Handbook of X-Ray Spectrometry Revised and Expanded (Practical Spectroscopy, V. 29)

Handbook of X-Ray Spectrometry......Page 1 Preface to the Second Edition......Page 3 Preface to the First Edition......Page 6 Table of Contents......Page 8 Contributors......Page 13 HISTORY......Page 15 Table of Contents......Page 0 III. GENERAL FEATURES......Page 16 A. Spectral Distribution......Page 17 B. Spatial Distribution and Polarization......Page 19 V. EMISSION OF CHARACTERISTICX-RAYS......Page 21 A. InnerAtomic Shell Ionization......Page 22 B. Spectral Series in X-rays......Page 23 C. X-ray Satellites......Page 25 F. FluorescenceYield......Page 26 G. Fine Features of X-ray Emission Spectra (Valence or Chemical Effects)......Page 30 VI. INTERACTION OF PHOTONSWITH MATTER......Page 31 A. Photoelectric Absorption......Page 33 B. Compton Scattering......Page 35 C. Rayleigh Scattering......Page 39 D. Total Mass Attenuation Coefficient......Page 40 E. Diffraction, Refraction, and Dispersion......Page 41 F. X-ray Raman Scattering......Page 44 A. Photon Excitation......Page 45 B. Electron Excitation......Page 47 VIII. IUPAC NOTATION FOR X-RAY SPECTROSCOPY......Page 48 APPENDIX I: CRITICAL ABSORPTIONWAVELENGTHS AND CRITICAL ABSORPTION ENERGIES......Page 50 APPENDIXII: CHARACTERISTICX-RAY WAVELENGTHS (A ) ANDENERGIES (keV)......Page 54 APPENDIX III: RADIATIVE TRANSITION PROBABILITIES......Page 63 APPENDIX IV: NATURALWIDTHS OF K AND L LEVELS AND Ka X-RAY LINES (FWHM), IN eV......Page 67 APPENDIX V: WAVELENGTHS OF KSATELLITE LINES (A )......Page 70 APPENDIX VI: FLUORESCENCE YIELDS AND COSTER^KRONIG TRANSITION PROBABILITIES......Page 72 APPENDIX VII: COEFFICIENTS FOR CALCULATING THE PHOTOELECTRIC ABSORPTION CROSS SECTIONS (BARNS=ATOM) VIA ln^ln REPRESENTATION......Page 82 APPENDIX VIII: COEFFICIENTS FOR CALCULATING THE INCOHERENT COLLISION CROSS SECTIONS C(BARNS=ATOM) VIATHE ln^ln REPRESENTATION......Page 88 APPENDIX IX: COEFFICIENTS FOR CALCULATING THE COHERENT SCATTERING CROSS SECTIONS R (BARNS/ATOM) VIATHE ln^ln REPRESENTATION......Page 90 APPENDIX X: PARAMETERS FOR CALCULATINGTHE TOTALMASSATTENUATIONCOEFFICIENTS INTHE ENERGYRANGE 0.1^1000 keV [VIA EQ. (78)]......Page 92 APPENDIX XI: TOTAL MASS ATTENUATION COEFFICIENTS FOR LOW-ENERGY K LINES......Page 101 APPENDIX XII: CORRESPONDENCE BETWEEN OLD SIEGBAHN AND NEWIUPAC NOTATION X-RAY DIAGRAMLINES......Page 105 REFERENCES......Page 106 I. INTRODUCTION......Page 109 II. FUNDAMENTALS OF WAVELENGTH DISPERSION......Page 114 III. LAYOUT OFA SPECTROMETER......Page 118 A. Sources......Page 119 1. Alternative Configurations......Page 121 2. Optimization......Page 122 5. Tubes with Rotating Anode......Page 124 6. Compact Flash X-Ray Sources......Page 127 7. High-Voltage Generator......Page 128 B. X-ray Tube Spectrum......Page 129 C. Collimators and Masks......Page 130 D. Dispersive Elements......Page 131 1. Crystals......Page 132 2. Multilayers......Page 138 3. Spectral Resolution......Page 148 E. The Goniometer......Page 150 F. Detectors......Page 153 1. Gas-Filled Detectors......Page 154 2. Scintillation Detectors......Page 158 3. Alternative Configurations......Page 159 5. Dead Timeand Shift of MaximumPulse Amplitude......Page 161 A. Background......Page 164 B. Qualitative Spectrometry......Page 167 C. Special Quantitative Applications......Page 169 D. Pattern Recognition......Page 172 2. Method of Nearest Neighbours......Page 173 5. Examples......Page 174 E. Analysis on the Basis of Neural Networks......Page 176 G. Limits of XRF......Page 178 1. Application Limits......Page 