Principles and Practice of X-Ray Spectrometric Analysis

Second Edition

Wilhelm Conrad Rontgen (1845-1923)

Discoverer of x-rays

Henry Gwyn Jeffreys Moseley (1887-1915)

Founder of x·ray spectrometry

For biographies of Rontgen and Moseley, see References (19) and (20), respectively.

Principles and

Practice of X-Ray Spectrometric Analysis Second Edition

Eugene P. Bertin RCA Laboratories David Sarnoff Research Center Princeton, New Jersey

KAPARCHIEF

Plenum Press' New York-London

Library of Congress Cataloging in Publication Data

Bertin, Eugene P 1921-Principles and practice of X-ray spectrometric analysis.

Bibliography: p. Includes index. 1. X-ray spectroscopy.

analysis. OC481 B544pj OD96.X2B47 1975

I. Title. [DNLM: 1. Radiation. 2. Spectrum

543'.085 74-28043

ISBN-13: 978-1-4613-4418-6 e-ISBN-13: 978-1-4613-4416-2 001: 10.1007/978-1-4613-4416-2

Photograph of W. C. Rontgen from Otto Glasser, Dr. W. C. Rontgen (2d ed.; Springfield, Illinois: Charles C Thomas,

1958); courtesy of Mrs. 0110 Glasser and the publisher.

Photograph of H. G. J. Moseley from Mary Elvira Weeks, Discovery 01 the Elements (6th ed.; Easton, Pennsylvania:

Journal of Chemical Education, 1960); courtesy of the publisher.

First Printing - April 1975 Second Printing - August 1978 Third Printing - November 1979

Fourth Printing - August 1984

© 1970,1975 Plenum Press, New York Softcover reprint of the hardcover 1 st edition 1975

A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y. 10013

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

Preface to the Second Edition

Since the first edition of this book was published early in 1970, three major developments have occurred in the field of x-ray spectrochemical analysis.

First, wavelength-dispersive spectrometry, in 1970 already securely established among instrumental analytical methods, has matured. Highly sophisticated, miniaturized, modular, solid-state circuitry has replaced elec­tron-tube circuitry in the readout system. Computers are now widely used to program and control fully automated spectrometers and to store, process, and compute analytical concentrations directly and immediately from ac­cumulated count data. Matrix effects have largely yielded to mathematical treatment. The problems associated with the ultralong-wavelength region have been largely surmounted. Indirect (association) methods have extended the applicability of x-ray spectrometry to the entire periodic table and even to certain classes of compounds. Modern commercial, computerized, auto­matic, simultaneous x-ray spectrometers can index up to 60 specimens in turn into the measurement position and for each collect count data for up to 30 elements and read out the analytical results in 1--4 min-all corrected for absorption-enhancement and particle-size or surface-texture effects­and wholly unattended. Sample preparation has long been the time-limiting step in x-ray spectrochemical analysis.

Second, energy-dispersive spectrometry, in 1970 only beginning to assume its place among instrumental analytical methods, has undergone phenomenal development and application and, some believe, may supplant wavelength spectrometry for most applications in the foreseeable future. There has been an amazing proliferation of highly sophisticated, computer-

v

vi PREFACE TO THE SECOND EDITION

controlled, energy-dispersive instrumentation using lithium-drifted silicon detectors, multichannel analyzers, and low-power x-ray tube and radio­isotope sources. Modern commercial, computerized, energy-dispersive x­ray spectrometers can substantially match the performance cited above for simultaneous wavelength-dispersive instruments; they cannot measure quite as many elements at once due to somewhat poorer resolution, and they must count a little longer due to lower maximum count rate.

Finally, a decreasing role of experimentation has accompanied the increasing role of mathematics, computers, electronics, and mechanics. More and more aspects of x-ray spectrometric analysis that previously required experimental ingenuity are now dealt with mathematically and automatically.

Great benefit derives from these developments. Modern computer­controlled automated instruments with their direct analytical readout enable us to get much more work done much more conveniently and in much less time. But we must forego the challenge, satisfaction-and fun!-of cir­cumventing difficulties by experimental ingenuity. To some x-ray spectro­chemists, this may seem a small price indeed. Others may share the writer's feeling that, to paraphrase the television commercial, we are analyzing more, but enjoying it less!

Analytical x-ray spectrometry continues to develop at a vigorous, wholesome pace. However, one senses an abatement in the development of instrumentation, theory, basic methods, and techniques. This trend is evident even in the younger discipline of energy-dispersion, where present activity is mostly in evaluation of performance, comparison with wave­length-dispersion, improvement of sensitivity and resolution, mathematical methods of quantitative analysis, and applications. The same applies to the ancillary field of electron-probe microanalysis. Perhaps the most sig­nificant indication of the maturity of x-ray spectrochemical analysis is the increasing attention of x-ray spectrochemists to other disciplines. One need but scan the programs of the major national and international meetings to note that the sessions previously devoted exclusively to x-ray fluores­cence spectrometry or electron-probe microanalysis are now increasingly concerned with the related fields of proton and heavy-ion excitation and "electron spectrometry for chemical analysis" (ESCA), including photo­and Auger-electron spectrometry. One also finds increasing numbers of papers on the actually unrelated fields of ion-scattering spectrometry (ISS) and secondary-ion mass spectrometry (SIMS).

Unaccountably, whereas comprehensive reference treatises have ap­peared for all other established instrumental analytical disciplines as they

PREFACE TO THE SECOND EDITION vii

matured, no such book has appeared in x-ray spectrochemistry. In under­taking this new edition, the writer was motivated by the need for such a manual, convinced that it would remain timely for many years, and en­couraged by the excellent reception of the first edition.

All material in the first edition has been retained in the second, but the book has been revised, updated, and greatly expanded. The magnitude of the expansion may be conveyed in terms of the 401 pages, 23 tables, 62 figures, 221 equations, and 362 references added to the 703 pages, 47 tables, 196 figures, 344 equations and 565 references, in the first edition; three of the new figures are in color. The updating includes significant publications through 1973 and even a substantial number from 1974. The first edition cited publications through late 1968.

Substantially all sections in the book have been expanded and/or updated, but by far the most attention has been given to energy dispersion and related subjects, including low-power x-ray tubes; radioisotope sources; multichannel analyzers; lithium-drifted silicon detectors; computer-con­trolled multichannel energy-dispersive spectrometer systems; processing, readout, and display of energy-spectral data; and energy-dispersive dif­fractometry-spectrometry (Giessen-Gordon method). Other especially ex­panded chapters and sections include those on pulse-height selection; matrix effects (absorption-enhancement, heterogeneity, particle-size, and surface-texture); mathematical methods, including the variable-take off­angle method; specimen preparation, especially the borax-glass fusion method; trace analysis; radioactive specimens; and electron-probe micro­analysis.

