Application Of Laser-induced Breakdown Spectroscopy Research Articles

Identification of vapor-phase chemical warfare agent simulants and rocket fuels using laser-induced breakdown spectroscopy

Application of laser-induced breakdown spectroscopy (LIBS) to the identification of security threats is a growing area of research. This work presents LIBS spectra of vapor-phase chemical warfare agent simulants and typical rocket fuels. A large dataset of spectra was acquired using a variety of gas mixtures and background pressures and processed using partial least squares analysis. The five compounds studied were identified with a 99% success rate by the best method. The temporal behavior of the emission lines as a function of chamber pressure and gas mixture was also investigated, revealing some interesting trends that merit further study.

Laser-Induced Breakdown Spectroscopy—Capabilities and Limitations

During the past decade there has been intense activity in the field of laser-induced breakdown spectroscopy (LIBS). This activity includes studies of laser ablation and properties of the laser spark, the development of methods to enhance LIBS detection capabilities, and the application of LIBS to specific analysis needs. The unique capabilities of LIBS make it particularly suited for applications that cannot be addressed by conventional analytical methods. Potential applications of the method are numerous and several applications have been realized, resulting in on-line operating instruments. Other applications will require that the method be developed further to improve analytical performance. Here we present an overview of the LIBS method, discussing its many advantages and some important limitations as an analytical method and how these relate to potential applications.

Detection of Uranium Using Laser-Induced Breakdown Spectroscopy

The goal of this work is a detailed study of uranium detection by laser-induced breakdown spectroscopy (LIBS) for application to activities associated with environmental surveillance and detecting weapons of mass destruction (WMD). The study was used to assist development of LIBS instruments for standoff detection of bulk radiological and nuclear materials and these materials distributed as contaminants on surfaces. Uranium spectra were analyzed under a variety of different conditions at room pressure, reduced pressures, and in an argon atmosphere. All spectra displayed a high apparent background due to the high density of uranium lines. Time decay curves of selected uranium lines were monitored and compared to other elements in an attempt to maximize detection capabilities for each species in the complicated uranium spectrum. A survey of the LIBS uranium spectra was conducted and relative emission line strengths were determined over the range of 260 to 800 nm. These spectra provide a guide for selection of the strongest LIBS analytical lines for uranium detection in different spectral regions. A detection limit for uranium in soil of 0.26% w/w was obtained at close range and 0.5% w/w was achieved at a distance of 30 m. Surface detection limits were substrate dependent and ranged from 13 to 150 microg/cm2. Double-pulse experiments (both collinear and orthogonal arrangements) were shown to enhance the uranium signal in some cases. Based on the results of this work, a short critique is given of the applicability of LIBS for the detection of uranium residues on surfaces for environmental monitoring and WMD surveillance.

Fast analysis of complex metallic alloys by double-pulse time-integrated Laser-Induced Breakdown Spectroscopy

Results are reported on the application of double-pulse Laser-Induced Breakdown Spectroscopy (LIBS) for fast analysis of complex metallic alloys. The approach followed for the determination of the composition of the alloys is based on the time-integrated acquisition of LIBS spectra emitted by plasmas induced by collinear double-pulse laser excitation. The spectra are analysed using the Partial Least Squares method, which allows the determination of sample composition even in the presence of strong spectral interferences. The results shown indicate the possibility of measuring the composition of complex metallic alloys in very short times and using relatively cheap LIBS instrumentation.

FEASIBILITY STUDY ON THE APPLICATION OF LASER INDUCED BREAKDOWN SPECTROSCOPY TO LUNAR EXPLORATION

The physical principle of laser induced breakdown spectroscopy(LIBS) was interpreted.How the pressure affects the laser induced plasma was analyzed.A LIBS experimental system for the low pressure condition was setup and the experiments at the different pressures were carried out.The experimental result expresses how the pressure affects the laser induced plasma quantitatively.The feasibility on the application of LIBS to lunar exploration was discussed.