179 2. Limits of Precision and Accuracy......Page 181 3. High-ZLimit......Page 182 V. CHEMICAL SHIFTAND SPECIATION......Page 183 A. Electrical and Electronic Features......Page 187 1. Sequential Spectrometerswith EWTor SWT......Page 188 2. Simultaneous Instruments......Page 191 3. Milliprobes......Page 192 1. Sequential Instruments......Page 193 2. Simultaneous Instruments with Sample Surface Up or Sample Surface Down......Page 201 3. Hybrid Instruments......Page 202 VII. FUTURE PROSPECTS......Page 203 REFERENCES......Page 205 I. INTRODUCTION......Page 213 II. X-RAY TUBE EXCITATION SYSTEMS......Page 214 A. Direct and Filtered Direct Excitation......Page 215 B. Primary Beam Filter Selection......Page 218 C. Secondary Target Excitation......Page 221 D. X-ray Tubes......Page 223 1. Side-Window Geometry......Page 224 3. TransmissionTarget Geometry......Page 226 A. Fabrication and Operating Principle......Page 228 B. Crystal Materials......Page 229 C. Cooling Systems......Page 231 D. Energy Resolution......Page 233 1. Escape Peaks......Page 235 2. Sum Peaks......Page 238 4. System Contamination Peaks......Page 239 F. Detection Efficiency and EntranceWindows......Page 241 G. Detector Background......Page 243 A. Sources of Electronic Noise......Page 244 B. Resolution and Count Rate......Page 246 C. Pulse Pileup......Page 247 D. Dead-Time Correction......Page 249 REFERENCES......Page 250 I. INTRODUCTION......Page 253 B. Information Content of a Spectrum......Page 254 2. Continuum......Page 256 4. Pileup and Sum Peaks......Page 257 6. Other Artifacts......Page 258 A. Fourier Transformation, Convolution, and Deconvolution......Page 259 B. Smoothing......Page 262 1. Moving Average......Page 263 2. Savitsky and Golay Polynomial Filters......Page 264 3. Low Statistics Digital Filter......Page 267 C. Peak Search Methods......Page 269 IV. CONTINUUM ESTIMATION METHODS......Page 274 A. Peak Stripping......Page 275 B. Continuum Estimation Using Orthogonal Polynomials......Page 276 A. Peak-Area Determination in EDXRF......Page 278 B. Net Count Rate Determination inWDXRF......Page 281 1. Theory......Page 282 2. Application......Page 284 B. Partial Least-Squares Regression......Page 286 1. Theory......Page 287 2. Application......Page 289 VII. LEAST-SQUARES FITTING USING ANALYTICAL FUNCTIONS......Page 292 A. Concept......Page 293 3. Bremsstrahlung Continuum......Page 294 1. Single Gaussian......Page 295 2. Energy and Resolution Calibration Function......Page 296 3. Response Function for an Element......Page 297 4. Modified Gaussians......Page 298 5. Absorption Correction......Page 302 6. Sum and Escape Peaks......Page 303 1. Constraints......Page 304 2. Weighting the Fit......Page 306 E. Examples......Page 307 F. Evaluation of Fitting Results......Page 309 1. Error Estimate......Page 310 2. Criteria for Quality of Fit......Page 311 G. Available Computer Codes......Page 312 A. Simulation of X-ray Spectra......Page 314 B. Spectrum Evaluation Using Monte Carlo Techniques......Page 318 A. Linear-Least Squares......Page 320 B. Least-Squares Fitting Using Orthogonal Polynomials......Page 323 1. Transformation to Linear Functions......Page 324 2. General Nonlinear Least Squares......Page 325 1. Savitsky and Golay Polynomial Smoothing......Page 329 2. Low Statistics Digital Filter......Page 330 B. Peak Search......Page 331 C. Continuum Estimation......Page 333 D. Filter-Fit method......Page 335 E. Fitting Using Analytical Functions......Page 338 1. Uniform Random-Number Generator......Page 341 3. Poisson Distributed Random