Appendixes on photon energies of principal spectral lines, absorption­edge jump ratios, and fluorescent yields have been added to the existing ones on wavelengths of principal K, L, and M spectral lines and absorption edges; K, L, and M excitation potentials; and mass-absorption coefficients. The existing table of data for 26 analyzer crystals and multilayer heavy­metal soap films has been expanded to 72. A comprehensive glossary of symbols has been added. Because problems of organization and retrieval increase with the length of the book, the detailed table of contents of the first edition has been retained and updated, the index has been made much more detailed, and the text is generously provided with cross-references.

However, the basic objectives and organization of the book remain the same as those outlined in the preface of the first edition, and the same 21 chapters in the same seven major divisions are retained. The book is still directed to those who are not content simply to operate the instrument and perform the analyses, but who want some understanding of the under-

viii PREFACE TO THE SECOND EDITION

lying principles. Thus, the book still emphasizes the practical experimental aspects, but also explains the principles underlying the instrumentation and analytical methods and techniques. These explanations are given in primarily descriptive, rather than mathematical, terms, but all essential mathematics is included. Rather than dealing with specific applications, the book still strives to present the widest range of analytical methods, techniques, con­cepts, and ideas possible in the available space, wherever possible with references for further study. Accordingly, the book does not deal specifically with the currently cogent applications of x-ray spectrochemical analysis to the environmental, biomedical, and forensic problems that beset our society; however, readers concerned with these fields will find all applicable tech­niques described and documented.

The book is still concerned primarily with x-ray fluorescence spectrom­etry as applied on commercial flat-crystal spectrometers and accessories. However, extensive treatment is also given to other x-ray analytical methods that can be conducted on such instruments and to ancillary methods requir­ing their own instrumentation. Energy-dispersion and electron-probe micro­analysis are given substantial treatment.

The errors in the first edition have been corrected, hopefully without the addition of too many new ones.

Harrison, New Jersey February 1975

Eugene P. Bertin

Preface to the First Edition

The first commercial x-ray secondary-emission (fluorescence) spec­trometer became available about 20 years ago. Within a decade, x-ray spectrometry had become a firmly established method of instrumental analysis for elements having atomic number down to 12 (magnesium) in concentrations down to a few tenths of a percent. During the last decade, several thousand commercial instruments have been placed in service in laboratories and factories, and the applicability of the method has been extended to trace and micro analysis and to substantially the entire periodic table. However, although many colleges and universities offer full courses in optical and electrical methods of instrumental analysis and in x-ray diffraction, very few offer courses in x-ray spectrometry. Proficiency in this method must be acquired by self-instruction, on-the-job training and experience, the workshops held by the instrument manufacturers, and the one- or two-week courses offered by a few universities.

This book is intended primarily as a textbook for three groups of readers: (1) students; (2) technicians newly assigned to the x-ray spectro­metric laboratory; and (3) technicians having practical experience, but little or no formal instruction, and therefore lacking a basic understanding of the method. The book is intended particularly for those who are not content simply to operate the instrument and perform the required analyses, but who want to understand the method and instrument. It is hoped that the book will also be useful to expert x-ray spectrochemists and to scientists and technicians in other disciplines who want to evaluate the applicability of x-ray spectrometry to their fields.

Pursuant to these objectives, the book emphasizes the practical aspects

ix

x PREFACE TO THE FIRST EDITION

of x-ray secondary-emission spectrometry, but also gives the principles underlying the method, instrumentation, and analytical techniques. Expla­nations are given primarily in descriptive rather than mathematical terms, but all equations of practical or tutorial value are included.

The applications of x-ray spectrometry are so numerous and varied that it would be hopeless to attempt even to summarize them in a book of reasonable length. Moreover, the writer has always believed that an under­standing of the principles and instrumentation of the method leads to profi­ciency in application of the method to specific problems. Consequently, rather than dealing with specific applications and materials, the book presents in general terms the widest range of analytical methods, techniques, concepts, and ideas possible in the available space. Specific examples are used only for illustration.

The book is concerned primarily with conventional x-ray secondary­emission spectrometry as applied on commercially available spectrometers and accessories. However, extensive treatment is also given to unconven­tional modes of operation of the instrument and to other x-ray analytical methods that can be conducted on commercial instruments. Related x-ray methods requiring their own instrumentation are also discussed.

An understanding of the instrumentation is necessary to full realiz.ation of its potentialities. Accordingly, the x-ray tube and generator, spectro­goniometer, and detection, measurement, and readout components are described schematically in considerable detail. However, specific commercial instruments are not described, except for special features.

The 21 chapters of the book fall into seven groups as follows. Chapters I and 2 deal with x-ray physics-the origin and nature of

continuous and characteristic x-ray spectra, primary and secondary excita­tion, fluorescent yield, absorption, scatter, and diffraction.

Chapters 3-9 constitute a detailed description of the x-ray spectrometer, its components, and their operation. A general description of the instrument and of the method and its scope, advantages, and limitations is given in Chapter 3. Chapter 4 (Excitation) gives the principles of secondary excita­tion and detailed descriptions of the x-ray tube and generator. Chapter 5 (Dispersion) is concerned primarily with conventional flat-crystal dispersion. However, most of the other flat- and curved-crystal dispersion arrangements and instruments based on them are also described. Chapter 6 (Detection) considers the construction, function, performance, properties, and prin­ciples of operation of proportional and scintillation counters. However, the relatively new solid-state detectors and other less common detectors are also described. Chapter 7 (Measurement) describes the instrumentation

PREFACE TO THE FIRST EDITION xi

and methods for measurement of line and background intensities. Chapter 8 is devoted to pulse-height analysis and "nondispersive" methods. Chapter 9 describes complete conventional manual and automatic spectrometers as well as special instruments having primary or radioisotope excitation and instruments for the ultralong-wavelength region.

Chapter 10 deals with qualitative and semiquantitative analysis. Chapters 11-13 consider performance criteria and other features of the

method: error, precision, and counting statistics (Chapter 11); specific, nonspecific, special, and unusual absorption-enhancement effects (Chapter 12); and sensitivity, resolution, and spectral-line interference (Chapter 13).

Chapters 14 and 15 present the basic methods of quantitative x-ray spectrometric analysis: standard addition and dilution; calibration standard­ization; internal standardization; standardization with scattered x-rays; matrix dilution; thin-film methods; special experimental methods; and mathematical correction of absorption-enhancement effects. Chapter 15 is devoted entirely to this last method.

Chapters 16 and 17 are devoted to specimen preparation and presentation of solids, small parts, powders, briquets, fusion products, liquids, and supported specimens.

