Laser-Induced Breakdown Spectroscopy (LIBS): Fundamentals and Applications

640 Pages·2006·10.38 MB·English

by  Andrzej W. Miziolek

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LASER-INDUCED BREAKDOWN SPECTROSCOPY (LIBS)
Laser-inducedbreakdownspectroscopy(LIBS)isanemergingtechniquefordetermining
elementalcompositioninreal-time.Withtheabilitytoanalyzeandidentifychemicaland
biologicalmaterialsinsolids,liquids,andgaseousformswithlittleornosamplepreparation,
itismoreversatilethanconventionalmethodsandisidealforon-siteanalysis.
ThisisthefirstcomprehensivereferencebookexplainingthefundamentalsoftheLIBS
phenomenon, its history, and its fascinating applications across 18 chapters written by
recognizedleadersinthefield.Over300illustrationsaidunderstanding.
Thisbookwillbeofsignificantinteresttoresearchersinchemicalandmaterialsanalysis
withinacademia,government,military,andindustry.
Andrzej W. MiziolekisaSeniorResearchPhysicistattheUSArmyResearchLabo-
ratory.Hisworkiscurrentlyconcentratedonnanomaterialsresearchandonthedevelopment
oftheLIBSsensortechnology.
Vincenzo Palleschi isaresearcherintheInstituteforChemical-PhysicalProcesses
attheItalianNationalResearchCounciland,inparticular,theAppliedLaserSpectroscopy
Laboratory.
Israel Schechter is Professor of Chemistry in the Department of Chemistry at the
Technion–IsraelInstituteofTechnology.Hismainscientificinterestisinnewmethodsfor
fastanalysisofparticulatematerials.

