Intensity enhancement in cross-beam pulsed laser ablation using two orthogonal targets

In this work we investigated a novel configuration of the orthogonal geometry for double pulse laser ablation. In this arrangement, a laser is focused onto a target generating a highly directed plume; after that, an additional laser produces a second plasma onto another perpendicular target. In this way, the second plume is expanded through the first plume region. Ablation of carbon was carried out in vacuum (10^− 4 Pa) by two delayed lasers. The first pulse corresponds to a Nd:yttrium–aluminum–garnet (YAG) (1064 nm) and the second one to an excimer (248 nm) laser. Results show that plasma interactions produce different species emission enhancement depending on the delay between lasers, laser fluences and the spatial overlapping between plumes. Approximately an 100-fold increase in emission signal was measured as the observation distance grows.     

Double pulse laser-induced breakdown spectroscopy of explosives: Initial study towards improved discrimination

Detecting trace explosive residues at standoff distances in real-time is a difficult problem. One method ideally suited for real-time standoff detection is laser-induced breakdown spectroscopy (LIBS). However, atmospheric oxygen and nitrogen contributes to the LIBS signal from the oxygen- and nitrogen-containing explosive compounds, complicating the discrimination of explosives from other organic materials. While bathing the sample in an inert gas will remove atmospheric oxygen and nitrogen interference, it cannot practically be applied for standoff LIBS. Alternatively, we have investigated the potential of double pulse LIBS to improve the discrimination of explosives by diminishing the contribution of atmospheric oxygen and nitrogen to the LIBS signal. These initial studies compare the close-contact (< 1 m) LIBS spectra of explosives using single pulse LIBS in argon with double pulse LIBS in atmosphere. We have demonstrated improved discrimination of an explosive and an organic interferent using double pulse LIBS to reduce the air entrained in the analytical plasma.     

Characterization of coal fly ash components by laser-induced breakdown spectroscopy

The high sensitivity of laser-induced breakdown spectroscopy (LIBS) for the detection of most of the fly ash components enables the analysis of these residues produced during the combustion of coal. Fly ash consists of oxides (SiO₂, Al₂O₃, Fe₂O₃, CaO…) and unburnt carbon which is the major determinant of combustion efficiency in coal fired boilers. For example, an excessive amount of residual carbon dispersed in the fly ash means a significant loss of energy (Styszko et al., 2004 [1]). Standard methods employed for the analysis of fly ash make not possible a control of boiler in real time. LIBS technique can significantly reduce the time of analysis, in some cases even an online detection can be performed. For this reason, some studies have been addressed in order to demonstrate the capability of the laser-induced breakdown spectroscopy technique for the detection of carbon content in high pressure conditions typical of thermal power plants (Noda et al., 2002 [2]) and for the monitoring of unburnt carbon for the boiler control in real time (Kurihara et al., 2003[3]).In particular, the content of unburnt carbon is a valuable indicator for the control of fly ash quality and for the boiler combustion. Depending on this unburnt carbon content, fly ash can be disposed as an industrial waste or as a raw material for the production of concrete in the construction sector. In this study, analyses were performed on specimens of various forms of preparation. Pressed pellets were prepared with two different binders. Presented results concern the nature and amount of the binder used to pelletize the powder, and the laser-induced breakdown spectroscopy parameters and procedure required to draw calibration curves of elements from the fly ash. Analysis “on tape” was performed in order to establish the experimental conditions for the future “online analysis”.     

Review: Applications of single-shot laser-induced breakdown spectroscopy

As applications for laser-induced breakdown spectroscopy (LIBS) become more varied with a greater number of field and industrial LIBS systems developed and as the technique evolves to be more quantitative that qualitative, there is a more significant need for LIBS systems capable of analysis with the use of a single laser shot. In single-shot LIBS, a single laser pulse is used to form a single plasma for spectral analysis. In typical LIBS measurements, multiple laser pulses are formed and collected and an ensemble-averaged method is applied to the spectra. For some applications there is a need for rapid chemical analysis and/or non-destructive measurements; therefore, LIBS is performed using a single laser shot. This article reviews in brief several applications that demonstrate the applicability and need for single-shot LIBS.     

