Particle-Induced X-Ray Emission Spectrometry (PIXE)

Transcription

1 Particle-Induced X-Ray Emission Spectrometry (PIXE) Edited by SVEN A. E. JOHANSSON Department of Nuclear Physics Lund Institute of Technology Lund, Sweden JOHN L. CAMPBELL Department of Physics University of Guelph Guelph, Ontario, Canada KLAS G. MALMQVIST Department of Nuclear Physics Lund Institute of Technology Lund, Sweden A WILEY-INTERSCIENCE PUBLICATION JOHN WILEY & SONS, INC. New York / Chichester / Brisbane / Toronto / Singapore

2 CONTENTS PREFACE CUMULATIVE LISTING OF VOLUMES IN SERIES xvn xix CHAPTER 1 INTRODUCTION TO PIXE Sven A. E. Johansson 1.1. A Brief History 1.2. Basic Principles References CHAPTER 2 INSTRUMENTATION, FUNDAMENTALS, AND QUANTIFICATION 19 John L. Campbell 2.1. Instrumentation Beam Preparation Instrumentation of Specimen Chamber Measurement of Beam Current and Integrated Charge Specimens X-Ray Production Processes Characteristic X-rays Continuous Background Electron Bremsstrahlung Gamma-Ray Background X-Ray Spectroscopy Choice of Spectrometer Si (Li) Detector Calibration Detector Lineshape and Escape Peaks Pile-up Distortion of Spectrum 49 ix

3 X CONTENTS Detection Efficiency X-Ray Absorbers Computer Modelling of PIXE Spectra Quantitative Analysis: Standardization Relationship Between X-ray Intensities and Concentrations Analysis of Thin Specimens: Thin-Target Sensitivity Curves Analysis of Major and Minor Elements in Thick Specimens Thick-Target Sensitivity Curves Analysis of Trace Elements in Thick Specimens Trace-Element Analysis in Specimens of Intermediate Thickness Film Thickness Measurement and Analysis of Multiple-Layer Specimens Data Base and Its Accuracy Extraction of X-Ray Intensities from PIXE Spectra Least-Squares Fitting and Model X-ray Spectrum Continuous Background Weighting of Differences Dynamic Analysis Method Software Packages Accuracy of PIXE Analysis Limits of Detection Projectiles Other Than Protons 92 References 94 CHAPTER 3 THE HIGH-ENERGY ION MICROPROBE 101 Frank Watt and Geoff W. Grime 3.1. Introduction High-Energy Ion Microbeam Techniques Particle-Induced X-Ray Emission Rutherford Backscattering Spectrometry 104

4 CONTENTS XI Nuclear Reaction Analysis Scanning Transmission Ion Microscopy Ion Microtomography Ionoluminescence Secondary Electron Imaging Microbeam Technology Probe-Forming Systems Target Chambers and Detectors Data Acquisition and Analysis Practical Hints on How to Achieve Small Spot Sizes Beam Broadening Due to Lens Aberrations Beam Broadening Due to External Sources System Performance Microbeam Applications Biomedicine Environmental Research Materials Science Art and Archaeology Earth Sciences Concluding Remarks 160 References 161 CHAPTER 4 BIOLOGICAL AND MEDICAL APPLICATIONS 167 Klas G. Malmqvist 4.1. Introduction Biomedicine Sampling Sample Size Effects Sample Preparation Macro-PIXE Drying Elimination of Organic Matrix 175

5 Xll CONTENTS Target Preparation Special Sample Preparation Techniques Micro-PIXE Cryopreparation Irradiation of Specimens Combination with Other Methods Evaluation of Data Applications Macro-PIXE Medicine Zoology Botany Environment Micro-PIXE Medicine Zoology Botany Limnology Concluding Remarks 228 References 230 CHAPTER 5 COMPOSITIONAL ANALYSIS OF ATMOSPHERIC AEROSOLS 237 Thomas A. Cahill 5.1. Introduction Nature of Atmospheric Aerosols Early Efforts in PIXE Analysis of Aerosols Collection of Atmospheric Aerosols Settling or Dry Deposition Filtration Optimizing Aerosol Sampling Protocols Impaction PIXE Analysis of Atmospheric Aerosols PIXE Analysis Matched to Aerosol Samples 255

6 CONTENTS Xlll Interpretation of PIXE Aerosol Data Quality Assurance of PIXE Data The Essential Transformation: PIXE Laboratory Doing Aerosols versus Aerosol Laboratory Doing PIXE Complementary Analytical Methods to PIXE Mass Forward Alpha-Scattering Technique Proton Elastic Scattering Analysis Other Complementary Techniques Atmospheric Optics, Visibility, and Global Climate Conceptual Framework for Visibility Research Sampling and Analysis of Causal Aerosols Sampling and Analysis of Tracer Aerosols IMPROVE Protocol 5.8. Future Possibilities PIXE and Highly Size Resolved Samples PIXE and Portable Samplers PIXE and Gas Analysis PIXE Microprobe and Aerosol Research PIXE and Global Climate References CHAPTER 6 APPLICATIONS IN EARTH SCIENCES 313 John L. Campbell 6.1. Introduction Sampling of Geological Material Bulk Material: Macro-PIXE Analysis 314

7 XIV CONTENTS Individual Grains and Crystallites: Micro-PIXE Analysis Practical Aspects of Analysis Specimens and Specimen Chamber Dynamic Range of PIXE Spectra Role of Matrix in Trace-Element Analysis Limits of Detection: Precision and Accuracy Applications Overview Extraterrestrial Material Mineralogy and Petrology of Massive Sulfide Ore Deposites Igneous Petrology and Mineralogy Chemical Zoning Studies Fluid Inclusions Various Applications Ancillary Techniques 360 References 362 CHAPTER 7 APPLICATIONS IN ART AND ARCHAEOLOGY 367 Klas G. Malmqvist 7.1. Introduction General Analytical Problems Material Properties External Beam Microbeams Applications Stone Material and Gern Stones Gern Stones Obsidians Surface Characterization Pottery and Related Materials Glass 384

8 CONTENTS XV Metals Bronze Copper and Copper Alloys Tin Iron Noble Metals Osteology "Paperlike" Materials Experimental Arrangement Inks and Printing Techniques Letter Identification Stamps Pigments and Paintings Conclusions 412 References 412 CHAPTER 8 COMPARISON WITH OTHER METHODS: FUTURE PROSPECTS 419 Sven A. E. Johansson and John L. Campbell References 433 INDEX 435