Physicochemical methods of mineral analysis

PHYSICOCHEMICAL METHODS OF MINERAL ANALYSIS PHYSICOCHEMICAL METHODS OF MINERAL ANALYSIS Edited by Alastair W Nicol Department of Minerals Engineering University of Birmingham Birmingham, England PLENUM PRESS • NEW YORK AND LONDON Library of Congress Cataloging in Publication Data Main entry under title: Physicochemical methods of mineral analysis Includes bibliographical references and index Mineralogy, Determinative Materials-Analysis I Nicol, Alastair W QE367.2.P49 549'.1 72-95070 ISBN-13: 978-1-4684-2048-7 e-ISBN-13: 978-1-4684-2046-3 DOl: 10.1007/978-1-4684-2046-3 ©1975 Plenum Press, New York Sofkover reprint of the hardcover I st edition 1975 A Division of Plenum Publishing Corporation 227 West 17th Street, New York, N.Y 10011 United Kingdom edition published by Plenum Press, London A Division of Plenum Publishing Company, Ltd Davis House (4th Floor), Scrubs Lane, Harlesden, London, NWI0 6SE, England All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher To Muriel and Laki CONTRIBUTORS H Bennett British Ceramic Research Association Queens Road, Penkhull Stoke-on-Trent ST4 7LQ, England K G Carr-Brion Warren Spring Laboratory P O Box 20, Gunnelswood Road Stevenage, Hertfordshire SG I 2BX, England v C Farmer Department of Spectrochemistry Macaulay institute for Soil Research Craigiebuckler, Aberdeen AB9 2QJ, Scotland G L Hendry Department of Geology University of Birmingham, P.O Box 363 Birmingham BI5 2TT, England V I Lakshmanan Department of Minerals Engineering University of Birmingham, P O Box 363 Birmingham BI5 2TT, England G J Lawson Department ofMinerals Engineering University of Birmingham, P.O Box 363 Birmingham BI5 2TT, England M H Loretto Department of Physical Metallurgy and Science ofMaterials University of Birmingham, P O Box 363 Birmingham BI5 2TT, England R C Mackenzie Macaulay Institute for Soil Research Craigiebuckler, Aberdeen AB9 2QJ, Scotland G D Nicholls Department of Geology University ofManchester Manchester MI3 9PL, England A W Nicol Department of Minerals Engineering University of Birmingham, P O Box 363 Birmingham BI5 2TT, England Department of Physical Metallurgy and Science of Materials University ofBirmingham, R O Box 363 Birmingham BI5 2TT, England H N Southworth M Wood Department of Geology University of Manchester Manchester MI3 9PL, England FOREWORD This book has developed from a short residential course organised by the Department of Minerals Engineering and the Department of Extra Mural Studies of the University of Birmingham The course was concerned mainly with physical methods of analysis of minerals and mineral products, and particular regard was given to 'non-destructive' methods, with special emphasis on newly available techniques but with a review of older methods and their recent developments included therein Mineral analysis is obviously of great importance in all the stages of mineral exploration, processing, and utilisation Selection of a method for a particular mineral or mineral product will depend upon a number of factors, primarily whether an elementary analysis or a phase or structure analysis is required It will also depend upon the accuracy required The chapters in the book covering the different methods show the range of useful applicability of the methods considered and should prove valuable as an aid in selecting a suitable method or methods for a given set of circumstances The book, referring as it does to the majority of the instrumental methods available today (as well as, for comparison, a useful contribution on the place of classical wet chemical analysis) will be valuable to the student as well as to those analysts, research workers, and process engineers who are concerned with the winning, processing, and utilisation of minerals and mineral products Stacey G Ward PREFACE The past decade has seen great strides being made in all branches of science, and nowhere more than in the field of analysis and characterisation of materials, both in the number and the variety of techniques that have become available In the specific area of physicochemical methods of analysis, based on monitoring the interaction of beams of electrons or electromagnetic radiation with matter, this has resulted not only in new and powerful additions to the analysts' repertoire but also in the upgrading of older methods to give them improved accuracy and flexibility, and a new lease on life for some We may cite, in particular, the electron probe microanalyser, the scanning electron microscope, Auger spectroscopy and non-dispersive X-ray fluorescence analysis, the development of which has allowed us not only to determine the elemental and phase compositions of a material, but also to look in detail at the distribution of the elements among the phases present, or study elemental concentrations in the extreme surface layers in a way that was quite impossible in previous years Such techniques are very appropriate to the particular problems encountered in the study and analysis of minerals and mineral products, such as glass, ceramics, cement, etc., and the information that they can give may prove crucial in explaining, for example, why a given lead-zinc ore is not amenable to beneficiation by froth flotation; investigation of one such 'problem' ore with the electron probe