Deviate......Page 342 1. Linear Regression......Page 343 2. Orthogonal Polynomial Regression......Page 344 3. Nonlinear Regression......Page 346 4. Matrix Inversion......Page 349 REFERENCES......Page 350 I. INTRODUCTION......Page 354 1. Primary Fluorescence by Monochromatic Radiation......Page 356 2. Secondary Fluorescence Excited by Monochromatic Radiation......Page 359 C. Some Observations......Page 362 A. Introduction......Page 363 1. Counting Statistics......Page 364 3. Detection Limit......Page 367 5. Other Instrument Errors......Page 368 6. Particle Statistics......Page 369 1. Selecting the Analytical Line......Page 370 2. Spectral Overlap......Page 371 B. Quality Control Specimens......Page 372 C. Drift-Correction Monitors......Page 373 D. Recalibration Standards......Page 374 A. Introduction......Page 375 B. Matrix Effect......Page 377 1. Scattered Radiation:Compton Scatter (in cooperationwithMark N. Ingham, British Geological Survey,Keyworth,UK)......Page 379 2. Internal Standard......Page 383 3. Standard Addition Methods......Page 385 4. Dilution Methods......Page 386 2. The Fundamental ParameterMethod......Page 387 3. Influence Coefficient Algorithms......Page 393 4. Algorithmswith Constant Coefficients......Page 396 5. Algorithms withVariable Coefficients......Page 401 6. Specimens with More thanTwo Compounds......Page 408 7. Application......Page 412 8. Algorithms with Empirical Coefficients......Page 413 VI. CONCLUSION......Page 415 REFERENCES......Page 416 SUGGESTIONS FOR FURTHER READING......Page 418 I. INTRODUCTION......Page 419 II. EMISSION--TRANSMISSION METHOD......Page 420 A. Accuracy and Limitations of the Emission--Transmission Method......Page 425 A. Absorption Corrections Based on Incoherent Scattered Radiation......Page 427 B. Absorption Corrections Based on Both Coherent and Incoherent Scattered Radiations......Page 428 A. Particle Size Effects in XRFAnalysis of Thin and Intermediate-Thickness Specimens......Page 435 1. Empirical Particle Size Correction Method Using Dual Measurements......Page 437 2. Applicability of the Particle Size CorrectionMethod......Page 438 3. Selection of the Optimum Measurement Conditions......Page 439 REFERENCES......Page 442 I. INTRODUCTION......Page 444 II. BASIC EQUATIONS......Page 446 A. Absorption of X-rays......Page 447 C. Scattered X-ray Intensities......Page 448 D. X-ray Fluorescence Analysis......Page 450 E. X-ray Preferential Absorption Analysis......Page 451 F. X-ray Scattering Analysis......Page 452 A. Radioisotope Sources......Page 453 1. Energy Resolution of the Detector......Page 456 2. Energy Resolution of Detector and Minimum Detectable Level......Page 459 3. Detector Efficiency for X-rays and Detector-Sensitive Area......Page 460 4. Ratio of Full-Energy Peak toTotal Spectrum......Page 464 6. Developments in Solid-State Detectors......Page 465 C. Electronics......Page 466 A. XRF Techniques Based on Solid-State Detectors......Page 467 B. XRF Techniques Based on Proportional Detectors......Page 470 C. XRF Techniques Based on Scintillation Detectors......Page 472 1. Filters......Page 474 3. Detector-Radiator Assemblies......Page 476 D. X-ray Preferential AbsorptionTechniques......Page 478 V. FACTORS AFFECTING THE OVERALL ACCURACYOF XRFANALYSIS......Page 480 A. Overall Accuracy and Time forAnalysis......Page 481 B. Uncertainties of Sampling and Sample Presentation......Page 482 1. Uncertainty Due to Sample Heterogeneity......Page 483 C. Choice of Radioisotope X-rayTechnique......Page 484 A. Identification of Alloys......Page 