The remaining chapters describe unconventional modes of operation of the spectrometer and related x-ray methods of analysis. Chapter 18 deals with measurement of composition and thickness of films and platings. Chapter 19 treats the analysis of small specimens and of small selected areas on large specimens by "x-ray probe" techniques. Chapter 20 describes polychromatic and monochromatic absorptiometry, absorption-edge spec­trometry, absorption-edge fine structure, microradiography, and analytical methods based on scattered x-rays. All these methods are treated with emphasis on their applicability to commercial spectrometers. This chapter also describes Auger-electron and x-ray-excited photoelectron spectrometry and x-ray-excited optical fluorescence. Chapter 21 is a brief description of the instrumentation and method of electron-probe microanalysis.

Each chapter is substantially self-contained, with many cross references to other pertinent sections and with some replication of material covered in other chapters.

Some readers may be disappointed by the absence of a chapter on micro and trace analysis. However, these subjects are dealt with in Chapters 16-19.

The Appendixes contain tables of wavelengths of spectral lines and absorption edges, excitation potentials, and mass-absorption coefficients. The Bibliography provides a list of books, reviews, bibliographies, and

xii PREFACE TO THE FIRST EDITION

tables that should be available in the x-ray spectrometric laboratory, and the 513 papers and reports referred to throughout the book. In general, papers published after 1968 are not included.

The writer gratefully acknowledges that in his task he benefited substan­tially from access to the excellent books on x-ray spectrometry already in print, especially those by Adler (1), Birks (8), Liebhafsky et 01. (26), and, particularly, Jenkins and de Vries (22). Finally, the writer is most grateful to Thomas J. Cullen, who read the entire manuscript and made many valuable suggestions.

Harrison, New Jersey November 1969

Eugene P. Bertin

Contents

PART I. X-RAY PHYSICS

Chapter 1. Excitation and Nature of X-Rays; X-Ray Spectra

1.1. Historical . . . . . . 3 1.2. Definition of X-Rays 6 1.3. Properties of X-Rays 8 1.4. Units of X-Ray Measurement 8

1.4.1. Frequency . 8 1.4.2. Wavelength 8 1.4.3. Energy . . 10 1.4.4. Intensity 11

1.5. The Continuous Spectrum 13 1.5.1. Nature . . . . . . 13 1.5.2. Generation . . . . 13 1.5.3. Short-Wavelength Limit 15 1.5.4. Origin of the Continuum 16 1.5.5. Effect of X-Ray Tube Current, Potential, and Target 17 1.5.6. Significance . . . . . . . 19

1.6. The Characteristic Line Spectrum 19 1.6.1. Atomic Structure 19 1.6.2. Nature and Origin . . 21

1.6.2.1. General . . . 21 1.6.2.2. Band Spectra . 24 1.6.2.3. Selection Rules 24 1.6.2.4. Notation. . . 24

xiii

xiv CONTENTS

1.6.2.5. Wavelength 1.6.2.6. Intensity . .

1.6.3. Excitation-General

26 30 31

1.6.4. Primary Excitation . 36 1.6.5. Secondary Excitation 38

1.6.5.1. X-Ray Absorption Edges 38 1.6.5.2. Principles . . . . . . . 40 1.6.5.3. Relationship of Absorption Edges and Spectral-

Line Series. . . . . . . . . . . . . . .. 41 1.6.5.4. Excitation with Polychromatic X-Rays . .. 43 1.6.5.5. Other Contributions to the Specimen Emission 43

1.7. Comparison of Primary and Secondary Excitation 44 1.7.1. X-Ray Tube Potential . . 44 1.7.2. Features ........ 45

1.8. Excitation by Ion Bombardment

Chapter 2. Properties of X-Rays

2.1. Absorption . . . . . . . . . . . . 2.1.1. X-Ray Absorption Coefficients 2.1.2. X-Ray Absorption Phenomena 2.1.3. Relationship of p,/ e, A., and Z 2.1.4. Absorption Edges . . . . . . 2.1.5. Comparison of X-Ray and Optical Absorption 2.1.6. Significance . . . . . . . . . . . . . . . 2.1.7. Half-Thickness and Absorption Cross Section

47

51 51 55 57 59 61 64 65

2.1.8. Inverse-Square Law 67 2.2. Scatter . . . . . . . . . . . . . 68

2.2.1. General . . . . . . . . . . 68 2.2.2. Modified (Compton) Scatter 68 2.2.3. Relationship of Unmodified and Modified Scatter 71 2.2.4. Significance . . . . . . . . . . . . 73

2.3. Diffraction by Crystals . . . . . . . . . . 73 2.4. Specular Reflection; Diffraction by Gratings 79

2.4.1. Specular Reflection. . . . 79 2.4.2. Diffraction by Gratings. . 80

2.5. Auger Effect; Fluorescent Yield. 81 2.5.1. Auger Effect 81 2.5.2. Fluorescent Yield 82 2.5.3. Satellite Lines . . 84

CONTENTS xv

PART II. THE X-RAY SPECTROMETER, ITS COMPONENTS, AND THEIR OPERATION

Chapter 3. X-Ray Secondary-Emission (Fluorescence) Spectrometry; General Introduction

3.1. Nomenclature . . . . . 89 3.2. Principle and Instrument 92

3.2.1. Principle . . . . 93 3.2.2. The X-Ray Spectrogoniometer 93 3.2.3. Electronic Readout Components . 96 3.2.4. Qualitative, Semiquantitative, and Quantitative Analysis 97 3.2.5. Phases of a Quantitative X-Ray Spectrometric Analysis 97

3.3. Appraisal . . . . . . . . . 98 3.3.1. Advantages . . . . . . . . . . . 98

3.3.1.1. X-Ray Spectra . . . . . . 98 3.3.1.2. Excitation and Absorption. 100 3.3.1.3. Absorption-Enhancement Effects 100 3.3.1.4. Spectral-Line Interference . 100 3.3.1.5. Nondestruction of Specimen 10 1 3.3.1.6. Specimen Versatility. . . . 101 3.3.1. 7. Operational Versatility 102 3.3.1.8. Versatility of Analytical Strategy 102 3.3.1.9. Selected-Area Analysis 103 3.3.1.10. Semiquantitative Estimations 103 3.3.1.11. Concentration Range. . 103 3.3.1.12. Sensitivity. . . . . . . 103 3.3.1.13. Precision and Accuracy 104 3.3.l.l4. Excitation. . . . . . . 104 3.3.1.15. Speed and Convenience 3.3.1.16. Operating Cost 3.3.1.17. Automation . . . . . . 3.3.1.18. Process Control . . . . 3.3.1.19. Use with Other Methods.