Analysis of two colliding laser-produced plasmas by emission spectroscopy and fast photography

In this work two colliding laser-induced plasmas (LIP) on Cu and C were studied by means of time resolved emission spectroscopy and fast photography. The experiments were performed using two opposing parallel targets of Cu and C in vacuum, ablated with two synchronized ns lasers. The results showed an increased emission intensity from copper ions Cu II (368.65, 490.97, 493.16, 495.37 and 630.10 nm) and Cu III (374.47 and 379.08 nm) due to the ionization that occurs during collisions of Cu and C species. It was found that the optimum delay between pulses, which yields the maximum emission enhancement of Cu ions, depends on the sampling distance. On the other hand, the emission intensity of C lines, C II (426.70 nm), C III (406.99 and 464.74 nm) and C IV (465.83 nm), decreased and the formation of C₂ molecules was observed. A comparison between the temporal evolution of the individual plasmas and their collision performed by combining imaging and the time resolved emission diagnostics, revealed an increase of the electron temperature and electron density and the splitting of the plume into slow and fast components.     

Influence of pulse-to-pulse delay for 532 nm double-pulse laser-induced breakdown spectroscopy of technical polymers

Laser induced breakdown spectroscopy (LIBS) is an emerging technique for fast and accurate compositional analysis of many different materials. We present a systematic study of collinear double-pulse LIBS on different technical polymers such as polyamide, polyvinyl chloride, polyethylene etc. Polymer samples were ablated in air by single-pulse and double-pulse Nd:YAG laser radiation (8 ns pulse duration) and spectra were recorded with an Echelle spectrometer equipped with an ICCD camera. We investigated the evolution of atomic and ionic line emission intensities for different delay times between the laser pulses (from 20 ns to 500 μs) at a laser wavelength of 532 nm. We observed double-pulse LIBS signals that were enhanced as compared to single-pulse measurements depending on the delay time and the type of polymer material investigated. LIBS signals of polymer materials that are enhanced by double-pulse excitation may be useful for monitoring the concentration of heavy metals in polymer materials.     

Absolute characterization of laser-induced breakdown spectroscopy detection systems

A quantitative comparison of the performance of four different laser-induced breakdown spectroscopy detection systems is presented. The systems studied are an intensified photodiode array coupled with a Czerny–Turner spectrometer, an intensified CCD coupled with a Czerny–Turner spectrometer, an intensified CCD coupled to an Echelle spectrometer, and a prototype multichannel compact CCD spectrometer system. A simple theory of LIBS detection systems is introduced, and used to define noise-equivalent spectral radiance and noise-equivalent integrated spectral radiance for spectral detectors. A detailed characterization of cathode noise sources in the intensified systems is presented.     

Double pulse laser-induced breakdown spectroscopy with femtosecond laser pulses

This paper presents results obtained in a study of collinear geometry double pulse femtosecond LIBS analysis of solids in ambient environment. LIBS signal enhancement of 3–10 fold, accompanied by significant improvement of signal reproducibility, in comparison with the single pulse case, has been found in different samples such as brass, iron, silicon, barium sulfate and aluminum when an optimum temporal separation between the two ablating pulses is used. The influence of the delay between pulses in the LIBS signal intensity was investigated and two intervals of interaction were established. A first transient regime from 0 to 50 ps, in which the LIBS signal increases until reaching a maximum, and a second regime that ranges from 50 to 1000 ps (maximum inter-pulse delay investigated) in which the signal enhancement remains constant. Emissions from both ionized and neutral atoms show the same pattern of enhancement with a clear tendency of lines arising from higher energy emissive states to exhibit higher enhancement factors.     

Quantitative analysis of arsenic in mine tailing soils using double pulse-laser induced breakdown spectroscopy

A double pulse-laser induced breakdown spectroscopy (DP-LIBS) was used to determine arsenic (As) concentration in 16 soil samples collected from 5 different mine tailing sites in Korea. We showed that the use of double pulse laser led to enhancements of signal intensity (by 13% on average) and signal-to-noise ratio of As emission lines (by 165% on average) with smaller relative standard deviation compared to single pulse laser approach. We believe this occurred because the second laser pulse in the rarefied atmosphere produced by the first pulse led to the increase of plasma temperature and populations of exited levels. An internal standardization method using a Fe emission line provided a better correlation and sensitivity between As concentration and the DP-LIBS signal than any other elements used. The Fe was known as one of the major components in current soil samples, and its concentration varied not substantially. The As concentration determined by the DP-LIBS was compared with that obtained by atomic absorption spectrometry (AAS) to evaluate the current LIBS system. They are correlated with a correlation coefficient of 0.94. The As concentration by the DP-LIBS was underestimated in the high concentration range (>1000 mg-As/kg). The loss of sensitivity that occurred at high concentrations could be explained by self-absorption in the generated plasma.     