485 B. Determination of Uranium and Gold in Ore......Page 490 C. On-Line Determination of CoatingMass......Page 491 D. On-Stream Analysis of Metalliferous Mineral Slurries......Page 492 E. On-Line Determination of the Ash Content of Coal......Page 493 G. Determination of Sulfur and Chlorine in Oil......Page 496 2. Air Particulates Monitoring in Stack Emissions andWorkplace Air......Page 500 3. Soil Screening for Inorganic Contaminants......Page 502 4. Analysis of Liquid HazardousWaste......Page 504 5. Analysis of LeadinWall Paint......Page 505 VII. FUTURE OF RADIOISOTOPE-EXCITEDXRFANALYSIS......Page 506 VIII. CONCLUSIONS......Page 507 APPENDIX: LIST OF COMPANIES THAT MANUFACTURE RADIOISOTOPE-BASED X-RAYANALYZERS AND SYSTEMS......Page 508 REFERENCES......Page 509 I. INTRODUCTION......Page 512 II. PROPERTIES OF SYNCHROTRON RADIATION......Page 514 III. DESCRIPTION OF SYNCHROTRON FACILITIES......Page 517 IV. APPARATUS FOR X-RAYMICROSCOPY......Page 518 A. Collimated X-Ray Microscopes......Page 520 B. Focused X-Ray Microscopes......Page 526 2. Photon Factory (1990)......Page 528 3. SRS (1990)......Page 529 5. LBL (1988)......Page 530 7. Cornell High Energy Synchrotron Source (CHESS)......Page 531 9. Advanced Photon Source (1998)......Page 532 C. Experiments at a Distance......Page 533 V. CONTINUUMANDMONOCHROMATIC EXCITATION......Page 534 VI. QUANTITATION......Page 535 VII. SENSITIVITIES ANDMINIMUMDETECTION LIMITS......Page 536 VIII. BEAM-INDUCED DAMAGE......Page 541 IX. APPLICATIONS OF SRIXE......Page 543 B. Biology/Medical: Calcified Tissue Studies......Page 545 C. Geology and Environmental Sciences......Page 550 D. Materials and Chemical Sciences......Page 552 X. TOMOGRAPHY......Page 553 XI. EXAFS ANDXANES......Page 556 XII. FUTURE DIRECTIONS......Page 562 ACKNOWLEDGMENTS......Page 565 REFERENCES......Page 566 I. INTRODUCTION......Page 570 II. PHYSICAL PRINCIPLES......Page 571 A. Excitation Sources forTXRF......Page 578 B. Sample Reflectors......Page 583 C. Detectors......Page 584 IV. CHEMICAL ANALYSIS......Page 585 A. Sample Reflectors and Their Cleaning......Page 586 B. Special Sample PreparationTechniques forTXRF......Page 587 C. General Sample Preparation......Page 588 D. Some Applications......Page 591 E. Quantification......Page 593 V. SURFACE ANALYSIS......Page 594 A. Quantification......Page 598 A. Depth Profiles......Page 599 B. Thin Films......Page 600 VII. SYNCHROTRON RADIATION EXCITATION......Page 601 VIII. LIGHT ELEMENTS......Page 606 A. X-ray Reflectometry......Page 608 B. Grazing Emission XRF......Page 609 REFERENCES......Page 610 I. INTRODUCTION......Page 614 A. Scattering of Nonpolarized Radiation......Page 616 B. Scattering of Linear Polarized Radiation......Page 618 C. Cartesian Geometry......Page 620 III. BARKLA SYSTEMS......Page 621 A. Scattering Material......Page 623 B. Geometry of the Polarization Unit......Page 624 C. X-rayTubes and Filters......Page 625 E. Multiple-Layer Scatterers......Page 626 F. Applications......Page 627 A. Orthogonal System......Page 629 B. Curved Crystals......Page 635 C. Applications......Page 636 VI. SECONDARY TARGETS......Page 638 VII. CONCLUSION......Page 639 REFERENCES......Page 640 I. INTRODUCTION AND HISTORICAL PERSPECTIVE......Page 642 A. Development of Microscopic X-ray Emission Analysis......Page 644 1. First-Generation Focusing Systems......Page 645 2. Second-Generation Focusing Systems......Page 646 3. X-ray Concentrators......Page 647 A. PhotonVersus Charged-Particle-Induced X-ray Emission......Page 648 1. Optical Theory of X-rays......Page 