QUANTITATIVE X-RAY FLUORESCENCE ANALYSIS

THEORY AND APPLICATION

Gerald R. Lachance
Formerly, Geological Survey of Canada

Fernand Claisse
Corpordtion Scientifique Claisse, Inc., Quebec, Canada Formerly Professor, Department of Mining and Metallurgy, Universite Laval, Canada

JOHN WILEY & SONS

Chichester New York Brisbane Toronto Singapore

CONTENTS

Preface Symbols, Definitions and Terminology PART I: THEORY Chapter 1. X-RAY PHYSICS 1.1 General Considerations 1.2 Atomic Structure 1.3 Binding Energies of Orbital Electrons 1.4* Critical Excitation Energy 1.5* Critical Excitation Wavelength 1.6* Characteristic X-radiations 1.7* Excitation Sources 1.7.1 Emanations from X-ray tubes 1.7.2 The continuous spectrum 1.7.3 Characteristic X-radiations from the target element 1.8* Attenuation of X-rays 1.8.1 Experimental determination of ^ 1.9* Relation between \x., Z and X; Absorption Edges 1.10 Scattering of X-rays 1.10.1 Coherent scatter " 1.10.2 Incoherent scatter 1.11* Line Intensities; Probability of Excitation 1.11.1 Absorption jump ratios 1.11.2 Relative line intensities within the K, L and M series 1.11.3 Fluorescence yield 1.12 Discussion 1.13 Summary

xv xix 1 3 3 4 6 8 9 9 11 12 12 15 18 20 21 24 24 25 26 27 28 30 31 32

viii

CONTENTS

Chapter 2. X-RAY FLUORESCENCE EMISSIONS 2.1 2.2 2.3* General Considerations Spectrometer Configurations Primary Fluorescence 2.3.1 Description of primary fluorescence 2.3.2 Intensity expression for primary fluorescence 2.3.3 Experimental verification 2.3.4 Primary fluorescence, polychromatic excitation source Secondary Fluorescence 2.4.1 Description of secondary fluorescence 2.4.2 Intensity expression for secondary fluorescence 2.4.3 Experimental verification 2.4.4 Secondary fluorescence, polychromatic excitation source Tertiary Fluorescence 2.5.1 Description of tertiary fluorescence 2.5.2 Intensity expression for tertiary fluorescence Relative Contribution from Primary, Secondary and Tertiary Emissions Discussion Summary

33 33 34 37 37 39 44 45 45 45 47 49 53 54 54 55 58 59 60 63 63 64 64 65 66 67 67 68 70 70 74 76 77 79 80 82

2.4*

2.5

2.6 2.7 2.8

Chapter 3. THE FUNDAMENTAL PARAMETERS APPROACH 3.1 3.2* General Considerations Concept of the Fundamental Parameters Approach 3.2.1 Replacing integrals by finite summations 3.2.2 Spectral distributions 3.2.3 Iteration procedure Classical Formalism 3.3.1 Primary emission 3.3.1.1 Numerical example of the calculation of P(i) and Pi 3.3.2 Secondary emission 3.3.2.1 Numerical example of the calculation of (Pi + Sij)x 3.3.2.2 Experimental confirmation Alternate Formalism 3.4.1 Primary fluorescence emission 3.4.1.1 Numerical example 3.4.2 Secondary fluorescence emission 3.4.2.1 Numerical example

3.3

3.4*

CONTENTS

IX

3.4.3 3.5

3.6*

General expression 3.4.3.1 Numerical example Discussion 3.5.1 Monte Carlo model 3.5.2 General expression for quantitative X-ray fluorescence analysis 3.5.2.1 Numerical examples Summary

83 83 86 86 87 89 90 93 93 94 95 95 95 96 97 97 97 98 99 100 102 104 105 107 109 111 112 112 115 116 120 121 125 125 126 129 130 132

Chapter 4. FUNDAMENTAL INFLUENCE COEFFICIENTS 4.1 4.2 4.3 4.4 General Considerations The Concept of Influence Coefficients The Domain of Fundamental Influence Coefficients Initial Developments 4.4.1 von Hamos 4.4.2 Beattie and Brissey 4.4.3 Lachance and Traill Introducing Polychromatic Excitation 4.5.1 Claisse and Quintin 4.5.2 Lachance Fundamental Influence Coefficient Algorithms 4.6.1 Tertian and Broil-Tertian formalisms 4.6.2 Rousseau formalism 4.6.3 Lachance formalism 4.6.4 De Jongh formalism Numerical Examples 4.7.1 Effect of target material 4.7.2 Effect of instrumental geometry 4.7.3 Effect of specimen composition 4.7.4 Effect of characteristic tube target lines 4.7.5 Binary A j arrays W 4.7.6 Fundamental influence coefficients, multielement specimens Discussion Summary