3.3.2. Disadvantages . . . . 3.3.2.1. Light Elements . . . . . . 3.3.2.2. Penetration. . . . . . . . 3.3.2.3. Absorption-Enhancement Effects 3.3.2.4. Sensitivity . . . . . 3.3.2.5. Qualitative Analysis. . . . . .

105 105 105 106 106 106 106 106 107 107 107

xvi CONTENTS

3.3.2.6. Standards 3.3.2.7. Instrument Preparation 3.3.2.8. Components . . . 3.3.2.9. Instrument Settings 3.3.2.10. Error . 3.3.2.11. Tedium . . . . . 3.3.2.12. Cost . . . . . .

3.4. Trends in X-Ray Spectrochemical Analysis.

Chapter 4. Excitation

4.1. Principles . . . . 4.1.1. General ..

107 108 108 109 109 109 110 110

113 113

4.1.2. Excitation by Monochromatic X-Rays 115 4.1.3. Excitation by Continuous Spectra 118

4.2. The X-Ray Tube . . . . . . . . 121 4.2.1. Function and Requirements. 121 4.2.2. Construction. . . . . . 121 4.2.3. Design Considerations . . . 122 4.2.4. Practical Considerations 124

4.2.4.1. Excitation Efficiency 124 4.2.4.2. Spectral-Line Interference 127 4.2.4.3. Temperature . . . . . . 128 4.2.4.4. Evaluation of the Condition of the X-Ray Tube 128

4.2.5. Special X-Ray Tubes. . . 129 4.2.5.1. Dual-Target Tube. . 129 4.2.5.2. End-Window Tube . 130 4.2.5.3. Demountable Tubes . 130 4.2.5.4. Tubes for Ultralong Wavelength 131 4.2.5.5. Low-Power Tubes 132 4.2.5.6. Field-Emission Tubes 136

4.3. X-Ray Power Supply ..... . 138 4.3.1. Function and Requirements . 138 4.3.2. Components and Operation. 138

4.3.2.1. High-Potential Supply. 140 4.3.2.2. X-Ray Tube Filament Supply 142 4.3.2.3. Operation . . . . . . . . . 143 4.3.2.4. Stabilization . . . . . . . . 145 4.3.2.5. Safety and Protective Devices 146

4.3.3. Practical Considerations ..... 4.3.3.1. Constant Potential . . . . 4.3.3.2. Maximum Target Potential 4.3.3.3. Operating Conditions

4.4. Filters in Secondary Excitation 4.4.1. Attenuation Filters . . . 4.4.2. Enhancement Filters . . 4.4.3. Enhancement Radiators.

4.5. Specimen Presentation

Chapter 5. Dispersion

CONTENTS xvii

147 147 149 149 156 156 156 158 158

5.1. Introduction. . 161 5.2. Collimators . . . 163

5.2.1. Function . 163 5.2.2. Features and Considerations 165

5.3. Radiation Path . . 169 5.4. Analyzer Crystals . 171

5.4.1. Introduction . 171 5.4.2. Features 172

5.4.2.1. Wavelength Range 172 5.4.2.2. Diffracted Intensity 174 5.4.2.3. Resolution . . . . 176 5.4.2.4. Peak-to-Background Ratio; Crystal Emission. 178 5.4.2.5. Thermal Expansion . . . . . . . . . 180 5.4.2.6. Miscellaneous Features . . . . . . . 181 5.4.2.7. Aligning and Peaking the Goniometer. 183

5.4.3. Other Dispersion Devices. . . . . . . . 186 5.4.3.1. Gratings and Specular Reflectors. . . 186 5.4.3.2. Multilayer Metal Films . . . . . . . 187 5.4.3.3. Metal Disulfide-Organic Intercalation Complexes 187 5.4.3.4. Multilayer Soap Films 188 5.4.3.5. Pyrolytic Graphite . . . 191

5.5. Basic Crystal-Dispersion Arrangements. 191 5.5.1. Multichannel Spectrometers . . . 192 5.5.2. Flat-Crystal Dispersion Arrangements 193

5.5.2.1. Bragg and Soller 193 5.5.2.2. Edge-Crystal . . . . . . . . 194 5.5.2.3. Laue .... . . . . . . . 195 5.5.2.4. Other Flat-Crystal Arrangements 197

xviii CONTENTS

5.5.3. Curved-Crystal Dispersion Arrangements 5.5.3.1. General . . 5.5.3.2. Transmission . . . . . . . . . 5.5.3.3. Reflection . . . . . . . . . . 5.5.3.4. Von Ramos Image Spectrograph.

5.6. Curved-Crystal Spectrometers . . . . . . . 5.6.1. Semi focusing Spectrometer . . . . . 5.6.2. Continuously Variable Crystal Radius 5.6.3. Naval Research Laboratory Design . 5.6.4. Applied Research Laboratories Design 5.6.5. Cauchois Spectrometer . . . . . . . 5.6.6. Spherically Curved-Crystal Spectrometers

5.7. Photographic X-Ray Spectrographs .....

Chapter 6. Detection

200 200 202 203 205 207 207 209 209 211 212 213 214

6.1. Introduction. . 219 6.2. Gas-Filled Detectors 220

6.2.1. Structure . . 220 6.2.1.1. Components, Classifications 220 6.2.1.2. Windows. . 221 6.2.1.3. Gas Fillings . . . . . . . 226

6.2.2. Operation . . . . . . . . . . . . 228 6.2.2.1. Phenomena in the Detector Gas Volume. 228 6.2.2.2. Proportionality in Gas Detectors . . . . 230 6.2.2.3. Gas Amplification; Types of Gas Detectors 232 6.2.2.4. Quenching . . . . . . . . . . . . . . 235

6.2.3. Proportional Counters . . . . . . . . . . . . 236 6.2.3.1. Phenomena in the Detector Gas Volume . 236 6.2.3.2. Detector Output; Escape Peaks . 240

6.3. Scintillation Counters . . . . . 241 6.3.1. Structure . . . . . . . . . 241

6.3.1.1. Scintillation Crystal . 241 6.3.1.2. Multiplier Phototube 243

6.3.2. Operation . . . . . . . . . 245 6.3.2.1. Proportionality in Scintillation Counters 245 6.3.2.2. Phenomena in the Scintillation Counter 245

6.4. Lithium-Drifted Silicon and Germanium Detectors 247 6.4.1. Structure 247 6.4.2. Operation . . . . . . . . . . . . . . . . 249

CONTENTS xix

6.4.3. Advantages . . . . 251 6.4.4. Limitations . . . . 255 6.4.5. Avalanche Detectors 257

6.5. Evaluation of X-Ray Detectors 6.5.1. Detector Characteristics.

6.5.1.1. Rise Time . . . 6.5.1.2. Dead Time 6.5.1.3. Resolving Time. 6.5.1.4. Recovery Time . 6.5.1.5. Linear Counting Range 6.5.1.6. Coincidence Loss 6.5.1.7. Choking 6.5.1.8. Plateau 6.5.1.9. Slope . 6.5.1.10. Inherent Noise and Background. 6.5.1.11. Quantum Efficiency . . . . . 6.5.1.12. Resolution . . . . . . . . .