microanalyser showed that the galena was heavily contaminated by zinc at the sub-micron level and comminution could not separate the two phases The methods also are important as the basis of sensors for automatic control systems which are currently being developed But, as ever, the main problem in applying all these techniques lies in translating the methods from the research laboratories, where they have been developed, to the industrial environment, where they are needed It is, moreover, a basic tenet of the Editor's method of teaching that a student will be able to understand a process better or apply a technique more sensibly and effectively if he is familiar with the scientific principles and the basic theory that underlie the process or technique Too often in analysis does the 'black box syndrome' raise its ugly head as the operator, working by rote, pushes button A, turns knob B until the pointer C reaches the line, and copies a number from the dial D, without ever really knowing how the reading is obtained or what factors may intrude to spoil the accuracy of the final figure This lack of knowledge of basic principles, especially in conjunction with an illuminated digital read-out, may result in xi Preface xii a touching, if sometimes disastrous, faith in the magical properties of the numbers that appear in the box, with no thought of what the number actually signifies in terms of the parameter being measured, of how this value is related to the required parameter, or of the degree of confidence that can be placed in the accuracy of the number It is all too easy to forget that the instrument records the signal that it receives from the test material, and not necessarily the signal that the analyst wants it to record Also, errors, and sometimes gross errors, can creep into an analysis if the interference caused by an apparently innocent 'other ion' is not identified and allowance made for it Reproducibility is so often confused with accuracy because people forget that high precision can mean simply that the instrument is making the same mistake on each reading! Therefore, this book, as was the Residential Course from which it sprang, has been planned to try to present an account of these new methods with particular reference to their use in mineral analysis It discusses the application of physicochemical methods of analysis, using principally electromagnetic and electron beam stimulation and sensing techniques, to materials of especial interest to the minerals engineer, and puts particular emphasis on the so-called 'non-destructive' methods of analysis Throughout the book, the aim has been two-fold, to introduce the various techniques and give a description of the type of information each provides together with an account of the good and bad points of the method, its problems, etc., and to show how each method works in terms of the basic scientific principles involved The book begins, therefore, with a chapter on basic principles, atomic theory, bonding, crystal field theory, the interaction of energy with matter, and an introduction to the detectors used in physko~hf''''-!'.:~! ~:!l~'~i~ Th;: ;;.;;;;:t f0ul dli:lptt:rs ciiscuss elemental analysis by optical and X-ray fluorescence methods, radiotracer techniques, and spark source mass spectrometry A chapter on the application of X-ray methods to automatic control follows, then a section phase analysis using X-ray diffraction, electron microscopy, thermal methods and infra-red spectroscopy The last two chapters present an account of some of the very new techniques for analysis, including electron probe microanalysis, scanning electron microscopy, Auger spectroscopy, and the field ion microscope, plus a review of analytical methods which relates the position of physicochemical analysis to absolute, wet chemical techniques and assesses the usefulness of these new methods in a variety of situations The original Course also included reflected light microscopy as one of its topics, but circuinstances outside the Editor's control have made it impossible to include this in the book Readers will find that each chapter contains a section on the basic theory particularly relevant to that topic, which may be omitted on a cursory read-through, but which is intended to improve the reader's understanding of the method, by supplementing the treatment given in Chapter Of course, a book such as this is not the work of one person, and I wish to record my most sincere thanks to all who helped me in its preparation on Preface xiii Firstly, my authors, who patiently bore every request made of them and allowed me to recast their chapters often to a considerable extent in a search for uniformity of coverage of the various methods Secondly, the many firms who supported the original Course and supplied photographs and figures for the book; acknowledgements are made separately throughout the chapters Thirdly, Professor Ward and Dr Lawson for their continuing help and support throughout the gestation period, and particularly Dr Lakshmanan for being my conscience at all times, and for providing much needed encouragement when it looked as if the end would never come! Fourthly, Dr I Langford of the Department of Physics for performing the invaluable service of editing my own chapter, on X-ray diffraction, and the office