Laser-induced Breakdown Spectroscopy Measurements Research Articles

Laser induced breakdown spectroscopy for composition monitoring of graded Al[sbnd]Cu alloy surface

Laser-induced breakdown spectroscopy (LIBS) is a powerful method for non-invasive elemental composition monitoring which can be applied for processing graded metal alloys, provided that challenges with reliable and rapid spectral data processing are overcome to enable composition analysis in real-time. In this study, we describe an integrated experimental-computational methodology for analyzing LIBS spectra data obtained from graded composition metal alloy surfaces with a mean rate of composition analysis up to 15.7 Hz. The accuracy and speed of this method was assessed via analysis of a graded AlCu film prepared by magnetron sputtering representing a gradient alloy processed by additive manufacturing. Using a pulsed femtosecond laser and gated sCMOS detector, a series of LIBS measurements were taken across the composition gradient of an AlCu sputtered alloy. Energy Dispersive Spectroscopy (EDS) was used both to calibrate composition measurements and quantify the error of the LIBS-based rapid analysis method demonstrated in this paper, which yielded a mean percent error relative to the EDS data in the composition measurement along the gradient as low as 1.4 % when optimized for the cumulative number of probe laser pulses on a single measurement spot. The femtosecond probe pulse method described in this paper allows for the alloy composition to be accurately measured in hundredths of a second, potentially allowing for real-time composition monitoring in gradient alloy processing, including thin film sputtering, additive manufacturing, and other rapid processing technologies for graded metal alloys.

Laser-induced breakdown spectroscopy as a method for millimeter-scale inspection of surface flatness

A non-contact method for millimeter-scale inspection of material surface flatness via Laser-Induced Breakdown Spectroscopy (LIBS) is investigated experimentally. The experiment is performed using a planished surface of an alloy steel sample to simulate its various flatness, ranging from 0 to 4.4 mm, by adjusting the laser focal plane to the surface distance with a step length of 0.2 mm. It is found that LIBS measurements are successful in inspecting the flatness differences among these simulated cases, implying that the method investigated here is feasible. It is also found that, for achieving the inspection of surface flatness within such a wide range, when univariate analysis is applied, a piecewise calibration model must be constructed. This is due to the complex dependence of plasma formation conditions on the surface flatness, which inevitably complicates the inspection procedure. To solve the problem, a multivariate analysis with the help of Back-Propagation Neural Network (BPNN) algorithms is applied to further construct the calibration model. By detailed analysis of the model performance, we demonstrate that a unified calibration model can be well established based on BPNN algorithms for unambiguous millimeter-scale range inspection of surface flatness with a resolution of about 0.2 mm.

Full correction of the self-absorption of laser-induced plasma beryllium emissions via sample preparation

Self-absorption effect is always encountered in laser-induced breakdown spectroscopy (LIBS) and immediately distorts the calibration curves especially for the elemental determination of complex materials. With the aim to provide an expeditious approach for LIBS measurements susceptible to self-absorption effect, an exploratory study for sample preparation by powder mixing is implemented, and the self-absorption of laser-induced plasma beryllium emissions is investigated as a function of the dilution factor. For comparison, boric acid and wax powder are separately used as typical binding agent to mix with beryl powder to produce two sets of pressed pellets with sequential gradient of beryllium content variation. For the resonant lines most prone to self-absorption of Be II emission doublet at 313.042 nm and 313.107 nm, the beryllium spectral line shapes can be directly regulated and improved in the case of both sets of pellets as the dilution factor increases. In addition, the self-absorption effect for the strongly emitting beryllium spectral lines is further assessed by calculating the self-absorption coefficients based on the radiation transport equation. With regard to the both types of binder as diluent, when the dilution factor for beryl increases to 10 with a weight percent of 0.386% for beryllium in the pellet, the SA values may exponentially increase in general to around 0.8 and eventually asymptotically approaches to 1 without exception. Thus the self-absorption effect of laser-induced beryl plasma emissions can be readily overcome with sample preparation by powder mixing. By contrast with laser pulse irradiance in the present work, the dilution factor for powder mixing plays a dominant role in eliminating self-absorption effect. This research proposes a potentially effective approach to reduce self-absorption in laser-induced plasma emissions.