LASER-INDUCED BREAKDOWN
SPECTROSCOPY (LIBS)
Fundamentals and Applications
Editedby
ANDRZEJ W. MIZIOLEK
USArmyResearchLaboratory
VINCENZO PALLESCHI
InstitutoperiProcessiChimico-Fisici,Italy
ISRAEL SCHECHTER
Technion–IsraelInstituteofTechnology,Haifa,Israel
cambridge university press
Cambridge, New York, Melbourne, Madrid, Cape Town, Singapore, São Paulo
Cambridge University Press
TheEdinburghBuilding,Cambridgecb22ru,UK
Published in the United States of America by Cambridge University Press, New York
www.cambridge.org
Information on this title: www.cambridge.org/9780521852746
© A. Miziolek, V. Palleschi and I. Schechter 2006
This publication is in copyright. Subject to statutory exception and to the provision of
relevant collective licensing agreements, no reproduction of any part may take place
without the written permission of Cambridge University Press.
First published in print format 2006
isbn-13 978-0-511-24529-9eBook (EBL)
isbn-10 0-511-24529-7 eBook (EBL)
isbn-13 978-0-521-85274-6hardback
isbn-10 0-521-85274-9 hardback
Cambridge University Press has no responsibility for the persistence or accuracy of urls
for external or third-party internet websites referred to in this publication, and does not
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Contents
List of contributors page x
Preface xv
1 HistoryandfundamentalsofLIBS 1
DavidA.CremersandLeonJ.Radziemski
1.1 Introduction 1
1.2 Basicprinciples 1
1.3 CharacteristicsofLIBS 5
1.4 LIBSasananalyticaltechnique 17
1.5 EarlyLIBSinstruments 27
1.6 ComponentsforaLIBSapparatus 30
1.7 Conclusion 36
1.8 References 36
2 Plasmamorphology 40
IsraelSchechterandValeryBulatov
2.1 Introduction 40
2.2 Experimentalimagingtechniques 41
2.3 Time-integratedmorphology 59
2.4 Time-resolvedmorphology:excitationbymediumlaserpulses
(1–100ns) 73
2.5 Time-resolvedmorphology:excitationbylonglaserpulses(>100ns) 110
2.6 Time-resolvedmorphology:excitationbyshortlaserpulses(fs–ps) 112
2.7 Time-resolvedmorphology:excitationbydoublelaserpulses 113
2.8 Conclusions 118
2.9 References 118
3 Fromsampletosignalinlaser-inducedbreakdownspectroscopy:acomplex
routetoquantitativeanalysis 122
E.Tognoni,V.Palleschi,M.Corsi,G.Cristoforetti,N.Omenetto,I.Gornushkin,
B.W.SmithandJ.D.Winefordner
3.1 Introduction 122
3.2 Thecharacteristicsoflaser-inducedplasmasandtheirinfluenceon
quantitativeLIBSanalysis 123
v
vi Contents
3.3 Quantitativeanalysis 148
3.4 Conclusions 164
3.5 Appendix.Tableofrepresentativelimitsofdetection 166
3.6 References 167
4 Laser-inducedbreakdowningases:experimentsandsimulation 171
ChristianG.Parigger
4.1 Introduction 171
4.2 Laser-inducedignitionapplication 172
4.3 Focalvolumeirradiancedistribution 173
4.4 HydrogenBalmerseriesatomicspectra 176
4.5 Diatomicmolecularemissionspectra 177
4.6 SimulationbyuseoftheprogramNEQAIR 179
4.7 Computationalfluiddynamicsimulations 186
4.8 Summary 189
4.9 References 191
5 AnalysisofaerosolsbyLIBS 194
UlrichPanneandDavidHahn
5.1 Introductiontoaerosolscience 194
5.2 Laser-inducedbreakdownofgases 209
5.3 AnalysisofaerosolsbyLIBS 217
5.4 ApplicationsofaerosolanalysisbyLIBS 242
5.5 Futuredirections 245
5.6 References 245
6 ChemicalimagingofsurfacesusingLIBS 254
J.M.VadilloandJ.J.Laserna
6.1 Introduction 254
6.2 LIBSchemicalimaging:operationalmodes 255
6.3 SpatialresolutioninLIBSimaging 258
6.4 ApplicationsofLIBSimaging 262
6.5 Concludingremarksandoutlook 277
6.6 References 279
7 BiomedicalapplicationsofLIBS 282
HelmutH.TelleandOtaSamek
7.1 Introduction 282
7.2 Investigationofcalcifiedtissuematerials 283
7.3 Investigationof“soft”tissuematerialswithcell
structure 295
7.4 Investigationofbio-fluids 301
7.5 Investigationofmicroscopicbio-samples 304
7.6 Concludingremarks 309
7.7 References 309
Contents vii
8 LIBSfortheanalysisofpharmaceuticalmaterials 314
SimonBe´chardandYvesMouget
8.1 Introduction 314
8.2 Needsofthepharmaceuticalindustry 316
8.3 ComparisonofLIBSwiththecurrenttechnologies 317
8.4 ComponentsofaLIBSinstrumentforapplicationsinthe
pharmaceuticalindustry 319
8.5 ApplicationsofLIBStotheanalysisofpharmaceutical
materials 323
8.6 Conclusions 330
8.7 References 331
9 CulturalheritageapplicationsofLIBS 332
DemetriosAnglosandJohnC.Miller
9.1 Introduction 332
9.2 Artandanalyticalchemistry 333
9.3 WhyLIBSinculturalheritage? 333
9.4 Physicalprinciples 335
9.5 Instrumentation 336
9.6 Analyticalparametersandmethodology 338
9.7 ExamplesofLIBSanalysisinartandarchaeology 344
9.8 LIBSincombinationswithothertechniques 357
9.9 Concludingremarks 363
9.10 References 363
10 CivilianandmilitaryenvironmentalcontaminationstudiesusingLIBS 368
J.P.Singh,F.Y.Yueh,V.N.Rai,R.Harmon,S.Beaton,
P.French,F.C.DeLucia,Jr.,B.Peterson,K.L.McNesbyand
A.W.Miziolek
10.1 Introduction 368
10.2 ApplicationsoftheADAportableLIBSunit 370
10.3 ApplicationsofDIAL’sportableLIBSsystem 381
10.4 Conclusion 396
10.5 References 396
11 IndustrialapplicationsofLIBS 400
ReinhardNoll,VolkerSturm,MichaelStepputat,AndrewWhitehouse,
JamesYoungandPhilipEvans
11.1 Introduction 400
11.2 Metalsandalloysprocessing 400
11.3 Scrapmaterialsortingandrecycling 409
11.4 Nuclearpowergenerationandspentfuelreprocessing 417
11.5 MiscellaneousindustrialapplicationsofLIBS 435
11.6 References 436
viii Contents
12 Resonance-enhancedLIBS 440
N.H.Cheung
12.1 Introductiontoresonance-enhancedLIBS 440
12.2 Basicprinciplesofspectrochemicalexcitationinlaser-induced
plasmas 441
12.3 RELIPSanalysisofsolids 451
12.4 Liquidsamples 463
12.5 Gaseoussamples 473
12.6 Conclusion:resonance-enhancedLIBSasananalyticaltool 473
12.7 References 474
13 Short-pulseLIBS:fundamentalsandapplications 477
R.E.Russo
13.1 Introduction 477
13.2 Effectofpulsedurationonablation 478
13.3 Effectofpulsedurationonplasma 479
13.4 Picosecond-inducedelectronplasma 480
13.5 Femtosecondplasma 482
13.6 Short-pulseLIBS 483
13.7 Conclusion 487
13.8 References 488
14 High-speed,high-resolutionLIBSusingdiode-pumpedsolid-statelasers 490
HolgerBetteandReinhardNoll
14.1 Introduction 490
14.2 Diode-pumpedsolid-statelasers 491
14.3 Stateoftheart 494
14.4 ScanningLIBS 498
14.5 Laser-inducedcratergeometryandspatialresolutionofhigh-speed,
high-resolutionscanningLIBSwithDPSSL 510
14.6 References 513
15 Laser-inducedbreakdownspectroscopyusingsequentiallaserpulses 516
JackPender,BillPearman,JonScaffidi,ScottR.Goodeand
S.MichaelAngel
15.1 Introduction 516
15.2 Dual-pulseLIBS 517
15.3 Summary 532
15.4 References 534
16 MicroLIBStechnique 539
PascalFichet,Jean-LucLacour,DenisMenut,PatrickMauchien,Annie
Rivoallan,Ce´cileFabre,JeanDubessyandMarie-ChristineBoiron
16.1 Introduction 539
16.2 Experimentalset-upforthemicroLIBSsystem 543
16.3 Resultsanddiscussion 547