staff of the Department of Minerals Engineering for their help in preparing parts of the typescript And finally, my wife for bearing the total chaos that reigned in our study while the magnum opus was becoming a reality Truly, without their help this book would never have been Alastair W Nicol University of Birmingham CONTENTS Chapter Introduction, Basic Theory and Concepts A W Nicol and V L Lakshmanan Chapter Optical Spectrometry G J Lawson 55 Chapter X-ray Fluorescence G L Hendry 87 Chapter Radiotracers in Minerals Engineering V I Lakshmanan and G Lawson 153 Chapter Elemental Analysis Using Mass Spectrographic Techniques G D Nicholls and M Wood 195 Chapter X-ray Techniques for Process Control in the Mineral Industry K G Ca"-Brion 231 Chapter X-ray Diffraction A W Nicol 249 Chapter Electron Microscopy M H Loretto 321 Chapter Infra-red Spectroscopy in Mineral Chemistry V C Farmer 357 Chapter 10 Thermal Analysis R C Mackenzie 389 Chapter 11 Scanning Electron Microscopy and Microanalysis H N Southworth 421 Chapter 12 Review of Analysis H Bennett 451 Subject Index 485 xv 494 measurement of, 383ff of minerals, 358, 373 of mineral dust, 374 of phosphates, 373, 375 of oxides and hydroxides, 375 of pigments, 373, 375 quantitative, 384f reflection, 383 of silicates, 375 transmission, 372ff Infra-red spectrometers, 378ff choice of, 380f differential recording, 383f double-beam, 380, 383 filter-grating, 380 prism, 380 spectral range of, 380 In-stream XRF analysis head, 235 Intensity ratio, 142 Interelement effects, 139,239 Interfer.ence, 218 chemical, 73 constructive, 259 correction for, 217, 220ff, 239 optical, 73ff, 76 second order, 226 Inter-laboratory tests, 463f, 467f Iodine, 174, 176 Ion, 208ff, 392 monoatomic, singly charged, 209,212,214,224 monoatomic, multiply charged, 209f,216, 224, 226 polyatomic, singly charged, 209, 217,224 polyatomic, multiply charged, 212f,216 polyatomic mixed, 217f population, 210 primary, 440 secondary, 440 trapped, 213, 221 Ion beam, 196, 210ff chopping of, 201, 222ff composite, 21 Of dispersion of, 196, 211 f energy selected, 211, 213 excitation of, 206ff intensity of composite, 224 pulse, 222f recording, 206f, 213ff Subject Index by electrical detector, 213, 224f electromagnetic peak scanning, 197, 225 by sensitised photoplate, 197, 213f,225 voltage peak switching, 225 resolution of, 216f spectrum, 215 interpretation of, 214ff Ion beam suppress assembly, 213, 222 Ion pairs, 32, 35, 39 Ion exchange, 74, 154, 172, 227, 382 liquid resin, 459 Ion probe microanalyser, 439f Ion sputtering, 440f Ion track, 181 Ionisation, 181 line of, 183 sample, 208 thermal, 227 Iridium, 176 Iron, 66, 82, 136, 176, 214, 216, 238ff, 459, 461, 465 pig, 188 Iron ore, 238 Irradiation, 165, 170 neutron, 165, 183 time ot, 166 Isomorphous substitution, 363, 367 disordered, 363f ordered, 363f Isotope, 154,214,446 daughter, 18, 156, 158, 177 half life, 155ff, 166, 173, 189 determination of, 157ff long lived, 158f mass defect in, 216f mass number of, 157, 216f, 376 parent, 157 radioactive, 18, 154ff short lived, 158f target, 165 Isotope dilution analysis, 178ff, 227 direct, 178 substoichiometric, 179 Isotope exchange reactions, 179 Subject Index Isotopic abundance, 166,173,216, 220f,227 Isotopic composition, 227 Isotopic substitution, 377 of H by D, 376f Isotopic weight, 24 Jaw crusher, 454f JCPDS File, 289ff, 301,304,331, 373,408 computer aided search of, 293f Kcxt!Kcx2 doublet, 253f, 276 KI3-line, 253f Kaolinile, 335,401,403,405 KBr disc, 382f KCl, 299, 382 K C0 ,457 KI,382 KOH,457 Kikuchi lines, 334, 342ff, 349 Kikuchi maps, 341, 342, 343ff, 351 Kikuchi pattern, 431 Kilchoanite, 33lff Kimberlite garnet, 315 Kinematical theory, 346 Kossel camera, 438 Kramer's formula, 93 Kyanite, 457, 467 LaB ,446 Lamp deuterium, 60 hollow cathode, 76f output modulation of, 78 storage rack for, 77 turret for, 77, 83 tungsten, 60 Lanthanum, 82, 176, 216,446f oxide, 134ff, 148, 150 Laser, 480ff He-Ne, 481 CO ,481 Laser light scattering analyser, 480 Laue diffraction, 250, 255, 306 495 Laue equations, 250, 255f Laue photographs, 256, 306f Laue zones, 334 Lauric acid, 189 LCAO theory, 11 Lead, 21,82, 143, 176,179,238, 242, 470f Lead castle, 160 Lead filter, 181 Lead glass disc, 206 Lead selenide, 481 Lead stearate, 103, 110, 432f, 437 LEED (see under Electron diffraction) Lens electromagnetic, 322, 431 intermediate, 323, 327f objective, 323, 328 projector, 323, 328 Lexan, 183 Libration, 360ff Ligand field theory, 12ff, 15, 436 Ligands, 13, 15 arrangements of, 14 Light, velocity of, 24, 48, 90 Light beam, monochromatic, 61 Light sources, 60, 64, 76 Light element analysis, 88, 92, 437, 440 Lime, 187f Linde A corundum, 301 Lindemann tube, 266 Line broadening, 261, 30lff, 342 instrumental, 302f experimental, 302f Line spectra, Line width at half maximum, 301 f Lithium, 82, 164, 465 carbonate, 129ff, 134, 148,457 tetraborate, 129ff, 134,457 Lunar dust, 198,206,227 Lutetium, 176 Mackinawite, 438 Magnesile, 457, 462 AN31 and AN32, 465 Magnesium, 82, 102, 146, 157, 176,185,217,459,465 (Mg,Fe )Si0 , 315 496 Mg(N03 h'6H saturated solution,402 MgO,372 Magnet current, 225 Magnetic anomaly, 13 Magnetic coils, 211 Magnetic moment, 13 Manganese, 82, 136, 180, l85f, 459,465 Manganic oxide, 459 Margarite, 364 Mass, 370, 395 reduced, 24, 376f Mass spectrometry (see under Spectrometry) Mass/charge