Оглавление
Jörg Flock. X-Ray Fluorescence Spectroscopy for Laboratory Applications
Table of Contents
List of Tables
List of Illustrations
Guide
Pages
X-ray Fluorescence Spectroscopy for Laboratory Applications
Preface
List of Abbreviations and Symbols
About the Authors
1 Introduction
2 Principles of X-ray Spectrometry. 2.1 Analytical Performance
2.2 X-ray Radiation and Their Interaction. 2.2.1 Parts of an X-ray Spectrum
2.2.2 Intensity of the Characteristic Radiation
2.2.3 Nomenclature of X-ray Lines
2.2.4 Interaction of X-rays with Matter
2.2.4.1 Absorption
2.2.4.2 Scattering
2.2.5 Detection of X-ray Spectra
2.3 The Development of X-ray Spectrometry
2.4 Carrying Out an Analysis. 2.4.1 Analysis Method
2.4.2 Sequence of an Analysis
2.4.2.1 Quality of the Sample Material
2.4.2.2 Sample Preparation
2.4.2.3 Analysis Task
2.4.2.4 Measurement and Evaluation of the Measurement Data
2.4.2.5 Creation of an Analysis Report
3 Sample Preparation. 3.1 Objectives of Sample Preparation
3.2 Preparation Techniques. 3.2.1 Preparation Techniques for Solid Samples
3.2.2 Information Depth and Analyzed Volume
3.2.3 Infinite Thickness
3.2.4 Contaminations
3.2.5 Homogeneity
3.3 Preparation of Compact and Homogeneous Materials. 3.3.1 Metals
3.3.2 Glasses
3.4 Small Parts Materials
3.4.1 Grinding of Small Parts Material
3.4.2 Preparation by Pouring Loose Powder into a Sample Cup
3.4.3 Preparation of the Measurement Sample by Pressing into a Pellet
3.4.4 Preparation of the Sample by Fusion Beads. 3.4.4.1 Improving the Quality of the Analysis
3.4.4.2 Steps for the Production of Fusion Beads
3.4.4.3 Loss of Ignition
3.4.4.4 Quality Criteria for Fusion Beads
3.4.4.5 Preparation of Special Materials
3.5 Liquid Samples
3.5.1 Direct Measurement of Liquids
3.5.2 Special Processing Procedures for Liquid Samples
3.6 Biological Materials
3.7 Small Particles, Dust, and Aerosols
4 XRF Instrument Types. 4.1 General Design of an X-ray Spectrometer
4.2 Comparison of Wavelength- and Energy-Dispersive X-Ray Spectrometers
4.2.1 Data Acquisition
4.2.2 Resolution
4.2.2.1 Comparison of Wavelength- and Energy-Dispersive Spectrometry
4.2.2.2 Resolution of WDS Instruments
4.2.2.3 Resolution of EDS Instruments
4.2.3 Detection Efficiency
4.2.4 Count Rate Capability
4.2.4.1 Optimum Throughput in ED Spectrometers
4.2.4.2 Saturation Effects in WDSs
4.2.4.3 Optimal Sensitivity of ED Spectrometers
4.2.4.4 Effect of the Pulse Throughput on the Measuring Time
4.2.5 Radiation Flux
4.2.6 Spectra Artifacts
4.2.6.1 Escape Peaks
4.2.6.2 Pile-Up Peak
4.2.6.3 Diffraction Peaks
4.2.6.4 Shelf and Tail
4.2.7 Mechanical Design and Operating Costs
4.2.8 Setting Parameters
4.3 Type of Instruments
4.3.1 ED Instruments
4.3.1.1 Handheld Instruments
4.3.1.2 Portable Instruments
4.3.1.3 Tabletop Instruments
4.3.2 Wavelength-Dispersive Instruments. 4.3.2.1 Sequential Spectrometers
4.3.2.2 Multichannel Spectrometers
4.3.3 Special Type X-Ray Spectrometers
4.3.3.1 Total Reflection Instruments
4.3.3.2 Excitation by Monoenergetic Radiation
4.3.3.3 Excitation with Polarized Radiation