Temporally modulating laser pulses to stabilize LIBS measurement locations under large gas temperature gradients

In combustion research, laser-induced breakdown spectroscopy (LIBS) has been widely employed in local equivalence ratio measurement. However, the potential temperature gradients in the probe volume can significantly affect the shape of induced plasmas, resulting in unstable measurement locations. In this work, we improved the stability of measurement locations by modulating the laser pulse duration. In a hot-cold gas flow interface with large temperature gradients, when using the original laser pulse with a full width at half maximum (FWHM) of 4 ns, the locations of initial plasma core were insensitive to gradient variations; however, the plasma expansion behaviors differed significantly after 3 ns. The hot spots of plasmas diverged bi-directionally under high temperature, resulting in two-lobe structures and unstable measurement locations. After the laser pulse was modulated to a shorter duration using a pressure chamber, the plasma expansion was suppressed which constrained the plasma volume. Specifically, using a modulated pulse with a FWHM of 1.9 ns, the two-lobe structure was eliminated across the interface, and the standard deviation of measurement locations was reduced to 0.27 mm. The measured equivalence ratios across the interface showed favorable agreement with the simulation.

Quality index for Martian in-situ laser-induced breakdown spectroscopy data

Laser-induced breakdown spectroscopy (LIBS) has been widely implemented in Mars explorations as a versatile technique for in-situ chemical analysis. Determination of elemental composition from Martian LIBS typically relies on uni/multi-variate models trained on specific laboratory datasets, which in turn requires similarities between this training dataset and Martian data. However, plasma excitation can affect this similarity. The inability to identify insufficiently excited data may ignore poor focusing for some observations or lead to unawareness of compositional uncertainty. This study establishes the LIBS Quality Index (LQI) for Martian LIBS data quality by evaluating the carbon ionic doublet emission around 658 nm for the Martian atmosphere, assessing its signal-to-noise ratio as well as its deviation from the line profile standard of the instrument-specific laboratory dataset. This method allows the LQI to be used as a confidence level for assessing LIBS excitation quality and measurement for similarity with instrument-specific laboratory datasets. The LQI evaluation routines were established for ChemCam, MarSCoDe, and SuperCam. Validation of LQI was carried out on the laboratory datasets and Mars data with known quality assessments of the three instruments. The index was verified to be sensitive to input irradiance, applicable with three current Mars LIBS instruments, robust against various material types (except carbonate), and moderate interference from H, Fe, and Ti. Applying the LQI, the study was able to identify the remote micro-imager (RMI) autofocus as an optimal mechanism, to discover the influence of environmental conditions on data quality, to discuss the impact of target material consolidation and morphology on data quality, and to investigate the contribution of data quality to quantification uncertainty. These application examples demonstrated the feasibility of LQI as a useful and sensitive tool to assess data quality and its potential to aid current and future Martian LIBS explorations.

In situ chemical analysis of duplex stainless steel weld by laser induced breakdown spectroscopy

The high corrosion resistance and good mechanical properties of duplex stainless steel (DSS) are due to its special chemical composition, which is a balanced phase ratio of ferrite (α) and austenite (γ). Many industrial applications require the integration of DSS components. For this, Gas tungsten arc welding (GTAW) is an excellent choice, as it allows an automated operation with high reproducibility. However, when the weld pool solidifies, critical ratios of α- and γ- phases can occur, which lead to solidification cracking, increased susceptibility to corrosion, and a decrease in ductility and critical strength. Previous studies have shown that these defects can be caused by the accumulation of manganese and chromium in the heat affected zone (HAZ), requiring ongoing monitoring of this accumulation. A suitable method for such monitoring is laser-induced breakdown spectroscopy (LIBS), which can be used in two operating modes: calibration using standard reference samples and calibration-free. Unlike conventional quantitative LIBS measurements, which require reference samples to generate a calibration curve, calibration-free LIBS (CF-LIBS) allows chemical compositions to be determined solely from the emission spectrum of the plasma. Numerous publications show that CF-LIBS is a fast and efficient analytical method for the quantitative analysis of metal samples. In this work, CF-LIBS is applied to spectra obtained during GTAW DSS welding and the result is compared with those obtained by PLS analysis. A good correlation was found between both types of analysis, demonstrating the suitability of the CF-LIBS method for this application. The CF-LIBS method has a significant advantage over conventional LIBS due to the rapid in situ measurement of concentrations of major alloying elements without calibration procedure. This, combined with fast feedback and appropriate adjustment of welding parameters, helps prevent welding defects.