ratio, 196,212, 2l4ff, 225 non-integral, 216 Masking agent, 172 Mathematical model, 234 Matrix, 198ff Matrix effect, 132, 136, 239 in solutions, 137ff Matthews Key-Sort Index, 289 Maxwell-Boltzmann distribution, 3, l6ff, 23, 57, 76 Mercury, 82, 176 Mesosiderite, 183 Metal, 126f, 129, 196 Metal-slag reaction, 187 Metallurgy, 185, 187 Meteorite, 183 Methane, 10,38, 105 Mica biotite, 128, 377 hydrobiotite, 404 illite, 403, 406 muscovite, 364, 377 phlogopite, 325 Microanalysis, 422, 430, 43lff, 470ff,478 Microdensitometer, optical, 218, 267,301,315 Micrograph, electron, 322ff, 427ff, 470ff stereo-pair, 322, 351, 418 Microscope electron scanning (see Scanning Electron Microscope) electron transmission (see Trans- Subject Index mission Electron Microscope) optical, 426, 431 travelling, 267 Microscopy chemical, 476 optical, 426, 431 scanning electron, 424ff, 476 transmission electron, 321 ff, 476,482 Microstructure, 422, 430, 438, 446 Miller Indices, 260, 339, 349, 353 notation, 258 Mineralogy, 234 Mirror plane, 256, 367 Mixed layering, 277 Mixing time, 382 Molecular bonding, 10, 57 Molecular dipole, 15 Molecular groupings, 70 Molecular orbital treatment, 13 Molecular spectra, Molybdenum, 82, 91, 176, 185, 238, 242, 370 Molybdenum trioxide, 327 Monitor circuit, 212 Monochromator optical, 78 grating, 83 for X-rays (see Crystal monochromator) Montmorillonite, 392, 403f, 408f abnormal, 406 exchange cation in, 404, 409 hydroxyl groups in, 392 iron in, 372, 377 interiayer water in, 392 Morphology, 430 Mortar agate, 38lf steel, 382 mullite, 381 Movements, atomic and molecular, 23ff Mowiol,129 Multi-channel analyser (see under Analyser) Multi-dilution technique, 466 Multiplication factor, 261, 297 Mull, 382f Mullite, 381 f, 467 Subject Index NaCl, 372, 383 NaBr,383 NaOH, 405, 457 Na2S204,405 NaxK I-xCI, 363f National Bureau of Standards, 401 Nebuliser unit, 71, 77 Negative intercept, 75 Nekoite,410 Nelson-Riley extrapolation function, 280, 296 Neodymium, 176 Neon, 108,444 Neutrino, 157 Neutron, 18, 154f fast, 164, 167, 169 resonance, 169 thermal, 18, 164, 167, 169 Neutron activation analysis, 18, 167f~ 186,474,482 Neutron flux, 167ff, 176 monitor for, 170 Neutron source, 167ff nuclear reactor, 169 portable, 184 sealed, 167 small accelerator, 168f, 174 Nickel, 12,65,82,185,214,217, 460 Nickel foil, 253 Nickel dimethylglyoxime, 12, 66 Niobium, 82, 176, 185f Noise, electronic, 44, 46 Non-crystalline compounds, 372, 385 Non-metallics, 185 Nuclear reactions, 18, 163ff Nuclear reactor, 18,165,169,178 pulsed, 169 Nucleons, 18, 216 Nucleus, 18, 154, 216, 326 activated, 18, 154ff, 165f daughter, 156, 158, 177 He ,177 parent, 19, 157f, 165 product, 165 target, 164f Nujol,383 Null balance, 62 497 O-D group, 367, 376 stretching vibration, 367 O-H group, 362, 367, 376 stretching vibration, 362, 367, 383 Optical absorption spectroscopy (see under Spectroscopy) Optical clarity, 62, 66 Optical density, 62, 78, 182, 2l8f, 221 Optical emission spectroscopy (see under Spectroscopy) Optical filter, 61 Optical wedge, 68 Orbital anti-bonding, 10 atomic, 5ff, 10ff, 19,22 bonding, 1Off d-, 14 hybrid atomic, 10 molecular, 1Off, 19, 22, 29, 39 Orbital splitting, 15 Ore, 186f, 261, 467 Ore assay, rapid, 184 Oscillation photograph, 308 Oscillators, 3, 360ff Osmium, 176, 185 Output modulation, 78 Oxidation, 377 Oxidation state, 65, 180,436, 442, 444 of iron, 377 Oxides, 367, 381 alkali, 381 alkaline earth, 381 Oxidising agent, 129 Oxygen, 110, 176, 185f, 432, 474 Pair production, 163 Palladium, 82, 96, 176, 185 Palladium/gold alloy, 426 Palygorskite, 404 Paper chart recorder (see Chart recorder) Particle, charged, 196 Particle shape, 370f Particle size, 234, 240, 401 f measurement, 301ff, 303f 498 Pauli exclusion principle,S PbC12 ,179 Pb(N0 h, 179 PbS, 98, 422 (see also Galena) Peak area, 395f, 409 Peak height, 63, 218 Peak intensity, 12If Peak overlap, 67, 102ff, 143f, 403, 408 Peak position, 120 Peak profile, 63, 109, 278f, 30 If, 436 Peak resolution, 43ff, 10 Iff, 107, 108f, 142f, 174f; 214ff, 270, 274 Peak shift, 15f, 104, 278f, 295, 363, 370f, 436 Peak scanning, electronic, 224f Peak search by computer, 118,304 Peak width, 63 (see also Line broadening) Pelleting, 235 Perkin-Elmer Company (see under Spectrometers) Pennine,404f Peridotite, 144 Periodate, 459 Permanganate ion, 65,459 Phase equilibria, 438 1,1 O-Phenanthroline, 459 Phosphate, 4;~ Phosphorus, 186f, 222,238,433 Photoelectric cell, 28ff, 62, 68 Photoelectric processes, 163 Photoemissive cell, 29 Photographic film, 26ff, 181, 252 blackening of, 26, 181 development of, 27 fogging of, 27f stripping of, 252 Photographic image, 26 Photographic plate, 25, 84, 181 Ilford Q2, 213ff, 219 Photographic recording, 213ff, 262ff,400 Photometer, flame, Off, 459, 465 Photomultiplier tube, 30, 40, 72, 77,81 Photon, 3f, 15, 18ff, 27, 33, 114, 163, 167 energy of, 3f, 90, 326, 443 wavelength, 90 Subject Index X-ray, 90, 106,259 X-ray elastically scattered, 260 X-ray inelastically scattered, 260 Photopeak, 174 Photoplate magazine, 213 Pipeline wear, 190 Piperidine, 405 Planchet, 161 Planck's constant, 3, 90, 325, 424 Plasma, 208 Plasmon interaction, 422 Platinum, 82,176,185,203,325 Plutonium, 114,241 p-njunction,41 Point of departure, 393f Polyethylene, 203 powder disc, 383 Polyethylene oxide, 458 Polymorphic transformations, 25, 392f