4.3.3.4 Instruments for Position-Sensitive Analysis
4.3.3.5 Macro X-Ray Fluorescence Spectrometer
4.3.3.6 Micro X-Ray Fluorescence with Confocal Geometry
4.3.3.7 High-Resolution X-Ray Spectrometers
4.3.3.8 Angle Resolved Spectroscopy – Grazing Incidence and Grazing Exit
4.4 Commercially Available Instrument Types
5 Measurement and Evaluation of X-ray Spectra. 5.1 Information Content of the Spectra
5.2 Procedural Steps to Execute a Measurement
5.3 Selecting the Measurement Conditions. 5.3.1 Optimization Criteria for the Measurement
5.3.2 Tube Parameters
5.3.2.1 Target Material
5.3.2.2 Excitation Conditions
5.3.2.3 Influencing the Energy Distribution of the Primary Spectrum
5.3.3 Measurement Medium
5.3.4 Measurement Time. 5.3.4.1 Measurement Time and Statistical Error
5.3.4.2 Measurement Strategies
5.3.4.3 Real and Live Time
5.3.5 X-ray Lines
5.4 Determination of Peak Intensity
5.4.1 Intensity Data
5.4.2 Treatment of Peak Overlaps
5.4.3 Spectral Background
5.5 Quantification Models. 5.5.1 General Remarks
5.5.2 Conventional Calibration Models
5.5.3 Fundamental Parameter Models
5.5.4 Monte Carlo Quantifications
5.5.5 Highly Precise Quantification by Reconstitution
5.5.6 Evaluation of an Analytical Method
5.5.6.1 Degree of Determination
5.5.6.2 Working Range, Limits of Detection (LOD) and of Quantification
5.5.6.3 Figure of Merit
5.5.7 Comparison of the Various Quantification Models
5.5.8 Available Reference Materials
5.5.9 Obtainable Accuracies
5.6 Characterization of Layered Materials. 5.6.1 General Form of the Calibration Curve
5.6.2 Basic Conditions for Layer Analysis
5.6.3 Quantification Models for the Analysis of Layers
5.7 Chemometric Methods for Material Characterization
5.7.1 Spectra Matching and Material Identification
5.7.2 Phase Analysis
5.7.3 Regression Methods
5.8 Creation of an Application
5.8.1 Analysis of Unknown Sample Qualities
5.8.2 Repeated Analyses on Known Samples
6 Analytical Errors
6.1 General Considerations
6.1.1 Precision of a Measurement
6.1.2 Long-Term Stability of the Measurements
6.1.3 Precision and Process Capability
6.1.4 Trueness of the Result
6.2 Types of Errors
6.2.1 Randomly Distributed Errors
6.2.2 Systematic Errors
6.3 Accounting for Systematic Errors
6.3.1 The Concept of Measurement Uncertainties
6.3.2 Error Propagation
6.3.3 Determination of Measurement Uncertainties
6.3.3.1 Bottom-Up Method
6.3.3.2 Top-Down Method
6.4 Recording of Error Information
7 Other Element Analytical Methods. 7.1 Overview
7.2 Atomic Absorption Spectrometry (AAS)
7.3 Optical Emission Spectrometry
7.3.1 Excitation with a Spark Discharge (OES)
7.3.2 Excitation in an Inductively Coupled Plasma (ICP-OES)
7.3.3 Laser-Induced Breakdown Spectroscopy (LIBS)
7.4 Mass Spectrometry (MS)
7.5 X-Ray Spectrometry by Particle Excitation (SEM-EDS, PIXE)
7.6 Comparison of Methods
8 Radiation Protection. 8.1 Basic Principles
8.2 Effects of Ionizing Radiation on Human Tissue
8.3 Natural Radiation Exposure
8.4 Radiation Protection Regulations. 8.4.1 Legal Regulations
9 Analysis of Homogeneous Solid Samples