A step towards the diagnostic of the ITER first wall: in-situ LIBS measurements in the WEST tokamak

Abstract As part of the development of proven diagnostics allowing the characterization of ITER’s PFUs (Plasma Facing Units) without dismantling, LIBS (Laser-Induced Breakdown Spectroscopy) is a serious candidate for determining the multi-elemental composition. In this article, we report a measurement campaign carried out within the WEST tokamak using an original device based on the following technological choices. (1) The laser source and the spectrometer are placed outside the tokamak. (2) The laser pulses are conveyed by an optical fiber. (3) The signals are collected by a second optical fiber. (4) The optical focusing and collection device is placed in the desired location by a remote handling arm (AIA, Articulated Inspection Arm). The processed signals allow the measurement of the composition of the irradiated material. The technological choices are discussed in the light of their implementation and proposals are made for a more efficient future version of the system.

Application of S-transform-based nonlinear processing for accurate LIBS quantitative analysis of iron ore slurry.

Real-time Fe content monitoring in iron ore slurry is crucial for evaluating concentrate quality and enhancing mineral processing efficiency. Laser-induced breakdown spectroscopy (LIBS) is a promising technique for the online monitoring of elemental content at industrial sites. However, LIBS measurements are hampered by the matrix effect and the self-absorption effect, limiting the precision of linear analytical processes. To overcome this, we propose to introduce a nonlinear processing unit based on the S-transform to incorporate nonlinearity into the data analysis process. This approach integrates a feature selection unit based on the spectral distance variable selection method (SDVS), a nonlinear processing unit based on the S-transform (ST), and a partial least squares regression model (PLS). To demonstrate the improvement in accuracy achieved through nonlinear processing, a comparative analysis involving five models, Raw-PLS, SDVS-PLS, ST-PLS, SDVS-ANN, and SDVS-ST-PLS, is conducted. The results reveal a significant improvement in the performance of the SDVS-ST-PLS model, effectively facilitating the successful application of the LIBSlurry analyzer to the mineral flotation process.

Non-Gaussian Signal Statistics’ Impact on LIBS Analysis

A detailed study has been carried out to reveal signal statistics’ impact on analysis sensitivity in laser-induced breakdown spectroscopy (LIBS) measurements. For several signals measured simultaneously, it was demonstrated that space-, spectra- and time-integrated plasma emission followed a normal distribution while the spectra- and time-resolved LIBS signal (atomic line intensity, plasma background emissions) distribution functions were biased compared to a Gaussian distribution function. For the first time in LIBS, the impact of a non-Gaussian distribution function on the limit of detection (LOD)’s determination has been studied in detail for single-shot spectra as well as for averaged spectra. Here, we demonstrated that the non-symmetrical distribution of the LIBS signals influenced the estimated LODs, so knowledge of a LIBS signal’s distribution function provides more reliable results, and the analysis sensitivity can be wrongly estimated if Gaussian distribution is presumed.

Estimating the yield stress of soft materials via laser-induced breakdown spectroscopy

Taking three typical soft samples prepared respectively by loose packings of 77-, 95-, and 109-μm copper grains as examples, we perform an experiment to investigate the energy-dependent laser-induced breakdown spectroscopy (LIBS) of soft materials. We discovered a reversal phenomenon in the trend of energy dependence of plasma emission intensity: increasing initially and then decreasing separated by a well-defined critical energy. The trend reversal is attributed to the laser-induced recoil pressure at the critical energy just matching the sample’s yield strength. As a result, a one-to-one correspondence can be well established between the samples’ yield stress and the critical energy that is easily obtainable from LIBS measurements. This allows us to propose an innovative method for estimating the yield stress of soft materials via LIBS with attractive advantages including in-situ remote detection, real-time data collection, and minimal destructive to sample.