Polytypism, 342 Population, atomic, 20 Positron, IS Potassium, 29, 70, 74, 82, 104, 121, 144, 146, 176, 185, 238, 242 Potassium borate, 457 Potassium carbonate, 201,457 Potassium perrhenate, 201 Powder, 232, 234, 238, 244f mUIluluiucfalic, 11e XRD analysis of, 250ff XRF analysis of, 127ff Praseodymium, 176 Precession camera, 309f, 314 Precipitate, 337, 341, 348ff Precipitation, 127, 17lf Precision, 121, 123, 146,176,198, 222,225,228,244,466,468 instrumental, 199,224,239 sampling, 199f, 222, 224 Preferred orientation, 245, 264, 281,290,383 Prism, 56, 60, 72, 77 alkali-halide, 380 quartz, 61, 84 Process control, 231 ff automatic, 231 continuous, 184 Process stream, 23 Iff Production control, 189 Promethium, 113 Subject Index Proportional region, 35 Proportional ionisation counter (see und~r Detector) Proton, 18, 154, 156, 167, 177, 377,440 Proton probe, 439f Pulse reading, 80 Pulse shift, 107f Pump oil-diffusion, 206 rotary vacuum, 207 vac-ion, 168 Pump-down time, 208 Purity, standards of, 483 Pyrite, 428 Pyrophyllite, 364, 367 abnormal, 406 Pyroxene, 378 Pyroxenoid,378 Pyrrhotite, 189 Quanta, 3, 30 Quantum energy, 3, 39,243 Quantum numbers, 5ff angular momentum,S magnetic, f principal, Sf spin,S Quantum theory, 2ff Quartz, 25, 128, 189, 245, 292f, 298,381,384,392 Quartzite, 143,457 Quencing, 35, 38 self-, 38 Radiation absorption of, 16, 21, 57, 358 (see also X-ray absorption) bremsstrahlung, 113, 178,439 electromagnetic,S, 15, 19ff, 56, 196,422 emission of, 16,57, 156,358 excitation of, 16ff, 70 (see also X-ray excitation) infra-red, 23, 28 ultra-violet, 28, 56, 67,443 visible, 22, 26, 28, 56 499 Radiation damage, 183 Radioactive decay, IS ff Radioactive species, formation of, 165ff Radioactivity, 165 (see also under Activity) induced, 164ff measurement of, 173ff spectrum of, 174 growth of, 156, 165 distribution of, 181 Radiochemical notation, 164 Radiochemical purity, 180 Radiochemical separation, 171, 186 Radiochemistry, 154 ff Radioisotope, source of, 163 (see also under Isotope) Radiotracer techniques, 186ff Radius atomic, 390 ionic, 390 Radon, 187 Raman spectrum, 24, 361, 366 Rapid survey work, 228 Rare earths, 92, 226, 242 Rare gas configuration, Rate law, first order, 155 Ratemeter, 47 Ratio method, 124f, 133, 139 Ratio standard, 124, 133, 139 Reaction, 403 kinetic rate of, 414 solid state, 189, 377f, 403 Reactivity, 390 Reagents optical spectroscopy, 60, 64, 66ff radioactive, 180 Receiving slit, 269f, 274 Receiving slit angle, 272, 274 Reciprocal lattice, 258, 305, 326, 331, 353f Reciprocal lattice explorer camera, 310 Reciprocal lattice point, 335, 346f Reciprocal space, 258 Recirculating loop, 233f Rediffraction, 347 Reference material, 393ff, 397f Refractive index, 346f, 380 Refractory wear, 190 500 Replicate measurements, 123 Replication, 324 Resolving power, 100, 300, 324, 380 Resolution, 40, 182, 2l6f, 426, 432 angular, 282 area, 428ff, 442, 444, 447f atomic, 444ff depth, 440ff, 448 spectral, 80 Retarding potential, 44lf Reyerite, 372, 376 dehydration of, 372, 374 zeolitic water in, 372, 376 R-factor (see Sensitivity factor, relative) Rhenium, 82,164,176,201 Rhodium, 82, 176 Rhodonite, 392 Riffles, 454 Ross-filter pair (see Absorption edge filter) Rotation photographs, 306f Rotation-retigraph camera, 310 Rotrode, 463 Rubidium, 82f, 104, 176,185,227 Rb-Sr geochronology, 227 Rule Angstrom, 266 Hilger Watts, 266 use of steel, 266 Ruthenium, 176 Rydberg constant, Safety, 49f, 88, 25lf Samarium, 176 Sample bulk, 58, 452f dilution of in DTA, 393, 403 in XRD, 264, 280 direct evaporation of, 80 fused glass, l29ff glass, 126 multimineralic, 198f presentation of, 114, 462, 466 representative, 125, 180, 232, 397,452ff Subject Index sub-, 136, 199 Sample bead, fused, 130 Sample cell, 62 Sample changer, 113 Sample coating, 324 Sample crushing, 454f Sample decomposition, 451, 457f by fusion, 20lf, 457f Sample fusion, 129ff, 148, 235, 239 Sample grinding, 170, 199, 235, 239,381,402,453 Sample holder, 119,273,322 Sample homogenisation, 180, 198, 201 Sample homogeneity, 126, 146, 381 Sample mixing, 198f Sample preparation, 58ff, 80, 88, 126ff, 169ff, 198ff, 235, 239, 264f, 273, 324f, 38lff, 433f, 45lff Sample sparking, 197 Sample splitters, 454 Sample splitting, 453ff Sample support, 324 Sample thickness, 277, 349 Sampling, 232ff, 381 bulk,452f Sampling precision, 199, 203 Sampling techniques, 233f, 381 Sand,239,457,46lf Saponite, 407 Saturable core reactor, 399 Scrueexpan~on,68,400 Scaler, 47 Scandium, 176, 185, 196,217 Scanned laser infra-red microscope, 481 Scanned laser photoluminescence microscope, 481 Scanning circle, 269 Scanning electron microscope (SEM), 44, 117, 422, 424ff, 447f, 482 absorptive mode, 428f, 431, 439 cathodoluminescent mode, 428f emissive mode, 428f, 431 quantitative studies in, 431 reflective mode, 428f, 430f X-ray mode, 428, 430, 439 Scanning procedure, 274f Subject Index Scanning speed, 119,274 Scatter lines, 136ff Scattering coherent, 97f Compton, 97, 98, 137f, 144, 163,174,260 -elastic, 260 forward, 347 incoherent, 97f inelastic, 343, 347 light, 66 mass, 97 photo-electron, 97 Raman, 366 Rayleigh, 97, 98,137, 144 X-ray, 98ff, 260 Scavenger, 171 f Scrap, melting of, 187f Second order contribution, 216 Secondary emission suppression plate, 214 Segregation, 234, 240 Selectivity, 81, 83, 172, 231, 235 Selenium, 176, 185,481 