9.1 Iron Alloys
9.1.1 Analytical Problem and Sample Preparation
9.1.2 Analysis of Pig and Cast Iron
9.1.3 Analysis of Low-Alloy Steel
9.1.4 Analysis of High-Alloy Steel
9.2 Ni–Fe–Co Alloys
9.3 Copper Alloys. 9.3.1 Analytical Task
9.3.2 Analysis of Compact Samples
9.3.3 Analysis of Dissolved Samples
9.4 Aluminum Alloys
9.5 Special Metals. 9.5.1 Refractories. 9.5.1.1 Analytical Problem
9.5.1.2 Sample Preparation of Hard Metals
9.5.1.3 Analysis of Hard Metals
9.5.2 Titanium Alloys
9.5.3 Solder Alloys
9.6 Precious Metals. 9.6.1 Analysis of Precious Metal Jewelry. 9.6.1.1 Analytical Task
9.6.1.2 Sample Shape and Preparation
9.6.1.3 Analytical Equipment
9.6.1.4 Accuracy of the Analysis
9.6.2 Analysis of Pure Elements
9.7 Glass Material. 9.7.1 Analytical Task
9.7.2 Sample Preparation
9.7.3 Measurement Equipment
9.7.4 Achievable Accuracies
9.8 Polymers. 9.8.1 Analytical Task
9.8.2 Sample Preparation
9.8.3 Instruments
9.8.4 Quantification Procedures. 9.8.4.1 Standard-Based Methods
9.8.4.2 Chemometric Methods
9.9 Abrasion Analysis
10 Analysis of Powder Samples
10.1 Geological Samples. 10.1.1 Analytical Task
10.1.2 Sample Preparation
10.1.3 Measurement Technique
10.1.4 Detection Limits and Trueness
10.2 Ores. 10.2.1 Analytical Task
10.2.2 Iron Ores
10.2.3 Mn, Co, Ni, Cu, Zn, and Pb Ores
10.2.4 Bauxite and Alumina
10.2.5 Ores of Precious Metals and Rare Earths
10.3 Soils and Sewage Sludges. 10.3.1 Analytical Task
10.3.2 Sample Preparation
10.3.3 Measurement Technology and Analytical Performance
10.4 Quartz Sand
10.5 Cement. 10.5.1 Analytical Task
10.5.2 Sample Preparation
10.5.3 Measurement Technology
10.5.4 Analytical Performance
10.5.5 Determination of Free Lime in Clinker
10.6 Coal and Coke. 10.6.1 Analytical Task
10.6.2 Sample Preparation
10.6.3 Measurement Technology and Analytical Performance
10.7 Ferroalloys. 10.7.1 Analytical Task
10.7.2 Sample Preparation
10.7.3 Analysis Technology
10.7.4 Analytical Performance
10.8 Slags. 10.8.1 Analytical Task
10.8.2 Sample Preparation
10.8.3 Measurement Technology and Analytical Accuracy
10.9 Ceramics and Refractory Materials. 10.9.1 Analytical Task
10.9.2 Sample Preparation
10.9.3 Measurement Technology and Analytical Performance
10.10 Dusts
10.10.1 Analytical Problem and Dust Collection
10.10.2 Measurement
10.11 Food. 10.11.1 Analytical Task
10.11.2 Monitoring of Animal Feed
10.11.3 Control of Infant Food
10.12 Pharmaceuticals. 10.12.1 Analytical Task
10.12.2 Sample Preparation and Analysis Method
10.13 Secondary Fuels. 10.13.1 Analytical Task
10.13.2 Sample Preparation. 10.13.2.1 Solid Secondary Raw Materials
10.13.2.2 Liquid Secondary Raw Materials
10.13.3 Instrumentation and Measurement Conditions
10.13.4 Measurement Uncertainties in the Analysis of Solid Secondary Raw Materials
10.13.5 Measurement Uncertainties for the Analysis of Liquid Secondary Raw Materials
11 Analysis of Liquids
11.1 Multielement Analysis of Liquids. 11.1.1 Analytical Task
11.1.2 Sample Preparation
11.1.3 Measurement Technology
11.1.4 Quantification
