Laser-induced breakdown spectroscopy (LIBS)

Cover......Page 1
Half-title......Page 3
Title......Page 5
Copyright......Page 6
Contents......Page 7
Contributors......Page 12
Preface......Page 17
1.2.1 Introduction......Page 21
1.2.2 Atomic emission spectroscopy......Page 23
1.2.3 The discovery of LIBS......Page 24
1.3.1 The LIBS method in brief......Page 25
1.3.2 The physics and chemistry of the laser plasma......Page 29
1.3.3 Forming the LIBS plasma in a gas, a liquid, and on solids......Page 33
Solids......Page 34
Variety of measurement scenarios......Page 37
No sample preparation......Page 39
Sample homogeneity......Page 40
Matrix effects......Page 41
Sampling geometry......Page 42
1.4.3 Analytical performance......Page 43
1.4.4 LIBS combined with other techniques......Page 46
1.5.2 Transportable instruments......Page 47
1.5.4 Industrial instruments......Page 49
1.6.2 Laser systems......Page 50
1.6.3 Methods of spectral resolution......Page 51
1.6.4 Detectors......Page 54
1.8 References......Page 56
2.1 Introduction......Page 60
2.2 Experimental imaging techniques......Page 61
2.2.2 Slitless spectrography......Page 62
2.2.4 Spectrometer slit imaging......Page 63
2.2.5 Direct CCD imaging......Page 65
2.2.6 Time-resolved imaging through tunable filters......Page 66
2.2.8 Time-resolved fiber-assisted simultaneous spectroscopy......Page 68
2.2.9 Streak cameras......Page 70
2.2.10 High-speed gated X-ray cameras......Page 73
2.2.11 Near-resonant photographic absorption/shadow imaging......Page 74
2.2.12 Fourier transform imaging spectroscopy......Page 75
2.2.13 Double-pulse holography......Page 76
2.2.15 Nonresonance laser-induced fluorescence......Page 77
2.2.16 Acousto-optical scanning of laser-enhanced ionization......Page 78
2.3.1 Spectrometer slit imaging......Page 79
2.3.2 Monochromatic imaging spectrometry......Page 86
2.3.3 Fourier transform imaging spectroscopy......Page 90
2.4 Time-resolved morphology: excitation by medium laser pulses (1–100 ns)......Page 93
2.4.1 Spectrometer slit imaging......Page 94
2.4.2 Direct CCD imaging......Page 103
2.4.3 Time-resolved imaging through tunable filters......Page 109
2.4.4 Single-fiber scanning......Page 114
2.4.5 Time-resolved fiber-assisted simultaneous spectroscopy......Page 115
2.4.6 Streak camera......Page 122
2.4.8 Near-resonant photographic absorption/resonance shadow imaging......Page 124
2.4.10 Resonance laser-induced fluorescence......Page 128
2.5.3 Single-fiber scanning......Page 130
2.5.5 Nonresonance laser-induced fluorescence......Page 131
2.6 Time-resolved morphology: excitation by short laser pulses (fs–ps)......Page 132
2.7.1 Time-resolved imaging through tunable filters......Page 133
2.7.2 Time-resolved plasma shadowgraphs......Page 134
2.9 References......Page 138
3.1 Introduction......Page 142
3.2 The characteristics of laser-induced plasma and their influence
on quantitative LIBS analysis......Page 143
3.2.1 Stoichiometric ablation: the interaction function......Page 145
Definition of thermodynamic equilibrium in laser-induced plasmas......Page 147
Measurement of plasma temperature......Page 149
Measurement of electron density......Page 152
Evaluation of thermodynamic equilibrium conditions in laser-induced plasmas......Page 153
3.2.3 The calibration function......Page 156
The analytical calibration function......Page 157
3.2.4 The detection efficiency function......Page 167
3.3 Quantitative analysis......Page 168
3.3.1 Methods based on internal standards......Page 169
3.3.2 Calibration curves......Page 170
Correction methods for shot-to-shot fluctuations......Page 171
Single shot analysis......Page 172
3.3.3 Detection limits......Page 173
3.3.4 Multivariate analysis......Page 174
3.3.6 Matrix effects......Page 175
Methods developed to correct for matrix effects on calibration curves......Page 177
The calibration-free technique......Page 180
3.4 Conclusions......Page 184
3.5 Appendix. Table of representative limits of detection......Page 186
3.6 References......Page 187
4.1 Introduction......Page 191
4.2 Laser-induced ignition application......Page 192
4.3 Focal volume irradiance distribution......Page 193
4.4 Hydrogen Balmer series atomic spectra......Page 196
4.5 Diatomic molecular emission spectra......Page 197
4.6 Simulation by use of the program NEQAIR......Page 199
4.6.2 Results and simulations......Page 202
4.7 Computational fluid dynamic simulations......Page 206
4.8 Summary......Page 209