Self attenuation, 170 Self diffusion, 186 Self shielding, 170 Semiconductor, 481 intrinsic, 41 Semiconductor detector (see under Detector) Sensing coil, 224 Sensitivity in activation analysis, 166, 176 in atomic absorption spectrometry, 75f, 8lf in Auger spectroscopy, 441, 448 in autoradiography, 182 in differential thermal analysis, 403 in electron spectroscopy for chemical analysis, 444, 448 in emission spectrometry, 75, 82 Ge(Li) detector, 175 in ion microprobe, 440, 448 in isotope dilution analysis, 178 limit, 176, 437 in mass spectrometry, 197,218, 228 in optical absorption spectrometry, 67, 75, 83 501 in trace element analysis, 183 in X-ray diffraction, 301 in X-ray fluorescence, 101, 114, 118,135,143,431,437 Sensitivity factor, relative, 220, 223 Sepiolite, 404 Sesquioxide, hydrated, 407 Shadowcasting, 325 Shadowgraph, Shape effects, 127ff, 370ff Shellac, 264 Sieves, brass, 143 Silic~201,378,457,463,466f determination of, 458f Silica ampoule, 170 Silica brick, BCS 314, 464 Silicate anion, 385 Silicate minerals, 127, 186, 196, 377, 399 Silicon, 82, 176, 186, 216, 220f, 240, 470ff lithium drifted (see under Detectors) Silicon carbide, 217, 371 SiO, nOf Si0 , 371 (see also Quartz) Si0 group, 367 Si2 Os poly-anion, 364, 367 SiOH group, 376, 378f Sillimanite BCS 309, 467 Silver, 26,82,96,176,185 Sintering, 186 Size effect, 240 Slag, 187,461,467 Slime, 239 Slit collector, 21lf, 218, 225 divergence, 270, 274 exit, 214, 224 receiving, 269f, 274 scatter, 270 Soller, 100, 270 system, 60, 77 width, 63ff, 68, 73, 272 Slope factor, 137, 139 Slurry, 232, 238ff, 242, 244f Slurry mixing, 199 Slurry presenter, 236 Slurry sampler, constant head, 233, 237 Sn02,298 502 Subject Index Sodium, 12, 70, 74, 82, 93, 105, 108, 146, 157,176, 185,441, 470f borate flux, 129,452 carbonate, 20lf, 457 hydroxide, 457 tetraborate, 146 Sodium iodide crystal, 39 (see also Detector, scintillation) Solution, 58, 62 solid, 295, 438 Solvent aqueous, 60, 172 organic, 59, 74, 172 Solvent contribution, 62, 64, 79 Solvent extraction, 59, 74, 154, 17lf, 186,459 Space group, 313, 336 Spacing, inter-planar, 258 Spark gap, 212, 224 Spark pulse length, 210, 223f Spark pulse repetition rate, 210 Spark voltage, 210 Sparking conditions, 210, 216, 223 Sparking procedure, 206ff, 228 Specific heat, 395 Specimen holder, 396, 397ff, 402 flat pan, 397, 402 Specimen reactivity, 399 Specimen stage 1-!_1 1:' _ _ _ _ _ _ _ _ _ _ 11 1.6.11 l.VU1}J''-'.lQ.\.U.lv, ., J~ J strain, 325 Spectra absorption, 19, 60ff electromagnetic, 3f, 12 electron emission, 422f flame emission, 19,70 fluorescence, 19 hydrogen emission, ion beam, 197 optical, 15, 55ff production of, 16ff ultra-violet, 22, 60 visible, 22, 60 X-ray, 92, 100, 114 Spectral response curve, 29, 42 Spectroflux, 130 Spectrograph, spark emission, 84 (see also Direct reading spectrograph) Spectrometer absorption, 60f, 64f, 68ff Spectrometer (con t 'd ) AEI-MS7 mass, 206ff, 221 atomic absorption, 76ff double beam, 68ff, 78, 380 infra-red, 378ff Perkin-Elmer 79,83,303 Perkin-Elmer 402UV, 68 Pye-Unicam SP500, 61 Pye-Unicam SP90, 83 Pye-Unicam SP900, 72f, 83 Pye-Unicam SP1900, 83 single beam, 60ff, 70, 78 Telsec portable XRF, 112 time of flight mass, 446 X-ray absorption edge, 113, l18f, 235,247 energy dispersive, ll4ff, 118, 236 on-line, 235 on-stream, 235 simultaneous dispersive, 118, 235f wavelength dispersive, 99ff, 118 Spectrometry atomic absorption, 21, 56, 58, 75ff, 176, 465f flame emission, 56, 58, 70ff, 81, n ""10 0-', L l 'Y-ray, 174 optical, 56ff, 460f, 482 optical absorption, 56, 60ff, 75, 83, 176 spark source mass, 176, 195ff, 460,48lf Spectroscopy Auger electron, 44lf, 448 electron for chemical analysis, 443f,448 emission, 70f, 476 fluorescence, 476 infra-red, 23, 357ff, 417, 476, 483 laser mass, 48 mass, 25, 58, 195ff, 414, 440, 478 opticaL 56ff,384,476 photoelectron, 443f Raman, 365 ultra-violet, 476 Subject Index X-ray fluorescence, 58, 87ff, 478 Spectrosil, 144 Spherical aberration, 328ff Spectrum scanning, 68,72,81,119 Spiking, 136 Spot, scanning, 426 Spurious reflection, 120, 337f Stacking fault, 277, 348ff Standard calibration, 133, 466 external, 132f, 136,276 internal, 135ff, 196, 198ff, 220, 239,276,299,301,331,463 international geochemical, 133 G-2, 148 W-1, 148, 150, 224, 226 reference, 124, 133, 146, 165, 170, 224, 393ff silicate, 148 synthetic, 136, 146, 446 U.S.G.S.,146ff Standard additions, methods of, 74 Standard deviation, 123 relative, 124 Standard solution, 71, 74 Standardisation, 74ff Steel, 185, 187,474 Stoneware, 467 Strontium, 70,82, 176, 185, 227 Structural analysis, 313f, 443,452, 469ff Structure factor, 260f, 297, 337 Sub stoichiometric method, 172f Sulphate, 59, 81, 358, 399,444 determination of, 67 Sulphide, 129,367,444 Sulphide minerals, 127, 189, 246, 381 Sulphide Ore 1, Canadian AAS, 150 Sulphur, 59, 143f, 176, 186f, 441, 444 Surface, erosion of, 440 Surface adsorption, 189 of water on clays, 402, 408f, 414 Surface analysis, 422, 44lff Surface coating, 426, 434f, 437 Surface effects in XRF, 126 Surface finish, 127, 434,437,466 503 Surface studies, 188f, 440ff Surface topography, 324, 430,440 Systematic absences, 313 Systematic row, 346f 426f, Talc, 361, 367 Mg-Ni in, 361f, 367 Tailing stream, 238f Take-off angle, 127, 131,270,431 Tantalum, 176, 185f, 196 Tantalum boat, 80 Tartrate, 66, 172 Teflon rod, 203 Tellurium, 