257 257 257 258 259 259 259 259 264 264 267 267 267 267

6.5.2. Comparison of Conventional Detectors 271 6.5.3. Modified Gas-Filled and Scintillation Detectors . 271

6.6. Other X-Ray Detectors 279 6.6.1. Photographic Film . . . . . . . . . . . 279 6.6.2. Photoelectric Detectors . . . . . . . . . 281

6.6.2.1. The Phosphor-Phototube Detector 281 6.6.2.2. Photoelectric Detectors for the Ultralong-Wave-

length Region 282 6.6.3. Crystal Counters. . . . . . . . . . . . . . . . . . 284

Chapter 7. Measurement

7.1. Instrumentation . . 7.l.l. Introduction. 7.1.2. Preamplifier . 7.1.3. Amplifier . . 7 .1.4. Pulse-Height Selectors

7.1.4.1. Pulse-Height Selector; Discriminator 7.1.4.2. Pulse Reverter . . . 7.1.4.3. Pulse-Shape Selector

7.l.5. Ratemeter and Recorder 7.1.6. Scaler and Timer 7.1.7. Computers

285 285 288 288 289 289 291 293 293 294 296

xx CONTENTS

7.2. Measurement of Intensity 7.2.1. Ratemeter Methods 7.2.2. Scaler-Timer Methods

7.2.2.1. Preset-Time Method 7.2.2.2. Preset-Count Method .. 7.2.2.3. Integrated-Count Method 7.2.2.4. Monitor and Ratio Methods.

7.2.3. X-Ray Dose and Dose Rate 7.3. Background ......... .

7.3.1. Definition and Significance 7.3.2. Origin and Nature. 7.3.3. Measurement . 7.3.4. Reduction. . . 7.3.S. Considerations .

Chapter 8. Pulse-Height Selection; Energy-Dispersive Analysis; Nondispersive Analysis

297 297 298 298 299 299 299 301 303 303 303 30S 308 313

8.1. Pulse-Height Selection . . . . . . . . 31S 8.1.1. Principle of Pulse-Height Selection 316 8.1.2. Pulse-Height Distribution Curves . 320

8.1.2.1. Introduction . . . . . . . 320 8.1.2.2. Single-Channel Pulse-Height Selector 322 8.1.2.3. Multichannel Pulse-Height Analyzer 323

8.1.3. Pulse-Height Selector Displays ..... 326 8.1.4. Pulse-Height Selector Operating Controls. . 330 8.1.S. Use of the Pulse-Height Selector. 331

8.I.S.1. Evaluation of Detector and Amplifier Char­acteristics . . . . . . . . . . . . . . . . . 331

8.I.S.2. Establishment of Pulse-Height Selector Settings 333 8.1.6. Applications and Limitations . . . . 337 8.1.7. Automatic Pulse-Height Selection . . 338 8.1.8. Problems with Pulse-Height Selection 342

8.1.8.1. General . . . . . . . . . . 342 8.1.8.2. Shift of Pulse-Height Distribution 342 8.1.8.3. Distortion of Pulse-Height Distribution 346 8.1.8.4. Additional Pulse-Height Distributions Arising

from the Measured Wavelength. . . . 347 8.1.9. Unfolding of Overlapping Pulse-Height Distributions. 3S0

8.1.9.1. Principle. . . . . . . . . . . . . . . .. 3S0

CONTENTS xxi

8.1.9.2. Application .... 352 8.1.9.3. Simplified Variations 353

8.2. Energy-Dispersive Analysis 356 8.2.1. Introduction. . . . 356

8.2.1.1. Principles 356 8.2.1.2. Advantages . 357 8.2.1.3. Limitations . 358

8.2.2. Instrumentation . . 361 8.2.2.1. General . . 361 8.2.2.2. Excitation by X-Rays 361 8.2.2~3. Excitation by Radioisotopes 366 8.2.2.4. Energy-Dispersive Multichannel X-Ray Spectrom-

eter Systems . . . . . . . . . . . . 373 8.2.3. Energy-Dispersive Diffractometry-Spectrometry 389

8.3. Nondispersive Analysis . . 394 8.3.1. Selective Excitation. 394 8.3.2. Selective Filtration . 397

8.3.2.1. Methods . . 397 8.3.2.2. X-Ray Transmission Filters 400

8.3.3. Selective Detection . . 401 8.3.4. Modulated Excitation 401

Chapter 9. Laboratory, Automated, and Special X-Ray Spectrometers

9.1. Introduction. . . . . . . . . . 9.2. Laboratory X-Ray Spectrometers

9.2.1. General ....... . 9.2.2. Instrument Arrangements . 9.2.3. Accessories . . . . . . .

9.3. Automated X-Ray Spectrometers 9.3.1. General . . . . . . . . . 9.3.2. Sequential Automatic Spectrometers 9.3.3. Simultaneous Automatic Spectrometers . 9.3.4. "Slewing" Goniometers .

9.4. Special X-Ray Spectrometers 9.4.1. Portable Spectrometer . 9.4.2. Primary Excitation . . . 9.4.3. Ultralong-Wavelength Spectrometry

9.5. X-Ray Safety and Protection . . . . . .

405 408 408 409 411 413 413 416 421 424 425 425 426 427 430

xxii CONTENTS

PART III. QUALITATIVE AND SEMIQUANTITATIVE ANALYSIS

Chapter 10. Qualitative and Semiquantitative Analysis

10.1. General . . . . . . . . 10.2. Recording the Spectrum. . 10.3. Instrument Conditions 10.4. Identification of the Peaks .