4.9 References......Page 211
5.1.1 Fundamentals of aerosols......Page 214
5.1.2 Chemical analysis of aerosols......Page 223
5.2 Laser-induced breakdown of gases......Page 229
5.3 Analysis of aerosols by LIBS......Page 237
5.3.1 Aerosol sampling with LIBS......Page 238
Ensemble averaging......Page 242
Conditional analysis......Page 247
Analysis of individual aerosol particles......Page 251
5.3.2 Indirect aerosol analysis by LIBS......Page 256
5.4 Applications of aerosol analysis by LIBS......Page 262
5.6 References......Page 265
6.1 Introduction......Page 274
6.2 LIBS chemical imaging: operational modes......Page 275
6.3.1 Lateral resolution......Page 278
6.3.2 Surface sensitivity......Page 279
6.3.3 Depth resolution......Page 281
6.4.1 Scan analysis (lateral distributions)......Page 282
6.4.2 Depth profiling......Page 284
6.4.3 Mapping......Page 286
6.5 Concluding remarks and outlook......Page 297
6.6 References......Page 299
7.1 Introduction......Page 302
7.2 Investigation of calcified tissue materials......Page 303
7.2.1 Methodology......Page 304
7.2.2 The analysis of teeth......Page 305
Spatial mapping of elemental content......Page 306
Determination of carious and heathy tissues......Page 308
Tracing environmental influences on teeth......Page 310
7.2.3 The analysis of bones......Page 311
7.2.4 The analysis of other calcified bio-samples......Page 312
7.2.5 On the problem of calibration standards......Page 314
7.3.1 Analysis of human and animal tissue......Page 315
7.3.2 Analysis of plants......Page 317
7.4 Investigation of bio-fluids......Page 321
7.5 Investigation of microscopic bio-samples......Page 324
7.7 References......Page 329
8.1 Introduction......Page 334
8.2 Needs of the pharmaceutical industry......Page 336
8.3 Comparison of LIBS with the current technologies......Page 337
8.4 Components of a LIBS instrument for applications in the
pharmaceutical industry......Page 339
8.5.2 Blend and tablet uniformity......Page 343
8.5.5 Drug and component mapping......Page 348
8.6 Conclusions......Page 350
8.7 References......Page 351
9.1 Introduction......Page 352
9.3 Why LIBS in cultural heritage?......Page 353
9.4 Physical principles......Page 355
9.5 Instrumentation......Page 356
9.6 Analytical parameters and methodology......Page 358
9.6.2 Irradiation-detection parameters......Page 359
9.6.3 LIBS analysis of objects of cultural heritage (qualitative analysis)......Page 361
9.6.4 Quantitative analysis......Page 363
9.7.1 Analysis of pigments......Page 364
9.7.2 Analysis of pottery......Page 372
9.7.3 Analysis of marble, stone, glass, and geological samples......Page 373
9.7.4 Analysis of metals......Page 374
9.7.6 Control of laser cleaning......Page 376
9.8.1 LIBS and Raman microscopy......Page 377
9.8.2 LIBS and fluorescence spectroscopy......Page 379
9.8.3 LIBS and mass spectrometry......Page 382
9.10 References......Page 383
10.1 Introduction......Page 388
10.2.1 The field-portable LIBS system......Page 390
Sierra Army Depot, CA......Page 392
10.2.3 Calibration......Page 395
Desert varnish......Page 398
Hydrothermal alteration......Page 400
10.3.1 DIAL LIBS system......Page 401
10.3.2 Continuous emission monitor......Page 402
10.3.3 Containment in liquid......Page 407
Liquid configuration for plasma formation......Page 408
LIBS signal enhancement in liquid application......Page 410
10.5 References......Page 416
11.2.1 Background......Page 420
11.2.2 Identification of pipe fittings......Page 421
11.2.3 Slag analysis......Page 424
11.2.4 Liquid steel analysis......Page 426
11.3.1 Background......Page 429
11.3.2 Identification of technical polymers for material specific recycling......Page 431
11.3.3 Classification of technical glasses during the recycling of electronic waste......Page 435
11.4.1 Background......Page 437
In situ batch identification of Magnox reactor control rods......Page 438
In situ compositional analysis of Advanced Gas-Cooled Reactor (AGR) superheater tubes......Page 440
In situ compositional analysis of economizer tubes within the sub-boiler annulus of an AGR pressure vessel......Page 444
In situ measurements of oxide thickness inside a Magnox nuclear reactor......Page 447
Identification of cooling-water tubes and reinforcing bars within Magnox reactor pressure vessels......Page 448
Non-invasive compositional analysis of radioactive contamination within a hot-cell......Page 450
Detection of surface contamination on high-level waste (HLW) containers......Page 452