Application of calibration-free laser-induced breakdown spectroscopy to radially resolved spectra from a copper-based alloy laser-induced plasma

In this work, the Calibration-Free approach for Laser-Induced Breakdown Spectroscopy (CF-LIBS) was applied for the first time to radially resolved spectra emitted by a laser-induced plasma. The radial profiles of plasma temperature and electron number density were used to calculate the local relative concentration of the elements of interest. We analyzed a set of profiles of the local spectral emission coefficient obtained previously by means of spatial deconvolution of the spectra from a copper-based alloy (Cu 93, Fe 5, Mn 1, Ni 1 wt.%) laser-induced plasma. A spatially integrated spectrum of the same plasma was also analyzed for comparison purpose. The relative abundance of the minor components Fe, Mn and Ni was calculated. The results obtained from the central region of the plasma were closer to the nominal concentrations than those obtained from the spatially integrated spectrum. However, an increasing deviation was observed towards the plasma edge. It is proposed that this deviation could be the result of a gradual departure from Local Thermodynamic Equilibrium (LTE) conditions due the significant decrease of the electron density at the external shells of the plasma.

Laser-induced breakdown spectroscopy for detection of explosives residues: a review of recent advances, challenges, and future prospects

In this review we discuss the application of laser-induced breakdown spectroscopy (LIBS) to the problem of detection of residues of explosives. Research in this area presented in open literature is reviewed. Both laboratory and field-tested standoff LIBS instruments have been used to detect explosive materials. Recent advances in instrumentation and data analysis techniques are discussed, including the use of double-pulse LIBS to reduce air entrainment in the analytical plasma and the application of advanced chemometric techniques such as partial least-squares discriminant analysis to discriminate between residues of explosives and non-explosives on various surfaces. A number of challenges associated with detection of explosives residues using LIBS have been identified, along with their possible solutions. Several groups have investigated methods for improving the sensitivity and selectivity of LIBS for detection of explosives, including the use of femtosecond-pulse lasers, supplemental enhancement of the laser-induced plasma emission, and complementary orthogonal techniques. Despite the associated challenges, researchers have demonstrated the tremendous potential of LIBS for real-time detection of explosives residues at standoff distances.

Early stage expansion and time-resolved spectral emission of laser-induced plasma from polymer

In the nanosecond laser ablation regime, absorption of laser energy by the plasma during its early stage expansion critically influences the properties of the plasma and thus its interaction with ambient air. These influences can significantly alter spectral emission of the plasma. For organic samples especially, recombination of the plasma with the ambient air leads to interfering emissions with respect to emissions due to native species evaporated from the sample. Distinguishing interfering emissions due to ambient air represents a critical issue for the application of laser-induced breakdown spectroscopy (LIBS) to the analysis of organic materials. In this paper, we report observations of early stage expansion and interaction with ambient air of the plasma induced on a typical organic sample (nylon) using time-resolved shadowgraph. We compare, in the nanosecond ablation regime, plasmas induced by infrared (IR) laser pulses (1064 nm) and ultraviolet (UV) laser pulses (266 nm). Nanosecond ablation is compared with femtosecond ablation where the post-ablation interaction is absent. Subsequent to the early stage expansion, we observe for each studied ablation regime, spectral emission from CN, a typical radical for organic and biological samples. Time-resolved LIBS allows identifying emissions from native molecular species and those due to recombination with ambient air through their different time evolution behaviors.

Evaluation of femtosecond laser-induced breakdown spectroscopy for explosive residue detection

Recently laser-induced breakdown spectroscopy (LIBS) has been investigated as a potential technique for trace explosive detection. Typically LIBS is performed using nanosecond laser pulses. For this work, we have investigated the use of femtosecond laser pulses for explosive residue detection at two different fluences. Femtosecond laser pulses have previously been shown to provide several advantages for laser ablation and other LIBS applications. We have collected LIBS spectra of several bulk explosives and explosive residues at different pulse durations and energies. In contrast to previous femtosecond LIBS spectra of explosives, we have observed atomic emission peaks for the constituent elements of explosives - carbon, hydrogen, nitrogen, and oxygen. Preliminary results indicate that several advantages attributed to femtosecond pulses are not realized at higher laser fluences.

Analysis of lead and sulfur in environmental samples by double pulse laser induced breakdown spectroscopy

In the present work, a model of double pulse laser-induced breakdown spectroscopy (LIBS) spectrometer has been developed and results from two different applications of double pulse LIBS for solving the problems of environmental interest are presented. In one case, laser induced breakdown spectroscopy has been applied to the determination of heavy and toxic metals (lead) in soil samples. In the second case, laser induced breakdown spectroscopy was used in preliminary experiments for the detection of sulfur content in coal, and on the basis of spectral features, ways to improve the sensitivity of laser induced breakdown spectroscopy detection of sulfur are proposed. The detection limit for lead in soil was estimated to be approximately 20 ppm that is lower than the regulatory standards for the presence of lead in soil.

