X-Ray Fluorescence Spectroscopy for Laboratory Applications

475 Pages·2021·15.279 MB·English

by  Jörg Flock, Michael Haller, Michael Haschke

X-rayFluorescenceSpectroscopyforLaboratoryApplications
X-ray Fluorescence Spectroscopy for
Laboratory Applications
MichaelHaschke
JörgFlock
MichaelHaller
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v
Contents
Preface xvii
ListofAbbreviationsandSymbols xix
AbouttheAuthors xxiii
1 Introduction 1
2 PrinciplesofX-raySpectrometry 7
2.1 AnalyticalPerformance 7
2.2 X-rayRadiationandTheirInteraction 11
2.2.1 PartsofanX-raySpectrum 11
2.2.2 IntensityoftheCharacteristicRadiation 13
2.2.3 NomenclatureofX-rayLines 15
2.2.4 InteractionofX-rayswithMatter 15
2.2.4.1 Absorption 16
2.2.4.2 Scattering 17
2.2.5 DetectionofX-raySpectra 20
2.3 TheDevelopmentofX-raySpectrometry 21
2.4 CarryingOutanAnalysis 26
2.4.1 AnalysisMethod 26
2.4.2 SequenceofanAnalysis 27
2.4.2.1 QualityoftheSampleMaterial 27
2.4.2.2 SamplePreparation 27
2.4.2.3 AnalysisTask 28
2.4.2.4 MeasurementandEvaluationoftheMeasurementData 28
2.4.2.5 CreationofanAnalysisReport 29
3 SamplePreparation 31
3.1 ObjectivesofSamplePreparation 31
3.2 PreparationTechniques 32
3.2.1 PreparationTechniquesforSolidSamples 32
3.2.2 InformationDepthandAnalyzedVolume 32
3.2.3 InfiniteThickness 36
3.2.4 Contaminations 37
3.2.5 Homogeneity 38
vi Contents
3.3 PreparationofCompactandHomogeneousMaterials 39
3.3.1 Metals 39
3.3.2 Glasses 40
3.4 SmallPartsMaterials 41
3.4.1 GrindingofSmallPartsMaterial 42
3.4.2 PreparationbyPouringLoosePowderintoaSampleCup 43
3.4.3 PreparationoftheMeasurementSamplebyPressingintoaPellet 44
3.4.4 PreparationoftheSamplebyFusionBeads 48
3.4.4.1 ImprovingtheQualityoftheAnalysis 48
3.4.4.2 StepsfortheProductionofFusionBeads 49
3.4.4.3 LossofIgnition 53
3.4.4.4 QualityCriteriaforFusionBeads 53
3.4.4.5 PreparationofSpecialMaterials 54
3.5 LiquidSamples 55
3.5.1 DirectMeasurementofLiquids 55
3.5.2 SpecialProcessingProceduresforLiquidSamples 58
3.6 BiologicalMaterials 58
3.7 SmallParticles,Dust,andAerosols 59
4 XRFInstrumentTypes 61
4.1 GeneralDesignofanX-raySpectrometer 61
4.2 ComparisonofWavelength-andEnergy-DispersiveX-Ray
Spectrometers 63
4.2.1 DataAcquisition 63
4.2.2 Resolution 64
4.2.2.1 ComparisonofWavelength-andEnergy-Dispersive
Spectrometry 64
4.2.2.2 ResolutionofWDSInstruments 66
4.2.2.3 ResolutionofEDSInstruments 68
4.2.3 DetectionEfficiency 70
4.2.4 CountRateCapability 71
4.2.4.1 OptimumThroughputinEDSpectrometers 71
4.2.4.2 SaturationEffectsinWDSs 72
4.2.4.3 OptimalSensitivityofEDSpectrometers 73
4.2.4.4 EffectofthePulseThroughputontheMeasuringTime 74
4.2.5 RadiationFlux 75
4.2.6 SpectraArtifacts 76
4.2.6.1 EscapePeaks 76
4.2.6.2 Pile-UpPeak 77
4.2.6.3 DiffractionPeaks 77
4.2.6.4 ShelfandTail 79
4.2.7 MechanicalDesignandOperatingCosts 79
4.2.8 SettingParameters 80
4.3 TypeofInstruments 80
4.3.1 EDInstruments 81
4.3.1.1 HandheldInstruments 82
4.3.1.2 PortableInstruments 83
Contents vii
4.3.1.3 TabletopInstruments 84
4.3.2 Wavelength-DispersiveInstruments 85