4.5

4.6*

4.7

4.8 4.9

Chapter 5. ALPHA COEFFICIENT CONCEPT 5.1 5.2 5.3 5.4* General Considerations Concept and Domain of Alpha Coefficients Concept of Theoretical Influence Coefficients Extension to Polychromatic Excitation 5.4.1 Binary Wij influence coefficient arrays

CONTENTS

5.5* 5.6* 5.7*

5.8

5.9

Linear Approximation of Binary my Arrays 5.5.1 Numerical example Hyperbolic Approximations of Binary my Arrays 5.6.1 Numerical example Third Element Effect 5.7.1 Cross-coefficient formalisms 5.7.2 Tertian formalism 5.7.3 Numerical examples Discussion 5.8.1 The equivalent wavelength concept 5.8.2 Variation of ay with specimen composition 5.8.3 Limited theoretical justification of alpha coefficient models Summary

134 138 139 140 143 144 146 147 152 152 153 154 156 159 159 160 161 163 166 168 170 171 173

Chapter 6. EMPIRICAL INFLUENCE COEFFICIENTS 6.1 6.2 6.3* 6.4* 6.5* 6.6* 6.7 6.8* 6.9 General Considerations Concept and Domain of Empirical Influence Coefficients Criss-Birks and Lachance-Traill Formalisms Method of Rasberry and Heinrich Method of Lucas-Tooth and Price Method of Lucas-Tooth and Pyne The Japanese Industrial Standard Method Discussion Summary

Chapter 7. GLOBAL MATRIX EFFECT CORRECTION APPROACHES 7.1 7.2* General Considerations 7.1.1 Analytical context The Double Dilution Method 7.2.1 Principle of the method 7.2.1.1 Numerical example 7.2.2 Effect of enhancement 7.2.3 Practical considerations Compton (Incoherent) Scatter Methods 7.3.1 Theoretical considerations 7.3.1.1 Numerical example The Internal Standard Method 7.4.1 Numerical example The Standard Addition Method 7.5.1 Numerical example

175 175 176 177 177 179 181 183 183 184 187 190 191 193 194

7.3*

7.4 7.5*

CONTENTS

XI

7.6* The High Dilution-Heavy Absorber Method 7.6.1 Numerical example 7.7* Matrix Matching Methods 7.7.1 Numerical example 7.8 Discussion 7.9 Summary Chapter 8. SPECIAL ANALYTICAL CONTEXTS 8.1 General Considerations 8.2* Low Z Analytes and Matrices 8.2.1 Low Z analytes 8.2.2 Low Z matrices 8.3 Limited Sample Quantity 8.4* Thin Specimens 8.5* Thin Films 8.5.1 Determination of film thickness 8.5.1.1 Numerical examples 8.5.2 Multi-layer thin films 86 Particulates 8.7 Oxide Systems 8.7.1 Numerical example 8.8* Fused Disc Specimens 8.8.1 Influence coefficients modified for 8.8.1.1 Numerical example 8.8.2 Correction for loss on fusion (LOF) 8.8.2.1 Numerical example 8.8.3 Correction for gain on fusion (GOF) 8.8.3.1 Numerical example 8.8.4 General theory of LOF and GOF 8.8.4.1 Numerical example 8.9 Liquids 8.10 Conclusions Chapter 9. ANALYTICAL STRATEGIES 9.1 9.2 General Considerations Analytical Context 9.2.1 Nature of samples submitted 9.2.2 Instrumental resources 9.2.3 Sample composition 9.2.4 Precision and accuracy 9.3* Specimen Preparation 9.3.1 Bulk solidsalloys, glasses, plastics, ceramics