653 2. X-ray Reflectivity......Page 654 3. Geometrical Aberrations......Page 655 III. INSTRUMENTATION FOR MICROBEAMXRF......Page 657 B. X-ray Optics......Page 658 1. Different Capillary Types......Page 659 2. X-ray Transport Inside Capillaries......Page 661 3. Ray-Tracing Models......Page 663 4. Practical Considerations......Page 664 5. Capillary Alignment......Page 666 C. Sample Movement and Visualization Equipment......Page 667 1. Monocapillary Setups......Page 670 2. Polycapillary Setups......Page 674 F. Commercial Equipment......Page 677 A. Static and Dynamic Scanning......Page 678 B. Spectrum Processing......Page 680 1. Color Encoding......Page 682 2. Automated Image Segmentation......Page 684 1. General Considerations......Page 688 2. Information Depth......Page 690 3. Self-Absorption Correction in Heterogeneous Samples......Page 691 4. Conditions for Local Homogeneity/Factors Determining Lateral Resolution......Page 696 5. Prediction of the Spectral Response of u-XRF Spectrometers......Page 697 6. Analytical Model for u-XRFAnalysis of Particles......Page 699 7. Detection of Systematic Variations in u-XRF Data Due to Topological Effects......Page 701 E. Fluorescent X-ray Microtomography......Page 703 1. Plating Thickness/Composition Gauging......Page 707 2. Microelectronics Industry......Page 708 3. Waste Characterization......Page 709 5. Materials Analysis in the Industrial Laboratory......Page 710 1. Individual Particulate Analysis......Page 711 2. Tree Ring Analysis......Page 712 1. Trace Element Mapping in Corroded Roman Glass......Page 715 3. Local Analysis of Bronze Statues......Page 716 4. Document Forgeries......Page 717 1. Hair Analysis......Page 721 2. Individual Particle Analysis......Page 722 REFERENCES......Page 723 I. INTRODUCTION......Page 729 1. Slowing Down of Charged Particles in Matter:Stopping Power......Page 730 2. Inner-Shell Vacancy Creation: Ionization and X-ray Production Cross Sections......Page 731 1. Electron Bremsstrahlung......Page 734 4. Other Sources of Background......Page 736 A. Accelerators......Page 737 1. Macro-PIXE inVacuum......Page 738 2. Nonvacuum Macro-PIXE......Page 741 3. Nuclear Microprobes......Page 742 2. Micro-PIXE......Page 747 A. Analysis of PIXE Spectra......Page 749 B. Quantitation for Thin Specimens......Page 750 C. Quantitation for Specimens of IntermediateThickness and for Infinitely Thick Specimens......Page 752 D. Detection Limits in Thin- and Thick-Target PIXE......Page 754 E. Precision and Accuracy in Thin- and Thick-Target PIXE......Page 757 A. General......Page 758 B. Specimen Preparation for Micro-PIXE......Page 759 A. Biological and Medical Samples......Page 760 1. Sample and Specimen Preparation......Page 761 2. Examples ofMacro-PIXE......Page 762 3. Examples of Micro-PIXE......Page 766 B. Atmospheric Aerosols......Page 771 1. Sampling Devices and Collection Surfaces......Page 773 2. Examples......Page 774 1. Combustion Sources......Page 781 2. Aqueous Environment......Page 782 3. Mineral Prospecting and Geology......Page 783 D. Applications in Arts and Archaeology......Page 785 1. SemiconductorMaterials......Page 789 3. Metals......Page 791 4. Cellulose Fibers......Page 792 A. Elastic Scattering Spectrometry and Related Techniques......Page 793 B. Nuclear Reaction Analysis......Page 795 C. Chemical and Structural Information......Page 798 1. Ion-BeamThermography......Page 799 2. Ionoluminescence......Page 800 VIII. CONCLUSIONS......Page 802 REFERENCES......Page 807 I. INTRODUCTION......Page 820 II. QUANTITATIVE ANALYSIS......Page 