4.3.2.1 SequentialSpectrometers 85
4.3.2.2 MultichannelSpectrometers 87
4.3.3 SpecialTypeX-RaySpectrometers 87
4.3.3.1 TotalReflectionInstruments 88
4.3.3.2 ExcitationbyMonoenergeticRadiation 90
4.3.3.3 ExcitationwithPolarizedRadiation 91
4.3.3.4 InstrumentsforPosition-SensitiveAnalysis 93
4.3.3.5 MacroX-RayFluorescenceSpectrometer 94
4.3.3.6 MicroX-RayFluorescencewithConfocalGeometry 95
4.3.3.7 High-ResolutionX-RaySpectrometers 96
4.3.3.8 AngleResolvedSpectroscopy–GrazingIncidenceandGrazing
Exit 96
4.4 CommerciallyAvailableInstrumentTypes 98
5 MeasurementandEvaluationofX-raySpectra 99
5.1 InformationContentoftheSpectra 99
5.2 ProceduralStepstoExecuteaMeasurement 101
5.3 SelectingtheMeasurementConditions 102
5.3.1 OptimizationCriteriafortheMeasurement 102
5.3.2 TubeParameters 103
5.3.2.1 TargetMaterial 103
5.3.2.2 ExcitationConditions 104
5.3.2.3 InfluencingtheEnergyDistributionofthePrimarySpectrum 105
5.3.3 MeasurementMedium 107
5.3.4 MeasurementTime 108
5.3.4.1 MeasurementTimeandStatisticalError 108
5.3.4.2 MeasurementStrategies 108
5.3.4.3 RealandLiveTime 109
5.3.5 X-rayLines 110
5.4 DeterminationofPeakIntensity 112
5.4.1 IntensityData 112
5.4.2 TreatmentofPeakOverlaps 112
5.4.3 SpectralBackground 114
5.5 QuantificationModels 117
5.5.1 GeneralRemarks 117
5.5.2 ConventionalCalibrationModels 118
5.5.3 FundamentalParameterModels 121
5.5.4 MonteCarloQuantifications 124
5.5.5 HighlyPreciseQuantificationbyReconstitution 124
5.5.6 EvaluationofanAnalyticalMethod 126
5.5.6.1 DegreeofDetermination 126
5.5.6.2 WorkingRange,LimitsofDetection(LOD)andof
Quantification 127
5.5.6.3 FigureofMerit 129
5.5.7 ComparisonoftheVariousQuantificationModels 129
viii Contents
5.5.8 AvailableReferenceMaterials 131
5.5.9 ObtainableAccuracies 132
5.6 CharacterizationofLayeredMaterials 133
5.6.1 GeneralFormoftheCalibrationCurve 133
5.6.2 BasicConditionsforLayerAnalysis 135
5.6.3 QuantificationModelsfortheAnalysisofLayers 138
5.7 ChemometricMethodsforMaterialCharacterization 140
5.7.1 SpectraMatchingandMaterialIdentification 141
5.7.2 PhaseAnalysis 141
5.7.3 RegressionMethods 143
5.8 CreationofanApplication 143
5.8.1 AnalysisofUnknownSampleQualities 143
5.8.2 RepeatedAnalysesonKnownSamples 144
6 AnalyticalErrors 149
6.1 GeneralConsiderations 149
6.1.1 PrecisionofaMeasurement 151
6.1.2 Long-TermStabilityoftheMeasurements 153
6.1.3 PrecisionandProcessCapability 154
6.1.4 TruenessoftheResult 156
6.2 TypesofErrors 156
6.2.1 RandomlyDistributedErrors 157
6.2.2 SystematicErrors 158
6.3 AccountingforSystematicErrors 159
6.3.1 TheConceptofMeasurementUncertainties 159
6.3.2 ErrorPropagation 160
6.3.3 DeterminationofMeasurementUncertainties 161
6.3.3.1 Bottom-UpMethod 161
6.3.3.2 Top-DownMethod 162
6.4 RecordingofErrorInformation 164
7 OtherElementAnalyticalMethods 167
7.1 Overview 167
7.2 AtomicAbsorptionSpectrometry(AAS) 168
7.3 OpticalEmissionSpectrometry 169
7.3.1 ExcitationwithaSparkDischarge(OES) 169
7.3.2 ExcitationinanInductivelyCoupledPlasma(ICP-OES) 170
7.3.3 Laser-InducedBreakdownSpectroscopy(LIBS) 171