11.2 Fuels and Oils
11.2.1 Analysis of Toxic Elements in Fuels
11.2.1.1 Measurement Technology
11.2.1.2 Analytical Performance
11.2.2 Analysis of Additives in Lubricating Oils
11.2.3 Identification of Abrasive Particles in Used Lubricants
11.3 Trace Analysis in Liquids. 11.3.1 Analytical Task
11.3.2 Preparation by Drying
11.3.3 Quantification
11.4 Special Preparation Techniques for Liquid Samples. 11.4.1 Determination of Light Elements in Liquids
11.4.2 Enrichment Through Absorption and Complex Formation
12 Trace Analysis Using Total Reflection X-Ray Fluorescence. 12.1 Special Features of TXRF
12.2 Sample Preparation for TXRF
12.3 Evaluation of the Spectra. 12.3.1 Spectrum Preparation and Quantification
12.3.2 Conditions for Neglecting the Matrix Interaction
12.3.3 Limits of Detection
12.4 Typical Applications of the TXRF
12.4.1 Analysis of Aqueous Solutions. 12.4.1.1 Analytical Problem and Preparation Possibilities
12.4.1.2 Example: Analysis of a Fresh Water Standard Sample
12.4.1.3 Example: Detection of Mercury in Water
12.4.2 Analysis of the Smallest Sample Quantities. 12.4.2.1 Example: Pigment Analysis
12.4.2.2 Example: Aerosol Analysis
12.4.2.3 Example: Analysis of Nanoparticles
12.4.3 Trace Element Analysis on Human Organs. 12.4.3.1 Example: Analysis of Blood and Blood Serum
12.4.3.2 Example: Analysis of Trace Elements in Body Tissue
12.4.4 Trace Analysis of Inorganic and Organic Chemical Products
12.4.5 Analysis of Semiconductor Electronics. 12.4.5.1 Ultra-Trace Analysis on Si Wafers with VPD
12.4.5.2 Depth Profile Analysis by Etching
13 Nonhomogeneous Samples
13.1 Measurement Modes
13.2 Instrument Requirements
13.3 Data Evaluation
14 Coating Analysis. 14.1 Analytical Task
14.2 Sample Handling
14.3 Measurement Technology
14.4 The Analysis Examples of Coated Samples
14.4.1 Single-Layer Systems: Emission Mode
14.4.2 Single-Layer Systems: Absorption Mode
14.4.3 Single-Layer Systems: Relative Mode. 14.4.3.1 Analytical Problem
14.4.3.2 Variation of the Specified Working Distance
14.4.3.3 Sample Size and Spot Size Mismatch
14.4.3.4 Non-detectable Elements in the Layer: NiP Layers
14.4.4 Characterization of Ultrathin Layers
14.4.5 Multilayer Systems. 14.4.5.1 Layer Systems
14.4.5.2 Measurement Technology
14.4.5.3 Example: Analysis of CIGS Solar Cells
14.4.5.4 Example: Analysis of Solder Structures
14.4.6 Samples with Unknown Coating Systems
14.4.6.1 Preparation of Cross Sections
14.4.6.2 Excitation at Grazing Incidence with Varying Angles
14.4.6.3 Measurement in Confocal Geometry
15 Spot Analyses
15.1 Particle Analyses. 15.1.1 Analytical Task
15.1.2 Sample Preparation
15.1.3 Analysis Technology
15.1.4 Application Example: Wear Particles in Used Oil
15.1.5 Application Example: Identification of Glass Particles by Chemometrics
15.2 Identification of Inclusions
15.3 Material Identification with Handheld Instruments. 15.3.1 Analytical Tasks
15.3.2 Analysis Technology
15.3.3 Sample Preparation and Test Conditions
15.3.4 Analytical Accuracy
15.3.5 Application Examples. 15.3.5.1 Example: Lead in Paint