Acoustic characteristics of laser-induced plasmas from the forming dynamics perspective

The acoustic signal has demonstrated its capabilities in assisting laser-induced breakdown spectroscopy (LIBS) measurements. In this study, the acoustic characteristics of laser-induced plasmas (LIPs) under different levels of energy deposition were analyzed, and their correlation with LIP forming dynamics was investigated. In the deposited energy space, two zones in the acoustic pressure and duration were observed, featuring a clear transition point in 100 mJ. The analysis based on self-emission spectra and images suggested that this transition is a result of the change in plasma forming dynamics. Above 100mJ, the plasma temperature and electron density were saturated; thus, any further increase in deposited energy only contributes to the plasma size. In this regime, the acoustic wave from the significantly elongated plasma no longer satisfied the ideal spherical assumption. The observation was also strengthened by the analysis in the frequency domain. Moreover, the correlation between acoustic and radiation signals was also changed significantly with plasma forming dynamics. This study offers a systematic analysis of LIP acoustic signals on the deposited energy space. The potential of using acoustic measurement to interpret the plasma forming dynamics was demonstrated, which could be beneficial for the successful implementations of acoustic-aided LIBS.

Vapor-Phase Contribution to Laser-Induced Plasma Emission of Magnesium in Liquid Aluminum.

Liquid aluminum containing the important alloying element magnesium in varying concentrations was analyzed using in-situ laser-induced breakdown spectroscopy (LIBS). Magnesium emission shows an exponential dependence on melt temperature that correlates well with the expected partial pressure of magnesium above the aluminum melt. Furthermore, comparison with LIBS measurements on corresponding solid samples supports the conclusion that a significant part of Mg emission from liquid metal samples originates from the vapor phase above the metal surface. Simultaneously, curves of growth measured over four orders of magnitude in Mg concentration reveal a level of self-absorption for liquid aluminum samples that is stronger than for solid aluminum samples having a corresponding Mg concentration, and beyond what is expected from conventional plasma models. The implications for measurements of volatile species in liquid metals in general are discussed.

LIBS depth profiling of Be-containing samples with different gaseous impurity concentrations

Understanding the interaction between the fusion plasma and the plasma-facing materials (PFMs) is crucial for achieving the optimal performance, safety, and lifetime of the fusion devices. Relevant materials have been intensely studied to determine fuel retention and the composition of the co-deposited layers on the PFMs by depth profile analysis using Laser-Induced Breakdown Spectroscopy (LIBS) and Calibration-Free (CF)-LIBS. However, the comparison between the layers containing a mixture of different (seeding) gases using LIBS, has not been studied systematically. Consequently, the aim of this work is the LIBS depth profile analysis of Be-based samples containing the fuel (D) and one of the seeding gases (N, Ne, He) with variable concentrations to study the potential impact on fuel retention in the PFMs. The LIBS measurements were performed using Nd:YAG laser (1064 nm) under Ar atmosphere (at 2 and 100 mbar). In LIBS the ablation rate was evaluated, spectral lines of all relevant elements except N and Ne were detected and compared with the SIMS depth profiles. The reasons for the non-detectability of Ne are discussed in detail.

Highly Precise Laser-Induced Breakdown Spectroscopy Analysis of Major Mineral Nutrients in Edible Salts Using Miniaturized Salt Ponds and Alternating Laser-Ablation Data Sampling.

In this work, we applied a hydrophilicity-enhanced solid substrate and an alternating laser-ablation data sampling (ALADS) scheme to improve laser-induced breakdown spectroscopy (LIBS) measurement precision and demonstrated the performance in analyzing K, Mg, Ca, and S contained in commercially available edible salt products. Five edible salt products from Australia, Bolivia, France, and South Korea were dissolved in water and a tiny volume of each solution was dropped on the solid substrate, that is, a miniaturized salt pond. After being dried, the residual salt crystals distributed still inhomogeneously, but the homogeneity could be significantly improved in comparison with that from typical drop-and-dry methods. The ALADS scheme was applied to extract three precise measurements from 9798 single-shot LIBS spectra covering the entire salt pond. The measurements obtained by ALADS were found to agree well with one another regardless of the inhomogeneous distribution of salt crystals. As a result, the measurement precision was proved remarkably. Limits of detection for K, Mg, Ca, and S were estimated to be 0.64, 1.7, 14, and 530 mg/kg, respectively, which are enough to analyze those elements contained in salts typically at the level of 100 parts per million (ppm) to ∼3 wt% for the purpose of salt quality assessment.