7.4 MassSpectrometry(MS) 172
7.5 X-RaySpectrometrybyParticleExcitation(SEM-EDS,PIXE) 173
7.6 ComparisonofMethods 175
8 RadiationProtection 177
8.1 BasicPrinciples 177
8.2 EffectsofIonizingRadiationonHumanTissue 178
8.3 NaturalRadiationExposure 179
Contents ix
8.4 RadiationProtectionRegulations 181
8.4.1 LegalRegulations 181
9 AnalysisofHomogeneousSolidSamples 183
9.1 IronAlloys 183
9.1.1 AnalyticalProblemandSamplePreparation 183
9.1.2 AnalysisofPigandCastIron 184
9.1.3 AnalysisofLow-AlloySteel 185
9.1.4 AnalysisofHigh-AlloySteel 187
9.2 Ni–Fe–CoAlloys 188
9.3 CopperAlloys 189
9.3.1 AnalyticalTask 189
9.3.2 AnalysisofCompactSamples 189
9.3.3 AnalysisofDissolvedSamples 189
9.4 AluminumAlloys 191
9.5 SpecialMetals 192
9.5.1 Refractories 192
9.5.1.1 AnalyticalProblem 192
9.5.1.2 SamplePreparationofHardMetals 192
9.5.1.3 AnalysisofHardMetals 193
9.5.2 TitaniumAlloys 194
9.5.3 SolderAlloys 194
9.6 PreciousMetals 195
9.6.1 AnalysisofPreciousMetalJewelry 195
9.6.1.1 AnalyticalTask 195
9.6.1.2 SampleShapeandPreparation 196
9.6.1.3 AnalyticalEquipment 197
9.6.1.4 AccuracyoftheAnalysis 198
9.6.2 AnalysisofPureElements 198
9.7 GlassMaterial 199
9.7.1 AnalyticalTask 199
9.7.2 SamplePreparation 200
9.7.3 MeasurementEquipment 202
9.7.4 AchievableAccuracies 202
9.8 Polymers 203
9.8.1 AnalyticalTask 203
9.8.2 SamplePreparation 204
9.8.3 Instruments 205
9.8.4 QuantificationProcedures 205
9.8.4.1 Standard-BasedMethods 205
9.8.4.2 ChemometricMethods 206
9.9 AbrasionAnalysis 209
10 AnalysisofPowderSamples 213
10.1 GeologicalSamples 213
x Contents
10.1.1 AnalyticalTask 213
10.1.2 SamplePreparation 214
10.1.3 MeasurementTechnique 215
10.1.4 DetectionLimitsandTrueness 215
10.2 Ores 216
10.2.1 AnalyticalTask 216
10.2.2 IronOres 216
10.2.3 Mn,Co,Ni,Cu,Zn,andPbOres 217
10.2.4 BauxiteandAlumina 218
10.2.5 OresofPreciousMetalsandRareEarths 219
10.3 SoilsandSewageSludges 221
10.3.1 AnalyticalTask 221
10.3.2 SamplePreparation 221
10.3.3 MeasurementTechnologyandAnalyticalPerformance 222
10.4 QuartzSand 223
10.5 Cement 223
10.5.1 AnalyticalTask 223
10.5.2 SamplePreparation 224
10.5.3 MeasurementTechnology 225
10.5.4 AnalyticalPerformance 226
10.5.5 DeterminationofFreeLimeinClinker 227
10.6 CoalandCoke 227
10.6.1 AnalyticalTask 227
10.6.2 SamplePreparation 228
10.6.3 MeasurementTechnologyandAnalyticalPerformance 229
10.7 Ferroalloys 230
10.7.1 AnalyticalTask 230
10.7.2 SamplePreparation 230
10.7.3 AnalysisTechnology 232
10.7.4 AnalyticalPerformance 234
10.8 Slags 235
10.8.1 AnalyticalTask 235
10.8.2 SamplePreparation 235
10.8.3 MeasurementTechnologyandAnalyticalAccuracy 236
10.9 CeramicsandRefractoryMaterials 237
10.9.1 AnalyticalTask 237
10.9.2 SamplePreparation 237
10.9.3 MeasurementTechnologyandAnalyticalPerformance 238
10.10 Dusts 239
10.10.1 AnalyticalProblemandDustCollection 239
10.10.2 Measurement 242
10.11 Food 242
10.11.1 AnalyticalTask 242
10.11.2 MonitoringofAnimalFeed 243
10.11.3 ControlofInfantFood 244
10.12 Pharmaceuticals 245
10.12.1 AnalyticalTask 245