10.4.1. Spectral-Line Tables 10.4.2. Identification of Peaks

10.5. General Procedures for Qualitative and Semiquantitative

435 436 438 441 441 447

Analysis . . . . . . . . . . . . . . 450 10.5.1. Normalization Factor Method. 451 10.5.2. Method of Salmon. . . . . . 452

PART IV. PER FORMANCE CRITERIA AND OTHER FEATURES

Chapter 11. Precision and Error; Counting Statistics

11.1. Error in X-Ray Spectrometric Analysis 459 11.1.1. Nature of Error . . 459 11.1.2. Elementary Statistics 462 11.1.3. Sources of Error. . 465

11.1.3.1. General. . 465 11.1.3.2. Instrumental and Operational Error 467 11.1.3.3. Specimen Error . 469 11.1.3.4. Chemical Effects. . . 471

11.2. Counting Statistics . . . . . . . . . 472 11.2.1. Nature of the Counting Error 472 11.2.2. Calculation of Counting Error 474

11.2.2.1. Counting Error for Accumulated Counts 474 11.2.2.2. Counting Error for Intensities . 476

11.2.3. Counting Strategy . . . . . . . . . . 480 11.2.3.1. Measurement of Net Intensity 480 11.2.3.2. The Ratio Method. 488

11.2.4. Figure of Merit . . . . . . . 490 11.3. Analytical Precision. . . . . . . . . 491

11.3.1. Nature of Analytical Precision 491

CONTENTS xxiii

11.3.2. Evaluation of Precision. . . . . 494 11.3.2.1. General Considerations . 494 11.3.2.2. Instrumental Instability . 495 11.3.2.3. Operational Error . . . 495 11.3.2.4. Specimen Error . . . . 496 11.3.2.5. Evaluation of Internal Consistency of Data. 498

Chapter 12. Matrix Effects

12.1. Introduction . . . . 12.2. Absorption-Enhancement Effects

12.2.1. General; Definitions .. 12.2.2. Effects on Calibration Curves 12.2.3. Prediction of Absorption-Enhancement Effects

12.2.3.1. K Lines ...... . 12.2.3.2. L Lines. . . . . . . . . . .

12.2.4. Nonspecific Absorption Effects . . . . 12.2.5. Specific Absorption-Enhancement Effects 12.2.6. Secondary Absorption-Enhancement Effects.

12.2.6.1. General .......... . 12.2.6.2. Secondary Absorption Effects . . 12.2.6.3. Secondary Enhancement Effects .

12.2.7. Unusual Absorption-Enhancement Effects 12.3. Particle-Size, Heterogeneity, and Surface-Texture Effects

Chapter 13. Sensitivity and Resolution; Spectral-Line Interference

13.1. Sensitivity . . . . . . . . . . . 13.1.1. Definitions ... . . . . 13.1.2. Factors Affecting Sensitivity.

13.1.2.1. Excitation Conditions 13.1.2.2. Specimen Conditions . 13.1.2.3. Optical System 13.1.2.4. Detector and Readout Conditions .

13.1.3. Photon Losses in the X-Ray Spectrometer 13.1.4. Sensitivity Performance

13.2. Resolution . . . . . . . . 13.2.1. Definitions ....

13.2.1.1. Resolution

501 502 502 505 507 507 509 510 514 517 517 518 520 521 524

529 529 532 532 533 534 535 535 540 546 546 546

xxiv CONTENTS

13.2.1.2. Dispersion .... 546 13.2.1.3. Divergence . . . . 547

13.2.2. Factors Affecting Resolution 548 13.3. Spectral-Line Interference . . . . . 552

13.3.1. Definition . . . . . . . . . 552 13.3.2. Origin of Interfering Spectral Lines 553

13.3.2.1. Wavelength Interference . 553 13.3.2.2. Energy Interference . . . 557 13.3.2.3. Common Sources of Spectral Interference . 559

13.3.3. Reduction of Spectral Interference. . . . . . .. 560 13.3.3.1. General Methods . . . . . . . . . .. 560 13.3.3.2. Excitation of Analyte and Interferant Lines. 561 13.3.3.3. Transmission and Detection of Analyte and

Interferant Lines. . . . . . . . . . . . . 563 13.3.3.4. Experimental and Mathematical Correction of

Spectral Interference . . . . . . . . . . . 564

PART V. QUANTITATIVE ANALYSIS

Chapter 14. Methods of Quantitative Analysis

14.1. Introduction . . . . . . . . . . . . 14.2. Standard Addition and Dilution Methods.

14.2.1. Principles and Considerations 14.2.2. Methods ........ .

14.2.2.1. Standard Addition. 14.2.2.2. Standard Dilution . 14.2.2.3. Multiple Standard Addition. 14.2.2.4. Slope-Ratio Addition. 14.2.2.5. Double Dilution.

14.3. Calibration Standardization . . . . 14.3.1. Principles . . . . . . . . . 14.3.2. Special Calibration Methods

14.3.2.1. Single-Standard Method 14.3.2.2. Two-Standard Method . 14.3.2.3. Binary-Ratio Method 14.3.2.4. Mutual Standards Method 14.3.2.5. Sets of Calibration Curves

14.4. Internal Standardization. 14.4.1. Principles . . . . . . . . . . . .

571 575 575 576 576 578 578 578 581 583 583 588 588 589 590 592 592 594 594

CONTENTS xxv

14.4.2. Selection of Internal-Standard Element . 596 14.4.3. Advantages and Limitations. . . . . . 599 14.4.4. Considerations. . . . . . . . . . . . 600 14.4.5. Special Internal-Standardization Methods. 602

14.4.5.1. Single-Standard Internal-Standard Method 602 14.4.5.2. Variable Internal-Standard Method 602

14.4.6. Other Standardization Methods . . . . . . . .. 603 14.4.6.1. Internal Control-Standard Method. . .. 603 14.4.6.2. Internal Intensity-Reference Standard Method 603 14.4.6.3. External-Standard Method 604

14.5. Standardization with Scattered X-Rays 14.5.1. Background-Ratio Method . . . . 14.5.2. Graphic Method ........ . 14.5.3. Scattered Target-Line Ratio Method. 14.5.4. Scattered Internal-Standard Line Method.

604 605 610 610 612

14.5.5. Ratio of Coherent to Incoherent Scattered Intensities 613 14.5.6. Slurry-Density Method 615

14.6. Matrix-Dilution Methods 617 14.6.1. Principles . 617 14.6.2. Discussion. 619

14.7. Thin-Film Methods 621 14.7.1. Principles . 621 14.7.2. Infinite (Critical) Thickness 624 14.7.3. Discussion. . . . . . . . 625

14.8. Special Experimental Methods . . 627 14.8.1. Emission-Absorption Methods. 627 14.8.2. Method of Variable Takeoff Angle 631

14.8.2.1. Basic Excitation Equations 631 14.8.2.2. Evaluation of Mean Wavelength and Excita-

tion Integral .............. 634 14.8.2.3. Mass per Unit Area of an Element Film from

Its Own Line . . . . . . . . . . . . . . 635 14.8.2.4. Mass per Unit Area of an Element Film from

a Substrate Line. . . . . . . . . . . . . 636 14.8.2.5. Mass per Unit Area and Composition of Multi­

element Films . . . . . . . . . . . . . . 636 14.8.2.6. Composition of Bulk Multielement Specimens 637