Analysis of size-classified fine and ultrafine particulate matter on substrates with laser-induced breakdown spectroscopy

Airborne particulate matter in the fine (0.1 µm–2.5 µm) and ultrafine (≤ 0.1 µm) size range is supposed to affect human health significantly. Smaller particles intrude more deeply into the lungs, so that an organism directly absorbs toxic compounds. Therefore, knowledge of the size-dependent composition of airborne particles is required to determine their health hazard. In this paper, we demonstrate the application of laser-induced breakdown spectroscopy to directly analyze size-classified particulate matter samples without any sample preparation. Samples analyzed are collected on filter substrates using a cascade impactor. Greased aluminum foils are used as filter substrate. To reduce ablation of the substrate material, low pulse energies of 0.6 mJ are used for plasma excitation. The plasma light is observed using an Echelle spectrometer. The effect of ambient gas and pressure on the line intensities is studied. Calibration samples for 14 elements relevant for human health were produced, and the system was calibrated for concentration ranges up to four orders of magnitude. Finally, the collected samples of particulate originating from steel-making processes were analyzed. The measurements show that the composition of these particles depends strongly on their size. For example, the elements lead, cadmium and copper are enriched within particles of about 200 nm diameter.

Laser-induced breakdown spectroscopy applications in the steel industry: Rapid analysis of segregation and decarburization

Rapid chemical analysis is increasingly a prerequisite in the steel making industry, either to check that a steel product complies with customers' specifications, or to investigate the presence of defects that may lead to mechanical property failure of the product. Methods conventionally used for assessment, such as the monitoring of decarburization and segregation, performed by chemical etching of a polished surface followed by optical observation, tend to be relatively fast, simple and applicable to large sample areas; however, the information obtained is limited to the spatial extent of the defect. Other techniques, such as electron probe microscopy and scanning electron microscopy — energy dispersive X-ray, can be used for providing detailed chemical composition at the micro-scale, for a better understanding of the mechanisms involved; however, their use is limited to analyzing comparatively very small sample areas (typically a few mm 2). The ability to rapidly generate chemical concentration maps at the micro-scale is one of the many positive attributes of laser-induced breakdown spectroscopy (LIBS) that makes it a useful tool for the steel industry as a laboratory or near-the-line analysis facility. Parameters that influence the detailed mapping of large sample areas were determined and optimized. LIBS scanning measurements were performed on samples displaying segregation and decarburization. A 60 × 60 mm 2 area, with a step size of 50 μm, was measured in 35 min on segregation samples, and a 4 × 1 mm 2 area with a step size of 20 μm in 2 min on a decarburization sample. The resulting quantified elemental maps correlated very well with data from the methods used conventionally. In the two examples above, the application of LIBS as a micro-analysis technique proved to bring very valuable information that was not accessible previously with other techniques on such large areas in such a short time.

Calculation of self-absorption coefficients of calcium resonance lines in the case of a CaCl 2–water plasma

The resonance escape factors for the lines emitted by a neutral calcium atom Ca I at 4226.73 Å and of ionic calcium Ca II at 3933.66 Å and at 3968.47 Å are calculated assuming a Voigt profile and in the case of CaCl 2–water plasma. The dependence of the escape factor on the optical thickness ґ 0 from the line center which itself depends on the two main spectral line shape broadening mechanisms (pressure and Doppler effects) are considered. The variation of the resonance escape factors with the temperature, the CaCl 2 molar proportion and the size of the plasma are also investigated. This calculation is useful for the application of Laser-Induced Breakdown Spectroscopy in the quantitative analysis of elemental composition. Its application allows us to reduce the non-linearities in the relation between resonance lines intensities of calcium in our case and its concentration.

Laser-induced breakdown spectroscopy: A versatile tool for monitoring traces in materials

Laser-induced breakdown spectroscopy (LIBS) is an emerging technique for simultaneous multi-elemental analysis of solids, liquids and gases with minute or no sample preparation and thus revolutionized the area of on-line analysis technologies. The foundation for LIBS is a solid state, short-pulsed laser that is focused on a sample to generate a high-temperature plasma, and the emitted radiation from the excited atomic and ionic fragments produced within the plasma is characteristic of the elemental composition of the sample that can be detected and analyzed using a suitable optical spectrograph. In the present paper, the applicability of LIBS for different solid samples having homogeneous (silver ornament, aluminum plate) or heterogeneous composition (soil) using nanosecond laser pulses is discussed. Nanosecond pulse laser makes plasma at the sample surface even at very low pulse energies and also allows for precise ablation of the substrate material with little damage to the surrounding area. We have also studied the penetration of different heavy metals inside the soil surface.