The quality monitoring of paracetamol medicament using a noninvasive microwave sensor

Environmental conditions, including temperature, humidity, and light, can impact the quality of drugs. Microwave-based approaches offer a fast and cost-effective way to detect quality variations, providing an alternative to traditional techniques in the pharmaceutical and cosmetic industries. This article proposes the use of a microwave sensor for monitoring the quality of pharmaceutical drugs at distinct temperature levels. A small planar sensor based on three hexagonal split ring resonators (TH-SRR) is fabricated. The design is manufactured on an FR-4 dielectric substrate. The sensor is tested on a 1000 mg paracetamol tablet, at temperatures ranging from 40 to 80 ^circC. The Variation in the permittivity that characterizes product degradation is translated into a shift in the frequency of the scattering matrix elements. To validate the microwave approach, drug quality is examined with the laser-induced breakdown spectroscopy (LIBS) technique, an optical emission laser used for both qualitative and quantitative investigations of elements contained in a sample. The existing elements are classified using the National Institute of Standards and Technology (NIST) database and categorized according to their spectral line wavelengths. The experiments show the presence of optimal wavelength values for carbon (C), hydrogen (H), nitrogen (N), and oxygen (O) at 247.92 nm, 656.49 nm, 244.23 nm, and 777.48 nm, respectively. The microwave experimental results show a shift frequency of approximately 1 MHz on average when the tablet is heated at 80 ^circC for 15 min. Meanwhile, the LIBS measurement shows a remarkable shift in terms of intensity of approximately 8884 and 812 for carbon and hydrogen, respectively. Understanding how paracetamol dries under high temperatures and improving the process settings of the microwave sensor are investigated and assessed in this work.

An Examination of Soil Crusts on the Floor of Jezero Crater, Mars

AbstractMartian soils are critically important for understanding the history of Mars, past potentially habitable environments, returned samples, and future human exploration. This study examines soil crusts on the floor of Jezero crater encountered during initial phases of the Mars 2020 mission. Soil surface crusts have been observed on Mars at other locations, starting with the two Viking Lander missions. Rover observations show that soil crusts are also common across the floor of Jezero crater, revealed in 45 of 101 locations where rover wheels disturbed the soil surface, two out of seven helicopter flights that crossed the wheel tracks, and four of eight abrasion/drilling sites. Most soils measured by the SuperCam laser‐induced breakdown spectroscopy (LIBS) instrument show high hydrogen content at the surface, and fine‐grained soils also show a visible/near infrared (VISIR) 1.9 μm H2O absorption feature. The Planetary Instrument for X‐ray Lithochemistry (PIXL) and SuperCam observations suggest the presence of salts at the surface of rocks and soils. The correlation of S and Cl contents with H contents in SuperCam LIBS measurements suggests that the salts present are likely hydrated. On the “Naltsos” target, magnesium and sulfur are correlated in PIXL measurements, and Mg is tightly correlated with H at the SuperCam points, suggesting hydrated Mg‐sulfates. Mars Environmental Dynamics Analyzer (MEDA) observations indicate possible frost events and potential changes in the hydration of Mg‐sulfate salts. Jezero crater soil crusts may therefore form by salts that are hydrated by changes in relative humidity and frost events, cementing the soil surface together.

Effect of laser wavelength on soil carbon measurements using laser-induced breakdown spectroscopy.

We investigate the effect of laser wavelength on laser-induced breakdown spectroscopy (LIBS) on the measurement of carbon in agricultural soils. Two laser wavelengths, 1064 nm and 532 nm, were used to determine soil carbon concentration. No chemical pretreatment, grinding, or pelletization was performed on soil samples to simulate in-field conditions. A multivariate calibration model with outlier filtering and optimized parameters in partial least squared regression (PLSR) was established and validated. The calibration model estimated carbon content in soils with an average prediction error of 4.7% at a laser wavelength of 1064 nm and 2.7% at 532 nm. The limit of detection (LOD) range for 532 nm was 0.34-0.5 w/w%, approximately half of the LOD range for 1064 nm laser wavelength. The improvement in prediction error and LOD of LIBS measurements is attributed to the increase in plasma density achieved at 532 nm.