14.8.3. Indirect (Association) Methods . . . . 638 14.8.4. Combinations of X-Ray Spectrometry and Other

Methods . . . . . . . . . . . . . . 639

xxvi CONTENTS

Chapter 15. Mathematical Correction of Absorption-Enhancement Effects

15.1. Introduction . . . . . 643 15.2. Geometric Methods. . 644 15.3. Absorption Correction 648 15.4. Empirical Correction Factors 651 15.5. Influence Coefficients . . . . 658

15.5.1. Introduction. . . . . 658 15.5.2. Derivation of the Basic Equations. 661

15.5.2.1. Birks' Derivation . . . . 661 15.5.2.2. MUller's Derivation; Regression Coefficients 665 15.5.2.3. Influence Coefficient Symbols 667

15.5.3. Solution of the Basic Equations. . . . 668 15.5.3.1. Simplified Solutions . . . . . 668 15.5.3.2. Evaluation of aij Coefficients to a First

Approximation ...... .... 670 15.5.3.3. Evaluation of au Coefficients to a Second

Approximation . . . . . . . . . . . . . 674 15.5.3.4. Simultaneous Evaluation of All a,j Coefficients 675 15.5.3.5. Other Methods for Evaluation of aij Coefficients 676

15.5.4. Variations of the Influence-Coefficient Method. . 678 15.5.4.1. Method of Sherman . . . . . . . . . 678 15.5.4.2. Method of Burnham, Hower, and Jones 679 15.5.4.3. Method of Marti . . . . . . . 682 15.5.4.4. Method of Traill and Lachance. . 683 15.5.4.5. Method of Lucas-Tooth and Pyne . 685 15.5.4.6. Method of Rasberry and Heinrich 689

15.6. Fundamental-Parameters Method. 690 15.7. Multiple-Regression Method . . . . . . . . . . . 696

PART VI. SPECIMEN PREPARATION AND PRESENTATION

Chapter 16. Specimen Preparation and Presentation-General; Solids, Powders, Briquets, Fusion Products

16.1. General Considerations . . . . . . 16.1.1. Introduction. . . . . . . . 16.1.2. Classification of Applications

701 701 706

16.1.3. Problems Specific to the Light Elements 16.1.4. Standards ........... .

16.1.4.1. General ........ . 16.1.4.2. Permanence of Standards . 16.1.4.3. Sources of Standards. . .

16.1.5. Effective Layer Thickness ..... 16.1.6. The Specimen-Preparation Laboratory

16.2. Solids . . . . . . . . . . . . . . . 16.2.1. Scope, Advantages, Limitations 16.2.2. Presentation . . . . . . . . .

16.2.2.1. Flat Specimens . . . 16.2.2.2. Fabricated Forms and Parts

16.2.3. Preparation . . . . . . . . . 16.2.4. Precautions and Considerations

16.3. Powders and Briquets. . . . . . . . 16.3.1. Scope, Advantages, Limitations 16.3.2. Powder and Briquet Standards 16.3.3. Preparation of Powders. 16.3.4. Presentation . . . . . .

16.3.4.1. Loose Powders 16.3.4.2. Briquets 16.3.4.3. Thin Layers. .

16.3.5. Precautions and Considerations 16.3.5.1. Particle-Size Effects 16.3.5.2. Additives . . . . . . 16.3.5.3. Briqueting. . . . . . 16.3.5.4. Other Considerations .

16.4. Fusion Products . . . . . . . . . . 16.4.1. Scope, Advantages, Limitations 16.4.2. Materials . . . . . . . . 16.4.3. Specific Fusion Procedures 16.4.4. Considerations . . . . . .

CONTENTS

Chapter 17. Specimen Preparation and Presentation-Liquids; Sup­ported Specimens

17.1. Liquid Specimens. . 17.1.1. Introduction. 17.1.2. Advantages . 17.1.3. Disadvantages

xxvii

708 71l 711 711 712 717 720 722 722 723 723 724 727 728 732 732 734 736 739 739 741 743 747 747 750 751 751 751 751 752 754 758

763 763 765 767

xxviii CONTENTS

17.1.4. Liquid-Specimen Cells . . . . 769 17.1.4.1. Forms and Materials. 769 17.1.4.2. General-Purpose Cell. 772 17.1.4.3. Somar "Spectro-Cup" 773 17.1.4.4. Cells for Use in Vacuum. 774 17.1.4.5. Uncovered Cell . . . 777 17.1.4.6. Frozen-Specimen Cell . . 778 17.1.4.7. Cell for Slurries . . . . . 780 17.1.4.8. High-Temperature Liquid-Specimen Cell 780 17.1.4.9. Other Liquid-Specimen Cells . . . . . 781

17.1.5. Precautions and Considerations . . . . . . . . 784 17.1.5.1. Interaction of the Primary Beam with Liquid

Specimens. . 784 17.1.5.2. Composition 786 17.1.5.3. Miscellany 787

17.2. Supported Specimens . . . . 788 17.2.1. General. . . . . . . 788 17.2.2. Specimens Derived from Liquids and Gases 791 17.2.3. Specimens Derived from Solids 795 17.2.4. Ion-Exchange Techniques 797

17.2.4.1. Principles . 797 17.2.4.2. Techniques 798

17.2.5. Ashing Techniques. 800 17.2.6. Bomb Techniques 801

17.3. Trace and Microanalysis 802 17.4. Radioactive Specimens . 806

PART VII. UNCONVENTIONAL MODES OF OPERATION; RELATED X-RAY METHODS

OF ANALYSIS

Chapter 18. Measurement of Thickness of Films and Platings 811

18.1. Principles and Basic Methods . . 811 18.2. Multiple-Layer and Alloy Platings . . . . . . . . 816

18.2.1. Multiple-Layer Platings. . . . . . . . . . 816 18.2.2. Alloy Platings-Composition and Thickness. 817

18.3. Special Techniques . . . . . . 821 18.3.1. Special Specimen Forms . . . . . . . . . 821

CONTENTS xxix

18.3.2. Selected-Area Analysis 823 18.3.3. Selective Excitation. . 824 18.3.4. Enhancement. . . . . 824 18.3.5. Excitation by Radioactive Sources 824 18.3.6. Energy-Dispersive Operation 825 18.3.7. Decoration 825 18.3.8. Dynamic Studies . 826