176 Telsec betaprobe, 92, 110 Temperature, 16, 19ff, 24, 57,155, 282f, 389, 397,403,412 control of, 24, 399 peak tip, 393f, 407 Temperature difference, 393, 397 Temperature difference versus temperature curve, 398 Temperature difference versus time curve, 393, 398, 402 Temperature environment, 393 Temperature gradient, 394 Temperature measurement, 393, 400f Temperature range, 396, 398, 401, 406 Terbium, 176 Thallium, 39, 185 Thallous chloride, 331 Thaumasite, 377 Thermal analysis, 25, 389ff simultaneous, 416 Thermal characteristics, 393 Thermal columns, 169 Thermal conductivity, 395,426 Thermal diffusivity, 395 Thermal energy, l6f, 23 Thermal expansion, 390 Thermal ionisation source, 227 Thermal neutron, 18, 164, 167, 169 Thermobalance, 41 Off Cahn electro-, 41 Of Chevenard, 41 Of 504 Perkin-Elmer, 412 Stanton, 410 Thermocouple, 28, 393f, 399 bimetallic, 32 calibration of, 401 chromel/alumel, 32,400 control, 399 Pt/Pt-Rh, 400 W/W-Re,400 Thermogravimetry (TG), 25, 377, 390f, 409ff, 416, 482 apparatus for, 409ff applications of, 413ff derivative (DTG), 390f, 409, 412,416 for mineral compositions, 414 quantitative, 413 simultaneous, 416 Thermogravimetric curves, 413f Thermopile, 32 Thorium, 18If, 185 Thulium, 176 Thyristor, 399 Tin, 82, 143,176, 185f, 219, 239f, 242 Titania, 459, 467 Titanium, 82,176, 185, 220f, 238, 459,465 Titanium dioxide pigment, 222 Tobermorite, 378f Topotaxy, 322 Townsend avalanche, 34, 39 Trace analysis, 35lf Trace element analysis, 129, 136, 143f, 184, 482 Tracer, radioactive, 178ff Transistor, field effect, 46 Transition moment, 367 Transmission electron microscope (TEM), 322ff, 424ff, 439 high voltage, 325 Tridecylarnine, 189 TRIGA reactor, 169 Tritium, 164, 167f Truscottite, 372 Tungsten, 176, 185f, 370 Tungsten carbide disc mill, 128, 143 Tuttle cold-seal vessel, 401 2(J angle, 120, 262, 266, 268, 287, 330 Subject Index 2(J to d-value, table of, 120, 267 Twin, 337f[ Twinning, 105 Carlsbad, 341 effect on diffraction patterns, 337ff Twinning axis, 338f Twin spots, 339 UKAEA Harwell, 474 Ultimate analysis, 452 Ultra light elements, 109ff Ultrasonic dispersion, 402 Ultra-violet light, 443 Units, 48ff, 251 angstrom, 48, 251 electron-volt, 48 kilohertz, 48 kX-,251 of radioactivity, IS 9f Systeme International, 48 wavenumber, 48 X-,251 Unit cell, 260f, 305, 360, 365ff derivation from powder data, 296 derivation from single crystal patterns, 334f direct, 258, 332 fractional coordinates in, 260, 337 parameters, 256 reciprocal, 258, 332, 339 refinement of parameters, 296 Universal scale of intensities, 301 Uranium, 94,101, 18If, 185f U-Zr hydride fuel, 169 Vacuum, 206ff, 324,441 Valence theory, 5ff Valency, 6ff, 370 Valleriite, 438 Valves flap, 213 sliding, 213 Vanadium, 82, 176, 185f Van der Waals' force, 358, 361 Subject Index Vegard's law, 296 Vermiculite, 377, 404f, 407 Vibrations AI-O,364 atomic, 16, 23ff, 358, 390, 392 bending, 23 Be-O,364f of complex anions, 366 coupled, 358, 367, 376 in crystals, 358ff degrees of freedom, 365 dipole, 359f, 367 infra-red active, 360ff infra-red inactive, 360ff interaction between, 358, 363 isolated, 358 libration, 360f modes of, 23, 360f quantised, 16, 23ff, 361 stretching, 23f, 360f, 367 Si-O,364f synchronous, 370f Vibrational coupling, 367, 376 Vibrational frequencies, 366, 369 shape effects, 37lf Vibrational mode acoustic, 360ff, 363f anti-symmetric, 367 bending, 363 optical, 360ff stretching, 360ff, 363 symmetric, 367 Vibrational states, 359 Vibrator electrode, 224 isolated, 358, 361 quantised, 16, 23ff, 361 Vibratory grinder, 382 Viscosity, 73 Voids, 350f Volatile, loss of, 385, 389, 415, 460 Volatilisation, 210 Voltage accelerating, 21, 93, 210, 225, 252, 322f, 326, 444 pulsed,222 reverse bias, 41 f Voltage peak switching, 225 Voltage regulator, 253 Voltage sources, 39f, 46 505 Voltage spread, Gaussian, 106 Water, 10,376,385 bending frequencies, 376 as catalyst, 392,401 of crystallisation, 357 loss of, 324, 377, 385,415,460 stretching frequencies, 376 surface adsorbed, 382, 402, 408, 414 zeolitic, 392, 414 Water vapour pressure, 392, 401 Wave amplitude diffracted, 348 direct, 348 Wave number, Wave theory, 258 Wave-particle nature of electron,S, 21,325 Wavelength, 2, 59, 77, 360ff of electron, 21, 325f integrated, 131 values of, 82 X-ray, 93f, 96, 254, 256f, 314, 437 Wavelength scan in XRF, 119 Wavelength range, 101 Weight change, 389, 393,403,409, 413 Weight change curves isobaric, 409 isothermal, 409 Weight fraction, 98, 297ff Weight loss, 25, 130,377 Weissenberg goniometer, 308f, 314 Wig-L-Bug grinder, 382 Window beryllium, 94, 126 deposition on, 237, 240 failure of, 126, 237 flashing of, 38, 105f, 237f lithium hydride, 287 Mylar, 38, 105 polycarbonate, 38, 105 polypropylene, 38, 105 rock salt, 383 W.1 granite standard, 148, 150, 224 Wolframite, 189 Wollastonite, 334, 378, 392 506 Subject Index Xanthogenate, 189 Xenon, 108 XOn polyhedron, 369 Xonotlite, 335, 342, 392 X-rays, 18, 21, 26, 38, 42, 87ff, 210, 23lff, 249ff Cauchy distribution of, 303 characteristic, 15, 22, 90, 93f, 108, 232, 239, 253, 424, 432, 437 cone of diffracted, 262f, 305f continuum, 93f, 241, 432 interelemental interference, 96, 139, 239f Gaussian distribution of, 107, 123,303 monochromatic, 90, 243, 253f, 257 nature of, 252ff primary, 9lff, 240, 432 production of, 252ff, 423 secondary, 126, 240 K-series, 15, 