Comparison of two laser-induced breakdown spectroscopy techniques for total carbon measurement in soils

The potentials of two advanced laser-induced breakdown spectroscopy (LIBS) techniques which are used to determine the total carbon content in soils have been examined. The first one is the combination of a single-pulse laser ablation with spark excitation of plasma plume triggering the gap between electrodes close to the target surface. The second one is a more conventional double-pulse LIBS. In both modes the calibration graphs have a nonlinear trend in the actual range of carbon contents and present a good R² value (0.97). In the combined laser-spark approach, using low-cost and portable laser instrumentation is possible, as well as inducing a micro-damage on the target surface. Certain regularities in the spectral line intensities of soil nutritious elements have been detected and appear to be connected to the total carbon content and to the soil origin.     

Polarization and fluence dependence of the polarized emission in nanosecond laser-induced breakdown spectroscopy

Several studies have appeared in the past two years reporting that the continuum emission produced by the laser ablation of solid materials is strongly polarized. In a paper that appears to conflict with these findings, Asgill et al. report that they did not observe a significant amount of polarization produced by nanosecond laser excitation of nitrogen gas and laser ablation of copper and steel ( M.E. Asgill, H.Y. Moon, N. Omenetto, D.W. Hahn, Investigation of polarization effects for nanosecond laser-induced breakdown spectroscopy, Spectrochim. Acta Part B (2010) xxx-xxx [7]). Here we show that the apparent discrepancy is resolved when laser fluence and polarization are taken into account. Using a 532 nm Nd:YAG laser to ablate Al samples in air, we find that the degree of polarization, P, of the continuum is greater for s- vs. p-polarized excitation and that P decreases with increasing fluence. We show that P would be < 10% under the conditions of Asgill et al., whereas P > 60% is obtained at low fluences with s-polarized excitation. We also confirm that at high fluence the polarization of the discrete emission is much smaller than that of the continuum.     

Time-resolved ultraviolet laser-induced breakdown spectroscopy for organic material analysis

Ultraviolet pulses (266 nm) delivered by a quadrupled Nd:YAG laser were used to analyze organic samples with laser-induced breakdown spectroscopy (LIBS). We present characteristics of the spectra obtained from organic samples with special attentions on the emissions of organic elements, O and N, and molecular bonds CN. The choice of these atomic or molecular species is justified on one hand, by the importance of these species to specify organic or biological materials; and on the other hand by the possible interferences with ambient air when laser ablation takes place in the atmosphere. Time-resolved LIBS was used to determine the time-evolution of line intensity emitted from these species. We demonstrate different kinetic behaviors corresponding to different origins of emitters: native atomic or molecular species directly vaporized from the sample or those generated through dissociation or recombination due to interaction between laser-induced plasma and air molecules. Our results show the ability of time-resolved UV-LIBS for detection and identification of native atomic or molecular species from an organic sample.     

Optimization of collinear double-pulse femtosecond laser-induced breakdown spectroscopy of silicon

This paper investigates the optimization of double-pulse collinear femtosecond laser-induced breakdown spectroscopy (FLIBS) for silicon. Double-pulse FLIBS signal enhancements were observed over an extended range of sample focal plane position compared to single pulse FLIBS. The FLIBS signal intensity was studied as a function of pulse energy, inter-pulse delay (0 ps‑80 ps) and sample position. Correlation between crater volume and signal intensity was measured over a limited range of the sample focal plane position. It was found that double-pulse FLIBS is superior to single pulse for certain focal plane positions.     