11.5.1 In situ compositional analysis of steel pipes at high temperature......Page 455
11.6 References......Page 456
12.1 Introduction to resonance-enhanced LIBS......Page 460
Continuum emissions......Page 461
Line emissions......Page 462
Line-to-continuum ratio......Page 464
12.2.2 Are LIBS plasmas ideal for spectrochemical analysis?......Page 466
12.2.3 Laser-induced cool plasmas......Page 467
12.2.4 Sustaining non-thermal plasmas......Page 469
12.2.5 A summary of the conceptual basis of RELIPS......Page 470
12.3.1 Experiments......Page 471
12.3.2 Resonance enhancements......Page 473
12.3.3 Important experimental parameters......Page 474
12.3.4 Multielement analysis......Page 476
12.3.5 Time-resolved characterization of the plasma plume......Page 478
12.3.6 RELIPS analysis of solids: a summary......Page 481
12.4.1 A model of photoresonant pumping of water molecules......Page 483
12.4.2 ArF laser ablation of aqueous samples......Page 485
12.4.3 Analytical performance......Page 488
12.4.4 Detection of sodium and potassium in single red blood cells......Page 490
12.4.5 Liquid analysis: a summary......Page 492
12.6 Conclusion: resonance-enhanced LIBS as an analytical tool......Page 493
12.7 References......Page 494
13.1 Introduction......Page 497
13.2 Effect of pulse duration on ablation......Page 498
13.3 Effect of pulse duration on plasma......Page 499
13.4 Picosecond-induced electron plasma......Page 500
13.5 Femtosecond plasma......Page 502
13.6 Short-pulse LIBS......Page 503
13.7 Conclusion......Page 507
13.8 References......Page 508
14.1 Introduction......Page 510
14.2 Diode-pumped solid-state lasers......Page 511
14.3 State of the art......Page 514
14.4.1 Set-up for high-speed, high-resolution LIBS......Page 518
14.4.2 Synchronization......Page 522
14.4.3 Maximum plasma generation frequency......Page 523
14.4.4 Results with high-speed scanning LIBS using DPSSL......Page 525
14.4.5 Detection of light elements......Page 527
14.5 Laser-induced crater geometry and spatial resolution of high-speed,
high-resolution scanning LIBS with DPSSL......Page 530
14.6 References......Page 533
15.1 Introduction......Page 536
15.2.1 Dual-pulse LIBS using an ablation pulse followed by a re-excitation pulse......Page 537
15.2.2 Pre-ablation spark dual-pulse LIBS......Page 540
15.2.4 The potential role of pre-ionization......Page 546
15.2.6 Pre-ablation spark dual-pulse results using combinations of nanosecond
and femtosecond laser pulses......Page 547
15.2.8 Dual-pulse LIBS in bulk aqueous solution......Page 550
15.3 Summary......Page 552
15.4 References......Page 554
16.1 Introduction......Page 559
16.2.1 Laser......Page 563
16.2.2 Microscope......Page 564
16.2.4 Experiment procedure......Page 566
16.3.1 Results on ceramics......Page 567
16.3.2 Results on steel......Page 571
16.3.4 Analysis of fluid inclusions present in natural or synthetic minerals......Page 572
16.5 References......Page 574
17.2 Introduction......Page 576
17.3.2 Photomultiplier detectors......Page 578
17.3.3 Solid-state detectors......Page 579
The interline CCD detectors......Page 580
The image intensifier......Page 581
17.3.4 Spectrometers......Page 582
Paschen–Runge mounting......Page 583
Echelle spectrometer......Page 584
17.4.1 Plasma diagnostics......Page 586
Temperature......Page 589
Electron density......Page 591
Calibration by single shot......Page 594
Limit of detection......Page 595
17.5 Advantages and limitations......Page 596
17.5.1 Advantages......Page 597
17.5.2 Limitations......Page 598
17.6.2 Comparison of systems based on ICCD and interline CCD......Page 600
17.7 Conclusions......Page 601
17.8 References......Page 602
18.1 Introduction......Page 605
18.2.1 Spark characteristics......Page 606
18.2.2 Detection systems......Page 608
Aerosol monitoring hardware and analytical methods......Page 610
Dry aerosol calibration system......Page 611
Speciation, particle size and realistic samples in aerosol measurements......Page 613
Interference measurements......Page 616
Soil monitoring hardware and analytical methods......Page 617
18.4 Applications and results......Page 619
18.4.1 Lead in airborne particulate application: firing range tests......Page 620
18.4.2 Soil results......Page 622
Potential interference from organic contamination......Page 631
18.5 Discussion and future directions......Page 633
18.6 References......Page 634
Index......Page 635