Characteristic of spatiotemporal evolution of hydrogen isotope in laser-induced plasma under low-pressure environment

The elemental analysis of hydrogen (H) and its isotopes, deuterium (D) and tritium (T) is important for fuel retention detections in plasma-facing materials of nuclear fusion devices, H abundance assessment in geochemistry and so on. Laser-induced breakdown spectroscopy (LIBS) is one of the most promising technology to analyze the H isotopes due to its excellent real-time and in situ analytical ability. However, the laser ablation plasma is a transient plasma with inhomogeneous spatiotemporal evolution. Especially in low-pressure background, the particles with different masses may separate in the plasma plume. This will result in the loss of accuracy of LIBS measurement. In this work, the characteristic of spatiotemporal evolution of spectra from laser-induced plasma on the frozen D2O-H2O mixture under low-pressure environment has been investigated. The spectral intensity of Dα and electron density decrease with radial direction and delay time. The intensities ratio of Dα and Hα, ID/(ID + IH), are almost constant at different radial positions and delay times under the background pressure of 1 × 10−1 mbar. However, when the pressure decreases to 1 × 10−4 mbar, ID/(ID + IH) decreases from the center to the edge of the plasma due to plume separation by the different atomic masses of isotopes. The degree of separation increases from the center to the edge of the plasma. The results will be useful for better understanding of characteristic of spatiotemporal evolution of LIBS plasma in low pressure and improvement of LIBS measurement for H isotopes.

Post-fire assessment of heating temperatures experienced by concrete using short video imaging, hyperspectral imaging and laser-induced breakdown spectroscopy

This study develops rapid post-fire analysis methods to predict the heating temperature to which the concrete was exposed. Short video imaging (SVI), hyperspectral imaging (HSI) and laser-induced breakdown spectroscopy (LIBS) were used for the first time to obtain spectra of concrete after high-temperature exposure (100–800 °C). The differences in colour levels and spectroscopic signals due to varying temperatures were observed. To handle the complex relationship between spectra and temperatures, machine learning models were used to extract meaningful information from spectra for the quantification of temperature. Furthermore, domain knowledge related to concrete composition and LIBS signal was integrated into machine learning to improve quantification performance. The highest coefficients of determination for prediction achieved based on SVI, HSI and LIBS measurements were 91.4, 94.8 and 98.6, respectively. These results demonstrate that SVI, HSI and LIBS can be fast and viable methods for assessing the fire temperature that the concrete has experienced.

Optical assessment of the spatial variation in total soil carbon using laser-induced breakdown spectroscopy

Soil carbon storage is a substantial factor in the global carbon cycle. Carbon sequestration in agricultural soils, and the assessment and validation of soil carbon storage, are crucial for the mitigation of agricultural greenhouse gas emissions and for steering towards sustainable farming practices. Enforcement and verification of carbon sequestration policies, methods, and models require extensive soil carbon monitoring capability. However, current conventional laboratory-based methods for soil carbon estimation are laborious, expensive, and time-consuming. In this work, we have developed a compact, robust, and field-capable experimental device based on laser-induced breakdown spectroscopy (LIBS) for the rapid assessment of total soil carbon content and its spatial distribution in mineral soils. The carbon content quantification was performed using a spectral line of carbon at a wavelength of 193.1 nm emitted from the laser-induced plasma plume. The LIBS measurements were performed on soil samples collected from 28 different locations and various depths (up to 1 m) of a test field cultivated with a forage legume (red clover - Trifolium pratense, L.) and grass (Timothy - Phleum pratense, L.) mixture in eastern Finland. A calibration model was established based on a limited and randomly chosen sample set and validated by comparing soil carbon estimates obtained from various locations in the test field using the dry combustion (LECO) method. Further, we demonstrate here the usefulness of LIBS methodology for mapping three-dimensional carbon distribution at the test field. We emphasize here that the calibration model can be generalized to other sample areas under similar soil type with a relative error of less than 10 % and possesses potential for fast on-site determination of spatial variation in total soil carbon, reducing substantially the need of time-consuming sample processing in laboratory. Therefore, LIBS enables frequent and extensive spatial and temporal soil carbon mapping and has the potential to become part of the future carbon monitoring network.