18.4. Considerations . . . . . 826

Chapter 19. Selected-Area Analysis 829

19.1. Principle and Scope. 829 19.1.1. Principle 829 19.1.2. Applications . 830 19.1.3. Advantages and Limitations. 832

19.2. Selected-Area Analysis on Standard Commercial X-Ray Spectrometers ...... 834 19.2.1. Specimen Irradiation 834 19.2.2. Selected-Area Apertures 837

19.2.2.1. General. 837 19.2.2.2. Pinholes 19.2.2.3. Slits . . 19.2.2.4. Resolution

19.2.3. Dispersion .....

837 840 843 844

19.3. Instruments for Selected-Area X-Ray Spectrometric Analysis 846 19.4. Specimen Techniques . . . . . . . . . . . . . 848

19.4.1. Preparation . . . . . . . . . . . . . . 848 19.4.2. Alignment of Selected Area and Aperture 848

19.5. Analytical Techniques 849 19.6. Performance . . . . . . . . . . . . . . . . . 852

Chapter 20. Other Analytical Methods Based on Emission, Absorption, and Scatter of X-Rays; Other Spectrometric Methods Involving X-Rays . . 859

20.1. X-Ray Absorption Methods 859 20.1.1. Polychromatic X-Ray Absorptiometry 860

20.1.1.1. Principles and Instrumentation 860 20.1.1.2. Advantages and Limitations 861

xxx CONTENTS

20.1.2. Monochromatic X-Ray Absorptiometry 862 20.1.2.1. Principles and Instrumentation 862 20.1.2.2. Advantages and Limitations 864

20.1.3. Applications of X-Ray Absorptiometry. 864 20.1.4. X-Ray Absorption-Edge Spectrometry (Differential X-

Ray Absorptiometry). . . . . . . . . 866 20.1.4.1. Principles and Instrumentation 866 20.1.4.2. Advantages and Limitations 871 20.1.4.3. Applications. . . . . . . . . 873

20.1.5. X-Ray Contact Microradiography . . . 878 20.1.6. X-Ray Absorption-Edge Fine Structure 879 20.1.7. Specimen Preparation for X-Ray Absorption 881

20.2. X-Ray Scatter Methods . . . . : . . . . 882 20.2.1. Coherent Scatter. . . . . . . . . 883 20.2.2. Coherent/Incoherent Scatter Ratio . 883 20.2.3. Determination of Dry Mass 884

20.3. Scanning X-Ray Microscopy. . . . . . . 885 20.3.1. Introduction. . . . . . . . . . . 885 20.3.2. Scanning X-Ray Emission Microscopy 886 20.3.3. Scanning X-Ray Absorption Microscopy 887

20.4. X-Ray Photoelectron and Auger-Electron Spectrometry 888 20.4.1. Introduction. . . . . . . . . . . 888 20.4.2. X-Ray Photoelectron Spectrometry 889 20.4.3. Auger-Electron Spectrometry . . . 890 20.4.4. Photo- and Auger-Electron Spectrometer 893

20.5. X-Ray-Excited Optical-Fluorescence Spectrometry 895 20.6. X-Ray Lasers . . . . . . . . . . . . . 897 20.7. X-Ray Appearance-Potential Spectrometry 899

Chapter 21. Electron-Probe Microanalysis

21.1. Introduction . . 21.2. Instrumentation. . . . . . . .

21.2.1. General ....... . 21.2.2. Electron-Optical Systems 21.2.3. Other Instrument Systems

21.3. Interaction of the Electron Beam and Specimen. 21.3.1. Interaction Phenomena . . .

21. 3 .1.1. Electron Phenomena 21.3.1.2. X-Ray Phenomena.

903 904 904 905 908 909 909 910 911

CONTENTS xxxi

21.3.1.3. Cathodoluminescence. . . . . 912 21.3.1.4. Potential Distribution Pattern . 912

21.3.2. Detection . . . . . . . . . . . . . . 913 21.3.2.1. Electron Detection . . . . . . 913 21.3.2.2. X-Ray, Luminescence, and Potential Detection 914

21.4. Modes of Measurement and Display 914 21.4.1. General. . . . . . . . . . . . . . . . . . . . . 914 21.4.2. Measurement at a Point . . . . . . . . . . . . . 915 21.4.3. Measurement along a Line (One-Dimensional Analysis) 915 21.4.4. Measurement over a Raster (Two-Dimensional Analysis) 918 21.4.5. Measurement Perpendicular to the Specimen Surface

(Three-Dimensional Analysis) . . . . . 927 21.4.6. Other Methods of Readout and Display 927 21.4.7. Color Displays 928 21.4.8. Considerations. . 930

21.5. Specimen Considerations 21.6. Quantitative Analysis . .

21.6.1. Principles . . . . 21.6.2. Intensity Corrections

21.7. Performance . . . . . . . 21.8. Applications . . . . . . . 21.9. Comparison with X-Ray Fluorescence Spectrometry

PART VIII. APPENDIXES, BIBLIOGRAPHY

Appendixes

Appendix 1. Wavelengths of the Principal X-Ray Spectral Lines of the Chemical Elements-K Series

Appendix 2. Wavelengths of the Principal X-Ray Spectral Lines of the Chemical Elements-L Series

Appendix 3. Wavelengths of the Principal X-Ray Spectral Lines of the Chemical Elements-M Series

Appendix 4. Photon Energies of the Principal K and LX-Ray Spectral Lines of the Chemical Elements

Appendix 5. Wavelengths of the K, L, and M X-Ray Absorption Edges of the Chemical Elements

Appendix 6. K, L, and M X-Ray Excitation Potentials of the Chemical Elements .

931 933 933 934 938 942 942

951

954

958

960

964

968

xxxii CONTENTS

Appendix 7A. X-Ray Mass-Absorption Coefficients of the Chemical Elements at 0.1-30 A . . . . . . . . . . . . . 972

Appendix 7B. X-Ray Mass-Absorption Coefficients of Elements 2-11 (He-Na) at 40-100 A . . . . . . . . . . . . . 976

Appendix 8. Values of the K and LIII Absorption-Edge Jump Ratios rand (r - I)/r of the Chemical Elements. . 977

Appendix 9. Average Values of the K, L, and M Fluorescent Yields of the Chemical Elements . . . . . . . . . . . . 980

Appendix 10. X-Ray Spectrometer Analyzer Crystals and Multi-layer Films . . . . . . . . . . . . . 981

Appendix IIA. Glossary of Frequently Used Notation 1003 Appendix lIB. Prefixes for Physical Units . . . . . . 1008 Appendix 12. Periodic Table of the Chemical Elements 1009

Bibliography

Books Periodicals

1011 1014

General Reviews . 10 14 Bibliographies . . 1015 Tables of Wavelengths, 2() Angles, and Mass-Absorption Coefficients 1016 Papers and Reports 1018

Index ............................ 1061