffraction through angular dispersion. These include the Debye-Scherrer,
focusing and pinhole methods [39]. However, here we focus on the method that
has been employed in the field of on-line mineralogical analysis, namely the
diffractometer method. A schematic diagram of the setup of a typical angle-
dispersive X-ray diffractometer is shown in Figure 2.5. The essential components
of a diffractometer are an X-ray tube, collimators to define the incident and
diffracted beams, a monochromator, sample, and a goniometer upon which a
sample stage and detector are mounted.
The X-ray tube emits a beam of polychromatic X-rays, which are
produced by an electron beam impacting a heavy metal target. The electrons are
accelerated toward the target due a large potential (typically tens of kilovolts)
created between the target and the electron emitting filament. A continuum of
X-ray energies are produced by electrons decelerating in the target. X-rays
produced by this process are called bremsstrahlung. The continuum extends up to
Figure 2.5 - Schematic of an ADXRD diffractometer. The beam emitted by the
X-ray tube is monochromated, collimated and passed onto the sample. A detector is
rotated about the sample so that the diffracted intensity as a function of angle is
measured.
57. 21
the operating voltage, for example an operating voltage of 100 kV produces
X-rays of up to 100 keV. Fluorescent X-rays characteristic of the target material
are also produced. An example spectrum is shown in Figure 2.6.
Figure 2.6 - Example X-ray tube spectrum for a tungsten target and operating voltage of
100 kV. The sharp lines are characteristic lines of the target.
In an ADXRD analyser, the polychromatic X-ray beam exiting the tube is
monochromated and then passed through collimator slits to produce a
unidirectional beam of X-rays directed at the sample. The monochromator is a
crystal set at an angle relative to the incident beam such that the X-ray wavelength
applicable for the measurement is selected by diffraction. This wavelength is
generally the K fluorescent radiation of the X-ray target material. Popular choices
of wavelengths include Mo Kα (0.711 Å), Cu Kα (1.542 Å), Co Kα (1.790 Å),
Fe Kα (1.937 Å) and Cr Kα (2.291 Å). In a typical laboratory measurement, the
sample is a loosely packed crystalline powder where in some cases the surface
subjected to the X-ray beam is polished to create a highly smooth surface. The
sample axis is rotated during measurement at half the angular velocity of the