Quantitative analysis of carbonaceous aerosols using laser-induced breakdown spectroscopy: a study on mass loading induced plasma matrix effects

We present results indicating mass loading induced plasma matrix effects on the application of quantitative laser-induced breakdown spectroscopy (LIBS) for estimation of carbon contents in aerosols. An in-house flow-controlled powder-dispersion system generated carbonaceous aerosols with varying bi-modal particle size distributions (∼1 µm and 10 µm median diameters), thereby resulting in a wide mass loading range. For ease of chemical handling and to eliminate toxic effects, common talcum powder was used as our standard aerosol. Normalized atomic species concentrations of C, i.e., [C]/[Si] ratios, were calculated from atomic emission lines of C I (248 nm), Si I (252 nm), and plasma temperatures estimated from a series of Mg I lines. The results show a decrease in [C]/[Si] ratio to about 65% of the initial value as relative mass loadings increased (5.5–100%) due to the increase in number concentrations of larger sized particles (∼10 µm median diameter). As a comparison, normalized ratio of [Mg]/[Si] did not exhibit any marked change with increased mass loading. The normalized total absorption of photon flux across the C I (248 nm) spectral line indicated a strong correlation to the percentage decrease in [C]/[Si] ratio. We used an impactor with a cut-off size of around 10 µm diameter to generate mono-modal aerosolized powders (∼1 µm median diameter) that had lower relative mass loadings (0.32–0.16%). Similar LIBS analysis on these did not indicate any of the matrix effects. We conclude that for aerosol systems with widely varying mass loadings, quantitative LIBS analysis can be significantly affected by plasma matrix effects, specifically for the C I (248 nm) emission line as noticed in this study. This bears significance for the application of quantitative LIBS in the chemical characterization of all forms of carbonaceous aerosols.

Application of laser-induced breakdown spectroscopy in analyzing microelements in three kinds of fruit samples

It is a relatively new task to apply the laser-induced breakdown spectrosopy(LIBS) to plant samples. To apply LIBS technique in the field related to foodstuff safety, we have done primary experiments using three kinds of fruit samples prepared by vacuum freeze-dried technique using the technique of discriminated LIBS spectra. The relative contents of six trace elements Ca, Na, K, Fe, Al and Mg in the samples were analyzed. By comparison we found that in apple samples the relative content of Na is the highest and the relative content of Ca is the lowest, and the contents of K, Fe, Mn, Mg are different for different fruit samples. Experiment results showed that LIBS technique is a valid means for measuring and comparing the content of trace elements in plant samples.

Numerical simulation of laser-induced breakdown spectroscopy: Modeling of aerosol analysis with finite diffusion and vaporization effects

The application of laser-induced breakdown spectroscopy (LIBS) to aerosol systems has been shown to provide quantitative analysis of particle-derived species; however, the exact nature of the plasma/particle interactions remains to be fully understood. Although the plasma/particle interaction may be idealized within a framework of instantaneous vaporization and analyte diffusion throughout the plasma volume, experimental evidence suggests that these processes actually occur on finite time scales relative to the plasma decay times at which measurements are frequently taken. In the present work, a numerical simulation of the temperature and species concentration fields of a plasma containing a single particle, including dissociation and diffusion on semi-empirical finite time scales, is developed. Using these results, the intensity of analyte emission is calculated as a function of time, and the standard ion/neutral ratios typical of aerosol-derived LIBS signals are calculated. Furthermore, the ratio of ion/neutral ratios for two different species was used to assess the temperature homogeneity of the particle-derived analytes in comparison to the overall plasma temperature field. From this numerical study, it is shown that the finite time scale of evaporation and diffusion of aerosol material results in a non-uniform spatial distribution in concentration. This results, in turn, in temperature and free electron density gradients within the plasma, leading to variation between the local conditions surrounding aerosol mass and the bulk conditions of the plasma as a whole.

