The precise measurement of Al, Mg, Ca, and Zn composition in copper slag is crucial for effective process control of copper pyrometallurgy. In this study, a remote laser-induced breakdown spectroscopy(LIBS) system was...The precise measurement of Al, Mg, Ca, and Zn composition in copper slag is crucial for effective process control of copper pyrometallurgy. In this study, a remote laser-induced breakdown spectroscopy(LIBS) system was utilized for the spectral analysis of copper slag samples at a distance of 2.5 m. The composition of copper slag was then analyzed using both the calibration curve(CC) method and the partial least squares regression(PLSR) analysis method based on the characteristic spectral intensity ratio. The performance of the two analysis methods was gauged through the determination coefficient(R^(2)), average relative error(ARE), root mean square error of calibration(RMSEC), and root mean square error of prediction(RMSEP). The results demonstrate that the PLSR method significantly improved both R^(2) for the calibration and test sets while reducing ARE, RMSEC, and RMSEP by 50% compared to the CC method. The results suggest that the combination of LIBS and PLSR is a viable approach for effectively detecting the elemental concentration in copper slag and holds potential for online detection of the elemental composition of high-temperature molten copper slag.展开更多
Double-pulse LIBS is a promising technique for deep-sea applications.LIBS measurements in shallow water with up to 400 mJ each pulse were done to select laser parameters which promote optimized spectral line emission ...Double-pulse LIBS is a promising technique for deep-sea applications.LIBS measurements in shallow water with up to 400 mJ each pulse were done to select laser parameters which promote optimized spectral line emission from plasma even at elevated pressures,where line broadening until loss of most of the spectral information can occur.Optical emission spectroscopy,using a Czerny-Turner spectrometer,has been applied to investigate the dependence of the emitted radiation on laser parameters and hydrostatic pressure.It has been found,that higher laser pulse energies,especially with short pulse delay as required in high water pressure,can also have an adverse effect on the measured spectrum.展开更多
Only a small amount of spectral information is collected because the collection solid angle of the optical fiber probe and lens is very limited when collecting spectral information.To overcome this limitation,this stu...Only a small amount of spectral information is collected because the collection solid angle of the optical fiber probe and lens is very limited when collecting spectral information.To overcome this limitation,this study presents a novel method for acquiring plasma spectral information from various spatial directions.A parabolic-shaped plasma spectral collection device(PSCD)is employed to effectively collect more spectral information into the spectrometer,thereby enhancing the overall spectral intensity.The research objects in this study were soil samples containing different concentrations of heavy metals Pb,Cr,and Cd.The results indicate that the PSCD significantly enhances the spectral signal,with an enhancement rate of up to 45%.Moreover,the signal-to-noise ratio also increases by as much as 36%.Simultaneously,when compared to the absence of a device,it is found that there is no significant variation in plasma temperature when the PSCD is utilized.This observation eliminates the impact of the spatial effect caused by the PSCD on the spectral intensity.Consequently,a concentrationspectral intensity relationship curve is established under the PSCD.The results revealed that the linear fitting R^(2)for Pb,Cr,and Cd increased by 0.011,0.001,and 0.054,respectively.Additionally,the limit of detection(LOD)decreased by 0.361 ppm,0.901 ppm,and 0.602 ppm,respectively.These findings indicate that the spectral enhancement rate elevates with the increase in heavy metal concentration.Hence,the PSCD can effectively enhance the spectral intensity and reduce the detection limit of heavy metals in soil.展开更多
