Changmao Li

Enhancement of optical emission from laser-induced plasmas by combined spatial and magnetic confinement

To enhance optical emission in laser-induced breakdown spectroscopy, both a pair of permanent magnets and an aluminum hemispherical cavity (diameter: 11.1 mm) were used simultaneously to magnetically and spatially confine plasmas produced by a KrF excimer laser in air from pure metal and alloyed samples. High enhancement factors of about 22 and 24 in the emission intensity of Co and Cr lines were acquired at a laser fluence of 6.2 J/cm2 using the combined confinement, while enhancement factors of only about 11 and 12 were obtained just with a cavity. The mechanism of enhanced optical emission by combined confinement, including shock wave in the presence of a magnetic field, is discussed. The Si plasmas, however, were not influenced by the presence of magnets as Si is hard to ablate and ionize and hence has less free electrons and positive ions. Images of the laser-induced Cr and Si plasmas show the difference between pure metallic and semiconductor materials in the presence of both a cavity and magnets.

Plasma confinement by hemispherical cavity in laser-induced breakdown spectroscopy

An aluminum hemispherical cavity (diameter: 11.1 mm) was used to confine plasmas produced by a KrF excimer laser in air from a steel target with a low concentration manganese in laser-induced breakdown spectroscopy. A significant enhancement (factor >12) in the emission intensity of Mn lines was observed at a laser fluence of 7.8 J/cm2 when the plasma was confined by the hemispherical cavity, leading to an increase in plasma temperature about 3600 K. The maximum emission enhancement increased with increasing laser fluence. The spatial confinement mechanism was discussed using shock wave theory.

Optimally enhanced optical emission in laser-induced breakdown spectroscopy by combining spatial confinement and dual-pulse irradiation

In laser-induced breakdown spectroscopy (LIBS), a pair of aluminum-plate walls were used to spatially confine the plasmas produced in air by a first laser pulse (KrF excimer laser) from chromium (Cr) targets with a second laser pulse (Nd:YAG laser at 532 nm, 360 mJ/pulse) introduced parallel to the sample surface to re-excite the plasmas. Optical emission enhancement was achieved by combing the spatial confinement and dual-pulse LIBS (DP-LIBS), and then optimized by adjusting the distance between the two walls and the interpulse delay time between both laser pulses. A significant enhancement factor of 168.6 for the emission intensity of the Cr lines was obtained at an excimer laser fluence of 5.6 J/cm(2) using the combined spatial confinement and DP-LIBS, as compared with an enhancement factor of 106.1 was obtained with DP-LIBS only. The enhancement mechanisms based on shock wave theory and reheating in DP-LIBS are discussed.

Sensitivity improvement in the detection of V and Mn elements in steel using laser-induced breakdown spectroscopy with ring-magnet confinement

To improve the detection sensitivity of vanadium (V) and manganese (Mn) elements in steel using laser-induced breakdown spectroscopy (LIBS), a ring magnet was employed to spatially and magnetically confine plasmas produced from steel samples using an Nd:YAG laser. The results showed that the optical emission and signal-to-noise ratios (SNRs) for both V I 437.92 nm and Mn I 403.08 nm lines were enhanced by the ring-magnet confinement. The enhancements were found to be due to an increase in the plasma temperature and electron density as a result of both spatial and magnetic confinement. The calibration curves of V I 437.92 nm and Mn I 403.08 nm with/without confinement were established. The 3σ-limits of detection (LoDs) for V and Mn in steels were 11 and 30 ppm with the ring magnet, lower than the 18 and 41 ppm with a degaussed magnet and the 41 and 56 ppm in open air, respectively.

Analytical-performance improvement of laser-induced breakdown spectroscopy for steel using multi-spectral-line calibration with an artificial neural network

A multi-spectral-line calibration (MSLC) approach based on an artificial neural network (ANN) was developed to improve the accuracy and precision of steel analysis using laser-induced breakdown spectroscopy (LIBS). The intensity ratios of multiple spectral lines of target and matrix elements were used to train an ANN. The resulting model was able to relate the spectra to the concentrations of target elements more accurately than the conventional internal calibration approach, which led to improvements in the accuracy and precision of the LIBS analysis. This approach was applied to LIBS analysis of steel samples to predict the Cr and Ni concentrations. Compared with a conventional internal calibration approach, the root-mean-square errors of cross-validation for Cr and Ni decreased from 0.018 and 0.067 wt% to 0.010 and 0.023 wt%, respectively, using the proposed MSLC, and the average values of the relative standard deviation for Cr and Ni decreased from 11.3 and 19.5% to 6.4 and 12.9%, respectively.