High resolution applications of laser-induced breakdown spectroscopy for environmental and forensic applications

Laser-induced breakdown spectroscopy (LIBS) has been used in the elemental analysis for a variety of environmental samples and as a proof of concept for a host of forensic applications. In the first application, LIBS was used for the rapid detection of carbon from a number of different soil types. In this application, a major breakthrough was achieved by using a multivariate analytical approach that has brought us closer towards a “universal calibration curve”. In a second application, it has been demonstrated that LIBS in combination with multivariate analysis can be employed to analyze the chemical composition of annual tree growth rings and correlate them to external parameters such as changes in climate, forest fires, and disturbances involving human activity. The objectives of using this technology in fire scar determinations are: 1) To determine the characteristic spectra of wood exposed to forest fires and 2) To examine the viability of this technique for detecting fire occurrences in stems that did not develop fire scars. These examples demonstrate that LIBS-based techniques are inherently well suited for diverse environmental applications. LIBS was also applied to a variety of proof of concept forensic applications such as the analysis of cremains (human cremation remains) and elemental composition analysis of prosthetic implants.

Femtosecond Laser-Induced Breakdown Spectroscopy: Physics, Applications, and Perspectives

Progress in technology and society continually places new demands on analytical science and more powerful and informative methods need to be developed. One among them is laser-induced breakdown spectroscopy (LIBS), sometimes also referred to as LIPS (laserinduced plasma spectroscopy). Typically, LIBS measurements are conducted with nanosecond time scale lasers. A review by Song et al.1 and two recently published books by Miziolek et al.2 and Cremers et al.3 give a good overview of instrumental developments in this area. However, new developments in laser technology have made ultra-short lasers available4 and have stimulated an interest in LIBS with ultra-short pulses. There are fundamental differences between the ablation processes of ultra-short ( 1 ps) and short ( 1 ps) pulses that result in different mechanisms of energy dissipation in the sample. In the case of ultra-short laser pulses, at the end of the laser pulse, only a very hot electron gas and a practically undisturbed lattice are found, which subsequently interact. However, for longer pulses above a certain energy threshold, the material undergoes transient changes in the thermodynamic states from solid, through liquid, into a plasma state.5,6 Based on this difference, consequences for the analytical performance of the method can be expected that in the future should lead to new aspects in instrumentation and applications of LIBS. The goal of this review is to summarize current knowledge of the instrumentation and physics of laser ablation with femtosecond lasers and to draw some conclusions concerning new possible applications that rely on these specific new features. It seems clear that even if a better performance in terms of analytical figures of merit compared to standard LIBS applications7 is found, a replacement of current technology cannot be expected soon due to the cost and complexity of chirped pulse amplification (CPA) laser systems. However, current trends in other fields of application of these laser systems, e.g., medical laser applications or material processing,8 may change this picture in the near future.

Investigation of the Parameters Influencing the Accuracy of Rapid Steelmaking Slag Analysis with Laser‐Induced Breakdown Spectroscopy

Laser‐Induced Breakdown Spectroscopy (LIBS) is used for the analysis of steelmaking slags (EAF, Ladle Furnace (LF) and Vacuum Ladle Degasser (VLD)). In view of the potential industrial application of LIBS for rapid slag analysis, relatively simple criteria were employed in order to obtain calibration curves for the elements of interest. The LIBS experiments were performed on samples prepared after crushing and milling to a size less than 0.2 mm and on as delivered solidified slag samples. In general, the analysis of the solidified as delivered slag samples exhibited better results than the corresponding analysis of the pressed slag, mainly for the elements distributed in the matrix. Thus, for LIBS application, the time consuming sample preparation of the slag can be avoided. According to the results obtained, the potential of LIBS technique for in‐situ, multi‐element analysis of slag was examined at the 60t‐ EAF of Helliniki Halyvourgia SA (HH‐Greece). The most important parameters that influence slag analysis are the laser pulse energy, the number of accumulated laser shots, the laser beam focusing conditions and the gating conditions of the detector. LIBS accuracy was found to depend on both the distribution of elements in the slag and on their environment (i.e. if they are embedded in the matrix or in a specific crystallized phase) as well. LIBS limitations for quantitative slag analysis are also discussed.The accuracy of FeOn LIBS analysis for as delivered solidified EAF and VLD slags of the steel plant of Georgsmarienhütte was satisfactory showing a Regression Coefficient (RC) of 0.93 and 0.95 respectively. The accuracy of SiO2 and MgO analysis of VLD slags with RCs of 0.94 and 0.86 respectively was also satisfactory. In contrast, for the EAF slags the RC for MgO and SiO2, due to the observed non‐homogeneous crystallized phases have shown insufficient values, with 0.55 and 0.43 respectively. Similar results were gained for the FeOn, MgO and SiO2 analysis of the HH slags. Due to the higher intensity of scattering, the analysis of CaO, Al2O3 and Cr2O3 was of lower accuracy than for FeOn, MgO and SiO2.