Vacuum ultraviolet laser-induced breakdown spectroscopy analysis of polymers

Laser-induced breakdown spectroscopy (LIBS) in the vacuum ultraviolet range (VUV, λ < 200 nm) is employed for the detection of trace elements in polyethylene (PE) that are difficult to detect in the UV/VIS range. For effective laser ablation of PE, we use a F₂ laser (wavelength λ = 157 nm) with a laser pulse length of 20 ns, a pulse energy up to 50 mJ, and pulse repetition rate of 10 Hz. The optical radiation of the laser-induced plasma is measured by a VUV spectrometer with detection range down to λ = 115 nm. A gated photon-counting system is used to acquire time-resolved spectra. From LIBS measurements of certified polymer reference materials, we obtained a limit of detection (LOD) of 50 µg/g for sulphur and 215 µg/g for zinc, respectively.The VUV LIBS spectra of PE are dominated by strong emission lines of neutral and ionized carbon atoms. From time-resolved measurements of the carbon line intensities, we determine the temporal evolution of the electronic plasma temperature, T_e. For this, we use Saha–Boltzmann plots with the electron density in the plasma, N_e, derived from the broadening of the hydrogen H-α line. With the parameters T_e and N_e, we calculate the intensity ratio of the atomic sulphur and carbon lines at 180.7 nm and at 175.2 nm, respectively. The calculated intensity ratios are in good agreement with the experimentally measured results.     

Fast vacuum slag analysis in a steel works by laser-induced breakdown spectroscopy

Samples taken from the liquid slag layer in a vacuum degasser station of a steel works are analyzed after solidification by laser-induced breakdown spectroscopy (LIBS) without any further sample preparation. The mass fractions of the major components of the vacuum slags are in the range of 50–60% for CaO, 0.5–12% for SiO₂ and 20–40% for Al₂O₃. The species are distributed heterogeneously in the solid samples having diameters of 35 mm. Furthermore the color and structure of the samples is varying significantly. A fast spatial averaging of representative sample areas is realized by spatial laser beam shaping. Multivariate calibration and its validation is carried out with calibration and validation sets of production samples which are analyzed by X-ray fluorescence measurements or as borate beads for reference. The laser-induced breakdown spectroscopy instrument is installed in the steel works at a distance of about 10 m from the vacuum degasser. The laser-induced breakdown spectroscopy analysis runs automatically after the sample placement and it takes 80 s including data transfer to the host computer of the steel works. Operational tests are carried out to demonstrate the feasibility of a fast slag analysis in the harsh environment of the vacuum degasser plant.     

Analysis of laser-induced breakdown spectroscopy spectra: The case for extreme value statistics

In most instances, laser-induced breakdown spectroscopy (LIBS) spectra are obtained through analog accumulation of multiple shots in the spectrometer CCD. The average acquired in the CCD at a given wavelength is assumed to be a good representation of the population mean, which in turn is implicitly regarded to be the best estimator for the central value of the distribution of the spectrum at the same wavelength. Multiple analog accumulated spectra are taken and then in turn averaged wavelength-by-wavelength to represent the final spectrum. In this paper, the statistics of single-shot and analog accumulated LIBS spectra of both solids and liquids were examined to evaluate whether the spectrum averaging approach is statistically defensible. At a given wavelength, LIBS spectra are typically drawn from a Frechet extreme value distribution, and hence the mean of an ensemble of LIBS spectra is not necessarily an optimal summary statistic. Under circumstances that are broadly general, the sample mean for LIBS data is statistically inconsistent and the central limit theorem does not apply. This result appears to be due to very high shot-to-shot plasma variability in which a very small number of spectra are high in intensity while the majority are very weak, yielding the extreme value form of the distribution. The extreme value behavior persists when individual shots are analog accumulated. An optimal estimator in a well-defined sense for the spectral average at a given wavelength follows from the maximum likelihood method for the extreme value distribution. Example spectra taken with both an Echelle and a Czerny–Turner spectrometer are processed with this scheme to create smooth, high signal-to-noise summary spectra. Plasma imaging was used in an attempt to visually understand the observed variability and to validate the use of extreme value statistics. The data processing approach presented in this paper is statistically reliable and should be used for accurate comparisons of LIBS spectra instead of arithmetic averaging on either complete or censored data sets.     