Acidity measurement of iron ore powders using laser-induced breakdown spectroscopy with partial least squares regression

Laser-induced breakdown spectroscopy (LIBS) with partial least squares regression (PLSR) has been applied to measuring the acidity of iron ore, which can be defined by the concentrations of oxides: CaO, MgO, Al₂O₃, and SiO₂. With the conventional internal standard calibration, it is difficult to establish the calibration curves of CaO, MgO, Al₂O₃, and SiO₂ in iron ore due to the serious matrix effects. PLSR is effective to address this problem due to its excellent performance in compensating the matrix effects. In this work, fifty samples were used to construct the PLSR calibration models for the above-mentioned oxides. These calibration models were validated by the 10-fold cross-validation method with the minimum root-mean-square errors (RMSE). Another ten samples were used as a test set. The acidities were calculated according to the estimated concentrations of CaO, MgO, Al₂O₃, and SiO₂ using the PLSR models. The average relative error (ARE) and RMSE of the acidity achieved 3.65% and 0.0048, respectively, for the test samples.

Determinations of trace boron in superalloys and steels using laser-induced breakdown spectroscopy assisted with laser-induced fluorescence.

Boron (B) is widely applied in microalloying of metals. As a typical light element, however, determination of boron in alloys with complex matrix spectra is still a challenge for laser-induced breakdown spectroscopy (LIBS) due to its weak line intensities in the UV-visible-NIR range and strong spectral interference from the matrix spectra. In this study, a wavelength-tunable laser was used to enhance the intensities of boron lines selectively. The intensities of B I 208.96 nm from boron plasmas were enhanced approximately 3 and 5.8 times while the wavelength-tunable laser was tuned to 249.68 and 249.77 nm, respectively. Utilizing the selective enhancement effect, accurate determinations of trace boron in nickel-based superalloys and steels were achieved by laser-induced breakdown spectroscopy assisted by laser-induced fluorescence (LIBS-LIF), with limits of detection (LoDs) of 0.9 and 0.5 ppm, respectively. The results demonstrated that LIBS-LIF can hopefully be used in boron determinations and has great potential for improving the ability of LIBS to determine light elements in alloys with a complex matrix.

Generation of high-temperature and low-density plasmas for improved spectral resolutions in laser-induced breakdown spectroscopy

Improved spectral resolutions were achieved in laser-induced breakdown spectroscopy (LIBS) through generation of high-temperature and low-density plasmas. A first pulse from a KrF excimer laser was used to produce particles by perpendicularly irradiating targets in air. A second pulse from a 532 nm Nd:YAG laser was introduced parallel to the sample surface to reablate the particles. Optical scattering from the first-pulse plasmas was imaged to elucidate particle formation in the plasmas. Narrower line widths (full width at half maximums: FWHMs) and weaker self-absorption were observed from time-integrated LIBS spectra. Estimation of plasma temperatures and densities indicates that high temperature and low density can be achieved simultaneously in plasmas to improve LIBS resolutions.

Sensitive determinations of Cu, Pb, Cd, and Cr elements in aqueous solutions using chemical replacement combined with surface-enhanced laser-induced breakdown spectroscopy.

In this study, chemical replacement combined with surface-enhanced laser-induced breakdown spectroscopy (CR-SENLIBS) was for the first time applied to improve the detection sensitivities of trace heavy metal elements in aqueous solutions. Utilizing chemical replacement effect, heavy metal ions in aqueous solution were enriched on the magnesium alloy surface as a solid replacement layer through reacting with the high chemical activity metallic magnesium (Mg) within 1 minute. Unitary and mixed solutions with Cu, Pb, Cd, and Cr elements were prepared to construct calibration curves, respectively. The CR-SENLIBS showed a much better detection sensitivity and accuracy for both unitary and mixed solutions. The coefficients of determination R2 of the calibration curves were above 0.96, and the LoDs were of the same order of magnitude, i.e., in the range of 0.016-0.386 μg/mL for the unitary solution, and in the range of 0.025-0.420 μg/mL for the mixed solution. These results show that CR-SENLIBS is a feasible method for improving the detection sensitivity of trace element in liquid sample, which definitely provides a way for wider application of LIBS in water quality monitoring.

Element dependence of enhancement in optics emission from laser-induced plasma under spatial confinement

In this study, the element dependence of spatial confinement effects in LIBS has been studied. Hemispheric cavities were used to confine laser-induced plasmas from aluminum samples with other trace elements. The enhancement factors were found to be dependent on the elements. Equations describing the element-dependent enhancement factors were successfully deduced from the local thermodynamic equilibrium conditions, which have also been verified by the experimental results. Research results show that enhancement factors in LIBS with spatial confinement depend on the temperature, electron density, and compression ratio of plasmas, and vary with elements and atomic/ionic emission lines selected. Generally, emission lines with higher upper level energies have higher enhancement factors. Furthermore, with enhancement factor of a spectral line, temperatures and electron densities of plasmas known, enhancement factors of all the other elements in the plasmas could be estimated by the equations developed in this study.