The present work aims to demonstrate the capabilities of Laser-induced Breakdown Spectroscopy(LIBS)coupled with a multivariate technique for rapid quantification and classification of old Indian coins made of various ...The present work aims to demonstrate the capabilities of Laser-induced Breakdown Spectroscopy(LIBS)coupled with a multivariate technique for rapid quantification and classification of old Indian coins made of various alloys.Thirteen old Indian coins in different years of circulation,(1922–1986)were selected for the study.The concentrations were determined by Calibration free LIBS(CF-LIBS)method.The concentration of cuprum(Cu)is negligible,and aluminum(Al)is maximum in the first five coins,and vice-versa in the remaining eight coins.Two different multivariate methods,Principal Component Analysis(PCA)and Soft Independent Modelling of Class Analogy(SIMCA)have been used to classify and identify the coins.PCA classified all thirteen samples into four main alloy categories.The discernment of unknown samples to their probable class membership of alloy was performed using SIMCA.The surface hardness(Brinell hardness number)is linearly correlated with the plasma temperature and LIBS intensity ratios.The sample surface of the first and fifth coin belongs to Al-alloy,having the least surface hardness,and it became harder for Cu–Ni alloy,Ni-brass alloy,and bronze alloy.The hardness of the surface is more for bronze sample twelve.It is also observed that the plasma temperature increases monotonically with the Brinell hardness number.This analysis provides valuable information on fabrication methodology and explains large diversification in the elementary composition of old coins.展开更多
The self-absorption effect in laser-induced breakdown spectroscopy(LIBS)reduces the accuracy of quantitative measurement results.The self-absorption-free LIBS(SAF-LIBS)has been proved to directly capture the optically...The self-absorption effect in laser-induced breakdown spectroscopy(LIBS)reduces the accuracy of quantitative measurement results.The self-absorption-free LIBS(SAF-LIBS)has been proved to directly capture the optically thin plasma spectra by setting an appropriate exposure time.In this work,a novel SAF-LIBS technique with high repetition rate acousto-optic gating is developed,in which an acousto-optic modulator is used as the shutter to diffract the optically thin fluorescence,and a high repetition rate laser is used to produce quasi-continuous plasmas to enhance the integral spectral intensity,so that the CCD spectrometer can replace an intensified CCD(ICCD)and echelle spectrometer in SAF-LIBS.Experimental results show that the average absolute prediction error of aluminum is reduced to 0.18%,which is equivalent to that of traditional SAF-LIBS.This technique not only effectively shields continuous background radiation and broadened spectral lines in optically thick plasma,but also has advantages of miniaturization,low cost,convenience and reliability.展开更多
基金supported by funding for research activities of postdoctoral researchers in Anhui Provincespecial funds for developing Anhui Province’s industrial “three highs” and high-tech industries。
文摘The precise measurement of Al, Mg, Ca, and Zn composition in copper slag is crucial for effective process control of copper pyrometallurgy. In this study, a remote laser-induced breakdown spectroscopy(LIBS) system was utilized for the spectral analysis of copper slag samples at a distance of 2.5 m. The composition of copper slag was then analyzed using both the calibration curve(CC) method and the partial least squares regression(PLSR) analysis method based on the characteristic spectral intensity ratio. The performance of the two analysis methods was gauged through the determination coefficient(R^(2)), average relative error(ARE), root mean square error of calibration(RMSEC), and root mean square error of prediction(RMSEP). The results demonstrate that the PLSR method significantly improved both R^(2) for the calibration and test sets while reducing ARE, RMSEC, and RMSEP by 50% compared to the CC method. The results suggest that the combination of LIBS and PLSR is a viable approach for effectively detecting the elemental concentration in copper slag and holds potential for online detection of the elemental composition of high-temperature molten copper slag.
基金funded by the Deutsche Forschungsgemeinschaft(DFG,German Research Foundation)–Project No.454848899。
文摘Double-pulse LIBS is a promising technique for deep-sea applications.LIBS measurements in shallow water with up to 400 mJ each pulse were done to select laser parameters which promote optimized spectral line emission from plasma even at elevated pressures,where line broadening until loss of most of the spectral information can occur.Optical emission spectroscopy,using a Czerny-Turner spectrometer,has been applied to investigate the dependence of the emitted radiation on laser parameters and hydrostatic pressure.It has been found,that higher laser pulse energies,especially with short pulse delay as required in high water pressure,can also have an adverse effect on the measured spectrum.