Lead determination in glasses by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) has been used to determine the lead content of different types of lead silicate glasses commercially designed as sonorous glass (which contain ∼ 10 wt.% PbO); crystal glass (with at least 24 wt.% PbO) and superior crystal glass (with at least 30 wt.% PbO). Seven different types of glass samples were selected, including historic-original, model and commercially available. The selected samples were artificially weathered under neutral, acid and alkaline attack. Analysis by LIBS was carried out in vacuum under excitation at 266 nm and results were compared with those obtained by conventional techniques used for glass characterization. Composition of the bulk glasses was analyzed by XRF (X-ray fluorescence) and the corroded surfaces were characterized by SEM/EDX (scanning electron microscopy/energy dispersive X-ray microanalysis). A linear correlation was obtained between the intensity of selected Pb lines in the LIB spectra and the PbO content. The effect of corrosion could be characterized by comparing successive LIB spectra recorded on the same area; acid attack resulted in a decrease of PbO, CaO and Na₂O content in the surface with respect to the bulk of the sample, while minor changes in the composition were noticed under alkaline attack. These results show LIBS as a useful technique to classify the different types of lead glasses by their lead content and to determine and asses the degree and type of corrosion.     

Spectrochemical study for the in situ detection of oil spill residues using laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) has been used to identify the differences or similarities between crude oil and fuel residues. Firstly, a man portable LIBS analyzer was used for the on-site environmental control and analysis of the oil spill from The Prestige. An exhaustive analysis of crude oil and oil spill residues (collected during the field campaign in the Galician Coast) was performed in the laboratory. Characteristics elements in petroleum such as C, H, N, O, Mg, Na, Fe and V were detected. In addition, contributions from Ca, Si and Al in the composition of residues have been found. The use of intensity ratios of line and band emissions in the original fuel (crude oil) and in the aged residues allowed a better characterization of the samples than the simple use of peak intensities. The chemical composition between the crude oil and the fuel residues was found completely different. As well, a statistical method was employed in order to discriminate residues. Although significant differences were observed, no conclusions in terms of age and provenance could be reached due to the unknowledgment in the origin of the samples.     

Analysis of powdered tungsten carbide hard-metal precursors and cemented compact tungsten carbides using laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) has been applied to the direct analysis of powdered tungsten carbide hard-metal precursors and cemented tungsten carbides. The aim of this work was to examine the possibility of quantitative determination of the niobium, titanium, tantalum and cobalt. The investigated samples were in the form of pellets, pressed with and without binder (powdered silver) and in the form of cemented tungsten carbides. The pellets were prepared by pressing the powdered material in a hydraulic press. Cemented tungsten carbides were embedded in resin for easier manipulation.

Several lasers and detection systems were utilized. The Nd:YAG laser working at a basic wavelength of 1064 nm and fourth-harmonic frequency of 266 nm with a gated photomultiplier or ICCD detector HORIBA JY was used for the determination of niobium which was chosen as a model element. Different types of surrounding gases (air, He, Ar) were investigated for analysis. The ICCD detector DICAM PRO with Mechelle 7500 spectrometer with ArF laser (193 nm) and KrF laser (248 nm) were employed for the determination of niobium, titanium, tantalum and cobalt in samples under air atmosphere. Good calibration curves were obtained for Nb, Ti, and Ta (coefficients of determination r² > 0.96). Acceptable calibration curves were acquired for the determination of cobalt (coefficient of determination r² = 0.7994) but only for the cemented samples. In the case of powdered carbide precursors, the calibration for cobalt was found to be problematic.     

Calibration Measurements in laser-induced breakdown spectroscopy using nanosecond and picosecond lasers

The influence of laser pulse duration on laser-induced breakdown spectroscopy (LIBS) calibration curves is investigated in the present work. Two Nd:YAG lasers providing pulses of 35 ps and 5 ns, respectively, both operating at 1064 nm, have been used to create plasmas on aluminium, manganese, iron, and silicon targets and on prepared stoichiometric samples of these metals in a matrix. The time-resolved, space-averaged plasma temperatures have been deduced using Boltzmann plots, while the electron number density has been determined from the broadening of spectral lines. The effect of laser pulse duration on the plasma characteristics is discussed, and comparisons are made with previously reported data measured under similar experimental conditions. The optimum experimental conditions (i.e., time delay, gate width, laser energy) have been determined for reliable use of LIBS for quantitative analysis for both pulse durations. For each of the metals of interest, calibration curves have been constructed for concentrations ranging up to 2%.