CONTRTOUTIONS TO PROCESS MONITORING BY LASER-INDUCED BREAKDOWN SPECTROSCOPY By DAVID ALEXANDER RUSAK A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA ACKNOWLEDGMENTS I would first like to thank Jim Winefordner for the opportunity to work in his laboratory. I have only recently begun to appreciate the vast resources and creative freedom available here. Next, I would like to thank Ben Smith who was responsible for introducing me to many ofthe resources in the lab and elsewhere, and who patiently watched and made suggestions as I learned how to do research. Together, Jim and Ben provided a perfect graduate school environment. I would also like to acknowledge the members ofthe Winefordner group who all, at some time, contributed either directly or indirectly to my research. Bryan Castle, Dr. Kobus Visser, Igor Gomushkin, and Rebecca Litteral were especially helpful. Martin Clara, who worked in the Winefordner lab for a number ofmonths, was an invaluable resource as well. There are certainly a number ofother people who contributed to my stay in Gainesville. IfI were to list them, Yannis Karayannis, Julie Cordek and Wendy Clevenger would be at the top. Thanks to everyone who shared some oftheir life with me during the last fouryears. Lastly, I would like to acknowledge Mariana Blackburn at Infometrix who provided the principal components analysis in the last chapter, the Engineering Research Center (ERC) for Particle Science and Technology at the University ofFlorida for financial support, and the members ofmy committee. 11 TABLE OF CONTENTS ACKNOWLEDGMENTS ABSTRACT CHAPTERS INSTRUMENTATION AND THEORY OF OPTICAL EMISSION 1 EXPERIMENTS 1 Instrumentation 1 Theory 6 Temperature Determination 15 Electron Number Density Determination 22 2 FUNDAMENTALS AND APPLICATIONS OF LASER-INDUCED BREAKDOWN SPECTROSCOPY 29 Introduction 29 Solids 32 Fundamental Studies 32 Analytical Results 40 Liquids 49 Fundamental Studies 49 Analytical Results 58 Bulk Liquids 58 Aerosols and Droplets 63 Gases 67 Fundamental Studies 67 Analytical Results 68 3 THE EFFECT OF TARGET WATER CONTENT ON PROPERTIES OF A LASER-INDUCED PLASMA 78 CaCOs Experiments 78 Introduction 78 Background 79 Experimental 82 Results and Discussion 86 111 Conclusions 87 Iron Ore Experiments 94 Introduction 94 Background 95 Experimental 95 Results and Discussion 98 Conclusions 100 4 LASER-INDUCED BREAKDOWN SPECTROSCOPY OF AQUEOUS SOLUTIONS 102 Introduction 102 Experimental 103 Results and Discussion 107 Conclusions Ill 5 USE OF A FIBER OPTIC LIBS PROBE TO DETERMINE TEMPORAL EVOLUTION OF ELECTRONNUMBER DENSITIES IN LASER-INDUCED PLASMAS ON METALS 114 Construction ofthe Fiber Optic Probe 114 Measurement ofTemporal Evolution ofElectron Number Densities 120 Introduction 120 Experimental 123 Results and Discussion 123 Conclusions 125 6 EXCITATIONAL, VIBRATIONAL, AND ROTATIONAL TEMPERATURES INNd:YAG AND XeCl LASER-INDUCED PLASMAS 129 Introduction 129 Background 131 Experimental 135 Results and Discussion 138 7 CONCLUSIONS AND FUTURE WORK 148 LIST OF REFERENCES 153 BIOGRAPfflCAL SKETCH 163 IV Abstract ofDissertation Presented to the Graduate School ofthe University ofFlorida in Partial Fulfillment ofthe Requirements for the Degree ofDoctor ofPhilosophy CONTRIBUTIONS TO PROCESS MONITORINGBY LASER-INDUCED BREAKDOWN SPECTROSCOPY By David A. Rusak May 1998 Chairman: James D. Winefordner Major Department; Chemistry When a pulsed laser ofsufficient energy and pulse duration is brought to a focus, multi-photon ionization creates free electrons in the focal volume. These electrons are accelerated in a process known as inverse Bremsstrahlung and cause collisional ionization ofspecies in the focal volume. More charge carriers are produced and the process continues for the duration ofthe laser pulse. The manifestation ofthis process is a visible spark or plasma which typically lasts fortens ofmicroseconds. This laser-induced plasma can serve as a source in an atomic emission experiment. Because the composition ofthe plasma is determined in large part by the environment in which it forms, elements in the lasertarget can be determined spectroscopically. The goal ofa laser-induced breakdown spectroscopy (LIBS) experiment is to establish a relationship between the concentration ofan element ofinterest in the target and the V intensity oflight emitted from the laser-induced plasma at a wavelength characteristic of that element. Because LIBS requires only optical access to the sample and can perform elemental determinations in solids, liquids, or gases with little sample preparation, there is interest in using it as an on-line technique for process monitoring in a number ofindustrial applications. However, before the technique becomes useful in industrial applications, many issues regarding instrumentation and data analysis need to be addressed in the lab. The first two chapters ofthis dissertation provide, respectively, the basics ofthe atomic emission experiment and a background oflaser-induced breakdown spectroscopy. The next two chapters examine the effect oftarget water content on the laser-induced plasma and the use ofLIBS for analysis ofaqueous samples. Chapter 5 describes construction ofa fiber optic LIBS probe and its use to study temporal electron number density evolution in plasmas formed on different metals. Chapter 6 is a study of excitation, vibrational, and rotational temperatures in plasmas formed by ultraviolet and infrared laser beams. The last chapter is a briefassessment of classification software for analysis ofLIBS data and a discussion offuture work. VI CHAPTER 1 INSTRUMENTATION AND THEORY OF OPTICAL EMISSION EXPERIMENTS Instrumentation There are three basic units ofinstrumentation which appear in some form in all emission experiments. They are an excitation source, wavelength selector, and radiant power monitor. The excitation source serves to produce free atoms from the sample and to excite the atoms to the upper energy levels. Excitation sources include flames, arcs, sparks, plasmas, low pressure discharges, and lasers. Flames are the oldest excitation source used in emission experiments. In the mid- 1800s Kirchhoffand Bunsen used a flame for qualitative identification ofmany elements and discovered the elements cesium and rubidium by use offlame emission.’ In the 1920s quantitative flame emission was established by Lundegardh for studying plant metabolism, and the first commercial instrument was produced in the mid-1930s by Siemens and Zeiss in Europe.* The flame is still used today for determination ofelements such as Na and Li which can have significant populations ofupper energy levels at relatively low temperature. Because flames did not provide for efficient excitation ofsome solids, particularly refractory materials, there was an interest in the years of WWII in developing a more 1 2 energetic excitation source. Arcs and sparks, which had seen very limited use until this time, were more thoroughly developed, particularly during the Manhattan Project, and used to excite nearly all the stable elements in the periodic table. The dc arc, because of its somewhat lesser stability, was used primarily for qualitative and semi-quantitative analysis, while the more stable (and more energetic) spark was used in quantitative determination. Arcs and sparks are still used as excitation sources in the analysis ofmany solids, and are also used as part ofthe sampling unit in techniques where the excitation is accomplished by another plasma. In the 1960s the development ofstable high-frequency and dc plasma devices offered an even more energetic excitation source.^ The higher degrees ofexcitation that could be achieved with these plasma sources translated into lower detection limits for many elements, and by the mid-1970s inductively coupled and dc plasmas were available commercially as excitation sources. Today, these plasma sources dominate the field of emission spectrometry. Low pressure discharges have been extensively characterized by physicists and have relatively recently been employed in spectrochemical analysis.^ Because the discharge operates at low pressure, the source must be evacuated by a vacuum pump every time the sample is changed and so rapid sample analysis is not possible. However, this source is unique in that it suffers much less from selective volatilization than any ofthe other sources mentioned and so has become ofinterest for researchers ifnot for commercial instrument manufacturers. Although the laser is included in the list ofexcitation sources, the actual emission produced in a laser plasma is very similarto that produced by a spark. The laser is unique. 3 however, in that only optical access to the sample is required to produce this spark, and the spark can be produced on non-conductive as well as conductive samples. The wavelength selector is the next unit ofinstrumentation in emission spectrometry. The purpose ofthe wavelength selector is to provide only a chosen range ofwavelengths to the detector at any one time. Wavelength selectors can be based on absorption, spatial dispersion, interference filters, or interferometry. Spatial dispersion devices are by far the most common; the prism and grating are the most common dispersive devices. In a spatial dispersion selector the light collected is resolved into its component wavelengths with a spectral dispersion which can be on the order of mm per nm. This mm implies that each ofthe spectrum contains light which covers a wavelength range of mm only 1 nm. Placing a 1 exit slit in the spectrum at a given position allows light of a wavelength range of1 nm to pass to the detector at any given time. The wavelength range passed can be changed with time by rotating the dispersive device so that a different portion ofthe spectrum falls on the exit slit at different times. In most modern spectrometers gratings are used as the dispersive element. A grating is a plane or concave plate that is ruled with closely spaced grooves. Different wavelengths oflight striking the plate are reflected and constructively interfere at different angles relative to the position ofthe plate. Hence, as the grating is rotated, different wavelengths oflight fall on the exit slit and reach the detector. The radiant power monitor (detector) is the third unit ofinstrumentation required for emission analysis. It is intimately connected to the wavelength selector, and the properties ofthe detector to be used in any experiment depend greatly on the characteristics ofthe wavelength selector. Photographic plates, photomultiplier tubes, photodiodes. 4 photodiode arrays, charge-coupled devices (CCDs) and charge-injection devices (CIDs) have all been employed as detectors ofradiant power. Photographic films or plates were the first used radiant power detectors. They consisted ofan emulsion containing silver halide crystals which were converted to silver atoms by incident photons. After exposure to incident photons, the plate was subjected to a complexing agent which removed remaining silver ions leaving only the exposed silver on the film. After development, a densitometer could be used to determine the spatial concentration ofsilver atoms across the film and thus the relative intensity ofthe light striking the film in the given region. Even by today’s standards, photographic plates are quite sensitive. Only about 10 incident visible photons are required to produce a discemable spot on the plate. The major drawback ofusing a photographic plate detector is the time required for development of the plate and subsequent analysis by densitometry. Moreover, the photographic plate has a limited dynamic range, although this can be dealt with to some extent by varying the exposure time. Despite these drawbacks photographic plates are still commonly used in astronomy for obtaining images of faint objects viewed through telescopes. The remainder ofthe photon detectors in wide usage operate by converting incident photons into an electrical signal. Photomultiplier tubes and photodiodes are inherently single channel detectors, producing a single output which is a Sanction ofthe total intensity ofradiation reaching them. They are less expensive than array detectors, CCDs, and CIDs, but can monitor only one wavelength at a time. In absorption or fluorescence experiments which attempt to determine only one element at a time, these detectors are