195 196 199 200 201 202

203 203 204 204 205 208 209 211 211 212 215 216 216 217 219 219 221 224 225 227 229 231 233 236 237 239 239 241 242 242 243 243 245 245

flux

Xll

CONTENTS

9.3.2 Pressed powder pellets 9.3.3 Fused discs 9.3.4 Liquids 9.4* Intensity Measurements 9.4.1 Precision, counting statistics 9.4.2 Excitation source selection 9.4.3 Line selection 9.4.4 Collimation 9.4.5 Crystal selection 9.4.6 Detector selection 9.4.7 Correction for background 9.4.8 Correction for spectral interference 9.4.9 Correction for dead time 9.5* Calibration 9.5.1 Definition 9.5.2 Mathematical models 9.6* The Analytical Process 9.6.1 Confirmation of the validity of a calibration 9.6.2 Counting monitors 9.6.2.1 Numerical example 9.6.3 Quality control 9.6.4 Analytical precision and the detection limit 9.6.5 Software 9.7 Summary PART II: APPLICATION II. 1 X-RAY PHYSICS II. 1.4 II. 1.5 II. 1.6 II. 1.7.1 II. 1.8.1 II. 1.8.2 II. 1.9 II. 1.11.1 II. 1.11.2 11.1.11.3 1.1.12 Critical Excitation (Binding) Energies Critical Excitation (Absorption Edge) Wavelengths Energies and Wavelengths of Characteristic X-radiations Experimentally measured spectral distributions Experimental determination of //. Algorithms for generating \L values Generating /* as a Function of Z and X Absorption jump ratios; absorption jump factors Relative line intensities within series Fluorescence yields Summary and Conclusions

246 247 250 251 251 252 253 253 254 254 255 256 258 259 260 261 266 266 267

268
270 271 273 275

279 281 281 282 283 284 285 286 290 294 295 296 297 299 299

II.2 X-RAY FLUORESCENCE EMISSIONS II.2.1 Two-theta Values for Characteristic Lines

CONTENTS

Xlll

11.2.2 11.2.3 11.2.4 11.2.5

Excitation Probability Factor Experimental Verification of Primary Emission Experimental Verification of Secondary Emission Summary

299 301 302 305 307 307 311 313 322 323 323 324 325 327 330 333 336 337 338 340
344

11.3 THE FUNDAMENTAL PARAMETERS APPROACH II.3.2 II.3.2.3 II.3.4 11.3.6 Concept of the Fundamental Parameters Approach The iterative process Comprehensive Tabulation of Pi + Si, AVi and EV] Data Summary and Conclusions

11.4 FUNDAMENTAL INFLUENCE COEFFICIENTS 11.4.6.1 Broil-Tertian formalism 11.4.6.2 Rousseau formalism 11.4.6.3 Lachance formalism 11.4.6.4 The de Jongh formalism 11.4.6.5 Typical analytical procedure 11.4.6.6 Interrelation between fundamental influence coefficients II.4.6.1 Summary and conclusions 11.5 ALPHA INFLUENCE COEFFICIENTS 11.5.4 11.5.5 II 5 " 1 7 The Lachance-Traill Algorithm The Modified Claisse-Quintin Algorithm
The C O L A A1

8orithm

ll'l't , The Tertian Algorithm

11.6 EMPIRICAL INFLUENCE COEFFICIENTS 11.6.3 II.6.3.1 11.6.4 11.6.5 11.6.6 II.6.8 The Lachance-Traill Model: Eqn (6.7) Numerical example The Rasberry-Heinrich Model: Eqn (6.11) The Lucas-Tooth and Price Model: Eqn (6.14) Lucas-Tooth and Pyne Model: Eqn (6.17) Discussion

348
351 351 354 355 357 358 358 361 361 362 364

11.7 GLOBAL MATRIX EFFECT CORRECTION METHODS 11.7.2 11.7.3 II.7.5 Double Dilution Method: Eqn (7.20) Compton (Incoherent) Scatter Methods: Eqn (7.30) Standard Addition Method

Xiv

CONTENTS

11.7.6 11.7.7

High Dilution-Heavy Absorber Method Matrix Matching Methods

365 365 367 367 368 369 370 371 372 374 378 383 387 395 398

11.8 SPECIAL ANALYTICAL CONTEXTS II.8.2 11.8.4 11.8.5 11.8.8 Low Z Analytes and Matrices Thin Specimens Thin Films, Film Thickness Fused Disc Specimens

11.9 ANALYTICAL STRATEGIES 11.9.1 11.9.2 11.9.3 11.9.4 Steels, Nickel-base, Copper-base, Broad Mixtures Cements and Raw Materials in the Cement Industry Geological Contexts Discussion and Summary

References and Bibliography Author Index Subject Index