22, 94, 96, 117, 120, 253f L-series, 22, 94, 96, 120, 432 M-series, 120 transmitted intensity, 240 white, 92, 110,253 X-ray absorption, 93, 96ff, 239f, ?77ff ?Q7 ., 4~1 - 4~4 , 4~~ efficiency of, 131 mechanism of, 96f, 259f X-ray absorption coefficient, 110, 126, I 34ff, 239,246, 253,280 characteristic, 136 of composite materials, 98 determination of, 135 linear, 96 mass, 95ff, 13lf, 137, 298ff matrix, 98, 13lf, 135f, 138, 239, 298ff,432,437 photoelectron, 97 self-, 88 X-ray absorption curves, 95, III X-ray absorption doubling, 279 X-ray absorption edge, 97f, I I Of, 246, 253f X-ray absorption edge filter, I I Off, 117,235, 253f, 273 balanced pair, I I Off, 235 cobalt, 254 - -~, ~ ~, iron, 254 manganese, 254 nickel, 254 palladium, 254 programmable, 117, 145 rhenium, 254 Ross-pair, 113 strontium, II Of vanadium, 254 yttrium, I I Of zirconium, I I Of, 254 X-ray absorption factor, 261 X-ray camera Debye-Scherrer powder, 262ff, 267,280,282 focussing, 267 Guinier-de Wolff, 267f, 282 Guinier-Lenne, 283f high pressure, 285f high temperature, 282f, 311 f Kossel,438 powder film, 262ff single crystal, 306ff X-ray diffraction, 100, 231, 250ff, 372,377,385,406,417,469,474, 478 angle, 100 energy dispersive, 243, 257,287 error sources, 276ff l! _ _ • , UJi);PJ.d\, I;;;JUtall, ","OV mechanical, 281 systematic,277f mechanism of, 258ff on-line, 242 on-stream, 242ff powder, 26lff single crystal, 305ff X-ray diffraction pattern, 243, 261ff X-ray electronic counter diffractometer, 99, 270ff, 301 automatic, 304 high pressure, 285f high temperature, 284 sample preparation for, 273 single crystal, 313 f X-ray electronic counter diffractometry, 268ff, 312f X-ray excitation, 90ff, 235f, 252ff direct electron, 90, 110, 252f, 430,432 Subject Index efficiency of, 131 ff, 240f by primary X-rays, 92, 94, 13lff,241 by radioisotopes, 92, 113, 117, 241 secondary enhancement, 132 X-ray film, 263ff, 300 measurement of, 266 shrinkage of, 266, 277 stripping, 252 X-ray film mounting van Arke1, 263 Bradley-Jay, 263, 282 Straumanis-Ievins, 263f X-ray fluorescence, 88ff, 252, 433 X-ray fluorescence analysis, 88ff, 231, 235ff, 456, 466ff, 473, 482 analytical procedures, 119ff calibration, 132ff calibration curves, 133ff comparison with chemical analysis, 150 crystal spectrometer for, 99ff, 235f,432f direct derivation of composition, 132 elemental ratios from, 437 energy dispersive, 114ff, 235ff, 430,482 error sources, 122ff, 437 correction of, 132, 437 counting statistics, 123 instrumental, 122 sampling, 125 heavy absorber method, l34f light elements, 109f, 437 matrix effects, 131 ff sample preparation, l26ff sample presentation, l26ff trace elements, 143 X-ray generators, 94ff, 252f, 271 stability of, 253, 271 X-ray intensities background, 123 corrected, 142 correction of, 132, 437 diffraction, 245, 260f, 262, 267, 276,292f fluorescent, l22ff, 432 matrix correction for, 132, 138, 298ff 507 peak, 123, 132,274 raw, 122ff, 140 relative, 290ff, 297, 301 universal scale, 301 X-ray intensity profile, 278f, 30lf, 436 corrected, 303 X-ray line overlaps, 102, 114, 135, l43f X-ray line shift, l5f, 104, 278f, 295,436 X-ray powder diffraction pattern, 276,482 comparison of film and counter, 282 indexing of, 295f interpretation of, 288ff computer aided, 293f, 295f graphically, 294 peak position, 276 quantitative, 297ff quantitative sensitivity, 301 recording of, 243, 274f, 300f sample preparation, 264, 273 X-ray scattering, 246, 260 Compton, 92, 137,260 intensity, 137, 240 mechanism of, 260 Rayleigh, 137 X-ray source, 269 chromium target, 95 contamination in, 144f copper target, 252 dual anode, 95 gas-filled, 252 gold target, 95 heavy element, 94 high energy point, 113 high power, 235, 243 interchangeable target, 252 light element, 95 low power, 113f, 236 molybdenum target, 95f polychromatic, 243 pumped, 110 radioactive isotope, 112, 117, 235f rotating anode, 252 sealed tube, 88, 95ff, 235, 252 stability of, 119,252 tungsten target, 95 508 X-ray spectra Ag K-lines, 254 Al K-lines, 144,443 Ca K -lines, 102, 109 Co K-lines, 252, 254 Cr K-lines, 144,254 Cu K-lines, 46, 252ff F K -lines, 109 Fe K-lines, 46, 106, 126, 252, 254 Hf L-lines, 107 K K-lines, 102 Mg K-lines, 443 Mo K-lines, 120, 252, 254 Na K-lines, 100, 109, 126 Nb K-lines, 246 Ni K-lines, 254 Np L-lines, 114 Pb K-lines, 240 Pb L-lines, 240 U L-lines, 114, 241 Zn K-lines, 98 Zr K-lines, 100, 107, 110, 246 Subject Index powder, 26lff, 274f single crystal, 305ff X-ray transmission, 246 X-ray wavelength, 93f, 96, 254, 256f, 314, 437 X-Y recorder, 398 Ytterbium, 176 Yb ,300 Yttrium, 96,176, 185 Zeolite, 392,433 Zero condition, 62, 64, 68f, 80 Zero point energy, 16 ~inc, 82, 90, 143, 146, 185, 238, 241f,459 ZnS, 98, 250,422 Zircon, 183 Zirconium, 185 ... Department of Minerals Engineering and the Department of Extra Mural Studies of the University of Birmingham The course was concerned mainly with physical methods of analysis of minerals and mineral. .. try to present an account of these new methods with particular reference to their use in mineral analysis It discusses the application of physicochemical methods of analysis, using principally... characterisation of materials, both in the number and the variety of techniques that have become available In the specific area of physicochemical methods of analysis, based on monitoring the interaction of