825 1. ZAFCorrections......Page 826 2. AnalysisMethod Based on Integration of Curves......Page 840 3. Evaluation of ZAF and Analytical Correction Procedures......Page 847 B. Empirical Approach to Quantitative Analysis......Page 849 C. ‘‘Standardless’’ Quantitative Electron Probe X-ray Microanalysis with EDS......Page 856 1. First-Principles Standardless Analysis......Page 857 2. ‘‘Fitted Standards’’Standardless Analysis......Page 860 3. Using Standardless Analysis......Page 863 1. Lateral and Depth Resolution......Page 866 1. Limits of Detection......Page 868 2. Limitations Imposed by FluorescenceY|eld......Page 871 3. Quantitative Analysis at Low Beam Energy......Page 872 1. Improvements toWavelength-Dispersive Spectrometry......Page 879 2. Microcalorimetry Energy-Dispersive Spectrometry......Page 880 A. Quantitative Analysis of Layered Specimens......Page 885 1. Methods Based on Calculation......Page 886 2. Methods Based onMonte Carlo Calculations......Page 891 3. Correction for Secondary Fluorescence......Page 892 B. Quantitative Analysis of Thin Specimens at HighVoltages......Page 898 C. Quantitative Analysis of Particles with Energy-Dispersive X-ray Spectrometry......Page 902 1. Normalization......Page 907 2. Particle Standards......Page 908 3. Geometric Modeling of Particle Shape......Page 909 4. Peak-to-Background Ratios......Page 915 A. x–y Mapping......Page 918 B. Composition-Composition Histograms......Page 932 REFERENCES......Page 935 I. INTRODUCTION......Page 941 II. SOLID SAMPLES......Page 942 A. Metallic Specimens......Page 943 B. Powdered Specimens......Page 946 1. Grinding......Page 947 2. Loose Powders......Page 948 3. Pelletizing......Page 950 A. Fluxes and Additives......Page 952 B. Fusion Procedures......Page 954 IV. LIQUID SPECIMEN......Page 956 A. Physical Preconcentration......Page 957 1. (Co)precipitationMethods......Page 959 2. Ion-ExchangeMethods......Page 962 3. Chelation and Sorption ImmobilizationMethods......Page 964 V. BIOLOGICAL SAMPLES......Page 966 A. Physical Methods of Sample Preparation......Page 967 B. Chemical Methods of Sample Preparation......Page 968 C. Sample Preparation forAnalysis with Spatial Resolution......Page 972 VI. ATMOSPHERIC PARTICLES......Page 973 VII. SAMPLE SUPPORT MATERIALS......Page 976 REFERENCES......Page 978 1. X-ray Physics / Andrzej A. Markowicz -- 2. Wavelength-dispersive X-ray Fluorescence / Jozef A. Helsen And Andrzej Kuczumow -- 3. Energy-dispersive X-ray Fluorescence Analysis Using X-ray Tube Excitation / Andrew T. Ellis -- 4. Spectrum Evaluation / Piet Van Espen -- 5. Quantification Of Infinitely Thick Specimens By Xrf Analysis / Johan L. De Vries And Bruno A. R. Vrebos -- 6. Quantification In Xrf Analysis Of Intermediate-thickness Samples / Andrzej A. Markowicz And Rene E. Van Grieken -- 7. Radioisotope-excited X-ray Analysis / Stanislaw Piorek -- 8. Synchrotron Radiation-induced X-ray Emission / Keith W. Jones -- 9. Total Reflection X-ray Fluorescence / Peter Kregsamer, Christina Streli And Peter Wobrauschek -- 10. Polarized Beam X-ray Fluorescence Analysis / Joachim Heckel And Richard W. Ryon -- 11. Microbeam Xrf / Anders Rindby And Koen H. A. Janssens -- 12. Particle-induced X-ray Emission Analysis / Willy Maenhaut And Klas G. Malmqvist -- 13. Electron-induced X-ray Emission / John A. Small, Dale E. Newbury And John T. Armstrong -- 14. Sample Preparation For X-ray Fluorescence / Martina Schmeling And Rene E. Van Grieken. Edited By René E. Van Grieken, Andrzej A. Markowicz. Includes Bibliographical References And Index.