基金supported by Department of Science and Technology of Jilin Province of China(Nos.YDZJ202301 ZYTS481,202202901032GX,and 20230402068GH)。
文摘Only a small amount of spectral information is collected because the collection solid angle of the optical fiber probe and lens is very limited when collecting spectral information.To overcome this limitation,this study presents a novel method for acquiring plasma spectral information from various spatial directions.A parabolic-shaped plasma spectral collection device(PSCD)is employed to effectively collect more spectral information into the spectrometer,thereby enhancing the overall spectral intensity.The research objects in this study were soil samples containing different concentrations of heavy metals Pb,Cr,and Cd.The results indicate that the PSCD significantly enhances the spectral signal,with an enhancement rate of up to 45%.Moreover,the signal-to-noise ratio also increases by as much as 36%.Simultaneously,when compared to the absence of a device,it is found that there is no significant variation in plasma temperature when the PSCD is utilized.This observation eliminates the impact of the spatial effect caused by the PSCD on the spectral intensity.Consequently,a concentrationspectral intensity relationship curve is established under the PSCD.The results revealed that the linear fitting R^(2)for Pb,Cr,and Cd increased by 0.011,0.001,and 0.054,respectively.Additionally,the limit of detection(LOD)decreased by 0.361 ppm,0.901 ppm,and 0.602 ppm,respectively.These findings indicate that the spectral enhancement rate elevates with the increase in heavy metal concentration.Hence,the PSCD can effectively enhance the spectral intensity and reduce the detection limit of heavy metals in soil.
文摘The present work aims to demonstrate the capabilities of Laser-induced Breakdown Spectroscopy(LIBS)coupled with a multivariate technique for rapid quantification and classification of old Indian coins made of various alloys.Thirteen old Indian coins in different years of circulation,(1922–1986)were selected for the study.The concentrations were determined by Calibration free LIBS(CF-LIBS)method.The concentration of cuprum(Cu)is negligible,and aluminum(Al)is maximum in the first five coins,and vice-versa in the remaining eight coins.Two different multivariate methods,Principal Component Analysis(PCA)and Soft Independent Modelling of Class Analogy(SIMCA)have been used to classify and identify the coins.PCA classified all thirteen samples into four main alloy categories.The discernment of unknown samples to their probable class membership of alloy was performed using SIMCA.The surface hardness(Brinell hardness number)is linearly correlated with the plasma temperature and LIBS intensity ratios.The sample surface of the first and fifth coin belongs to Al-alloy,having the least surface hardness,and it became harder for Cu–Ni alloy,Ni-brass alloy,and bronze alloy.The hardness of the surface is more for bronze sample twelve.It is also observed that the plasma temperature increases monotonically with the Brinell hardness number.This analysis provides valuable information on fabrication methodology and explains large diversification in the elementary composition of old coins.
基金National Key R&D Program of China(No.2017YFA0304203)National Energy R&D Center of Petroleum Refining Technology(RIPP,SINOPEC),Changjiang Scholars and Innovative Research Team in University of Ministry of Education of China(IRT_17R70)+3 种基金National Natural Science Foundation of China(Nos.61975103,61875108,61775125 and 11434007)Major Special Science and Technology Projects in Shanxi(No.201804D131036)111 Project(No.D18001)Fund for Shanxi’1331KSC’。
文摘The self-absorption effect in laser-induced breakdown spectroscopy(LIBS)reduces the accuracy of quantitative measurement results.The self-absorption-free LIBS(SAF-LIBS)has been proved to directly capture the optically thin plasma spectra by setting an appropriate exposure time.In this work,a novel SAF-LIBS technique with high repetition rate acousto-optic gating is developed,in which an acousto-optic modulator is used as the shutter to diffract the optically thin fluorescence,and a high repetition rate laser is used to produce quasi-continuous plasmas to enhance the integral spectral intensity,so that the CCD spectrometer can replace an intensified CCD(ICCD)and echelle spectrometer in SAF-LIBS.Experimental results show that the average absolute prediction error of aluminum is reduced to 0.18%,which is equivalent to that of traditional SAF-LIBS.This technique not only effectively shields continuous background radiation and broadened spectral lines in optically thick plasma,but also has advantages of miniaturization,low cost,convenience and reliability.
基金National Key R&D Program of China(2016YFD0800902-2),the Anhui Province Major Science and Technology Projects(16030801117),and the National High-Tec hnology Research and Development Program of China(2014AA06A513)。