15.3.5.2 Example: Scrap Sorting
15.3.5.3 Example: Material Inspection and Sorting
15.3.5.4 Example: Precious Metal Analysis
15.3.5.5 Example: Prospecting and Screening in Geology
15.3.5.6 Example: Investigation of Works of Art
15.4 Determination of Toxic Elements in Consumer Products: RoHS Monitoring
15.4.1 Analytical Task
15.4.2 Analysis Technology
15.4.3 Analysis Accuracy
15.5 Toxic Elements in Toys: Toys Standard. 15.5.1 Analytical Task
15.5.2 Sample Preparation
15.5.3 Analysis Technology
16 Analysis of Element Distributions. 16.1 General Remarks
16.2 Measurement Conditions
16.3 Geology. 16.3.1 Samples Types
16.3.2 Sample Preparation and Positioning
16.3.3 Measurements on Compact Rock Samples
16.3.3.1 Sum Spectrum and Element Distributions
16.3.3.2 Object Spectra
16.3.3.3 Treatment of Line Overlaps
16.3.3.4 Maximum Pixel Spectrum
16.3.4 Thin Sections of Geological Samples
16.4 Electronics
16.5 Archeometric Investigations. 16.5.1 Analytical Tasks
16.5.2 Selection of an Appropriate Spectrometer
16.5.3 Investigations of Coins
16.5.4 Investigations of Painting Pigments
16.6 Homogeneity Tests. 16.6.1 Analytical Task
16.6.2 Homogeneity Studies Using Distribution Analysis
16.6.3 Homogeneity Studies Using Multi-point Measurements
17 Special Applications of the XRF. 17.1 High-Throughput Screening and Combinatorial Analysis
17.1.1 High-Throughput Screening
17.1.2 Combinatorial Analysis for Drug Development
17.2 Chemometric Spectral Evaluation
17.3 High-Resolution Spectroscopy for Speciation Analysis. 17.3.1 Analytical Task
17.3.2 Instrument Technology
17.3.3 Application Examples. 17.3.3.1 Analysis of Different Sulfur Compounds
17.3.3.2 Speciation of Aluminum Inclusions in Steel
17.3.3.3 Determination of SiO2 in SiC
18 Process Control and Automation. 18.1 General Objectives
18.2 Off-Line and At-Line Analysis. 18.2.1 Sample Supply and Analysis
18.2.2 Automated Sample Preparation
18.3 In-Line and On-Line Analysis
19 Quality Management and Validation. 19.1 Motivation
19.2 Validation
19.2.1 Parameters
19.2.2 Uncertainty
Appendix A Tables
Appendix B Important Information. B.1 Coordinates of Main Manufacturers of Instruments and Preparation Tools
B.2 Main Suppliers of Standard Materials
B.2.1 Geological Materials and Metals
B.2.2 Stratified Materials
B.2.3 Polymer Standards
B.2.4 High Purity Materials
B.2.5 Precious Metal Alloys
B.3 Important Websites. B.3.1 Information About X-Ray Analytics and Fundamental Parameters
B.3.2 Information About Reference Materials
B.3.3 Scientific Journals
B.4 Laws and Acts, Which Are Important for X-Ray Fluorescence. B.4.1 Radiation Protection
B.4.2 Regulations for Environmental Control
B.4.3 Regulations for Performing Analysis
B.4.4 Use of X-ray Fluorescence for the Chemical Analysis. B.4.4.1 General Regulations
B.4.4.2 Analysis of Minerals
B.4.4.3 Analysis of Oils, Liquid Fuels, Grease
B.4.4.4 Analysis of Solid Fuels
B.4.4.5 Coating Analysis
B.4.4.6 Metallurgy
B.4.4.7 Analysis of Electronic Components
References
Index
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