Laser-induced breakdown spectroscopy(LIBS) is a qualitative and quantitative analytical technique with great potential in the cement industrial analysis. Calibration curve(CC) and support vector regression(SVR) method...Laser-induced breakdown spectroscopy(LIBS) is a qualitative and quantitative analytical technique with great potential in the cement industrial analysis. Calibration curve(CC) and support vector regression(SVR) methods coupled with LIBS technology were applied for the quantification of three types of cement raw meal samples to compare their analytical concentration range and the ability to reduce matrix effects, respectively. To reduce the effects of fluctuations of the pulse-to-pulse, the unstable ablation and improve the reproducibility, all of the analysis line intensities were normalized on a per-detector basis. The prediction results of the elements of interest in the three types of samples, Ca, Si, Fe, Al, Mg, Na, K and Ti, were compared with the results of the wet chemical analysis. The average relative error(ARE),relative standard deviation(RSD) and root mean squared error of prediction(RMSEP) were employed to investigate and evaluate the prediction accuracy and stability of the two prediction methods. The maximum average ARE of the CC and SVR methods is 34.62% instead of 6.13%,RSD is 40.89% instead of 7.60% and RMSEP is 1.34% instead of 0.43%. The results show that SVR method can accurately analyze samples within a wider concentration range and reduce the matrix effects, and LIBS coupled with it for a rapid, stable and accurate quantification of different types of cement raw meal samples is promising.展开更多
Continuous-wave cavity ring-down spectroscopy(CW-CRDS)is an important technical means to monitor greenhouse gases in atmospheric environment.In this paper,a CW-CRDS system is built to meet the needs of atmospheric met...Continuous-wave cavity ring-down spectroscopy(CW-CRDS)is an important technical means to monitor greenhouse gases in atmospheric environment.In this paper,a CW-CRDS system is built to meet the needs of atmospheric methane monitoring.The problem of mode matching is explained from the perspective of transverse mode and longitudinal mode,and the influence of laser injection efficiency on measurement precision is further analyzed.The results of cavity ring-down time measurement show that the measurement precision is higher when the laser is coupled with the fundamental mode.In the experiment,DFB laser is used to calibrate the system with standard methane concentration,and the measurement residual is less than±4×10^(-4)μs^(-1).The methane concentration in the air is monitored in real time for two days.The results show the consistency of the concentration changes over the two days,which further demonstrates the reliability of the system for the measurement of trace methane.By analyzing the influence of mode matching,it not only assists the adjustment of the optical path,but also further improves the sensitivity of the system measurement.展开更多
Calibration-free laser-induced breakdown spectroscopy can overcome the matrix effect and the huge application prospects of in situ and on-line measurement, so it has been studied and applied to many analytical samples...Calibration-free laser-induced breakdown spectroscopy can overcome the matrix effect and the huge application prospects of in situ and on-line measurement, so it has been studied and applied to many analytical samples by numerous researchers since it was first proposed in 1999.However, its accuracy is always lower than other analytical techniques and traditional quantitative analysis methods of laser-induced breakdown spectroscopy. The goal of this paper is to review the improvement of accuracy in the experimental setup and spectral analysis,especially after 2010, but not limited to it. The main contents include the accurate measurement of spectral intensity, the spatial and temporal window of local thermodynamic equilibrium and the accurate calculation of temperature and electron density. Due to the requirement of one or more standard samples, the combination of standard samples and CF-LIBS is discussed as a separate section. Finally, a simple conclusion is offered to relevant researchers who want to use CF-LIBS for quantitative analysis.展开更多
The optimal spectral excitation and acquisition scheme is explored by studying the effect of the lensto-sample distance(LTSD)on the spatial homogeneity and emission spectra of flat-top laser converging spot induced pl...The optimal spectral excitation and acquisition scheme is explored by studying the effect of the lensto-sample distance(LTSD)on the spatial homogeneity and emission spectra of flat-top laser converging spot induced plasma.The energy distribution characteristics before and after the convergence of the laser beam with quasi flat-top intensity profile used in this study are theoretically simulated and experimentally measured.For an aspheric converging mirror with a focal length of100 mm,the LTSD(106 mm≥LTSD≥96 mm)was changed by raising the stainless-steel sample height.The plasma images acquired by ICCD show that there is air breakdown when the sample is below the focal point,and a ring-like plasma is produced when the sample is above the focal point.When the sample is located near the focal point,the plasma shape resembles a hemisphere.Since the spectral acquisition region is confined to the plasma core and the image contains all the optical information of the plasma,it has a lower relative standard deviation(RSD)than the spectral lines.When the sample surface is slightly higher than the focal plane of the lens,the converging spot has a quasi flat-top distribution,the spatial distribution of the plasma is more uniform,and the spectral signal is more stable.Simultaneously,there is little difference between the RSD of the plasma image and the laser energy.In order to further improve the stability of the spectral signal,it is necessary to expand the spectral acquisition area.展开更多
基金supported by National Natural Science Foundation of China (Grant Nos. 61505223, 41775128)the Knowledge Innovation Program of the Chinese Academy of Sciences (Grant No. Y03RC21124)+1 种基金the External Cooperation Program of Chinese Academy of Sciences (Grant No. GJHZ1726)the project of China State Key Lab. of Power System (Grant Nos. SKLD18KM11, SKLD18M12)
文摘Laser-induced breakdown spectroscopy(LIBS) is a qualitative and quantitative analytical technique with great potential in the cement industrial analysis. Calibration curve(CC) and support vector regression(SVR) methods coupled with LIBS technology were applied for the quantification of three types of cement raw meal samples to compare their analytical concentration range and the ability to reduce matrix effects, respectively. To reduce the effects of fluctuations of the pulse-to-pulse, the unstable ablation and improve the reproducibility, all of the analysis line intensities were normalized on a per-detector basis. The prediction results of the elements of interest in the three types of samples, Ca, Si, Fe, Al, Mg, Na, K and Ti, were compared with the results of the wet chemical analysis. The average relative error(ARE),relative standard deviation(RSD) and root mean squared error of prediction(RMSEP) were employed to investigate and evaluate the prediction accuracy and stability of the two prediction methods. The maximum average ARE of the CC and SVR methods is 34.62% instead of 6.13%,RSD is 40.89% instead of 7.60% and RMSEP is 1.34% instead of 0.43%. The results show that SVR method can accurately analyze samples within a wider concentration range and reduce the matrix effects, and LIBS coupled with it for a rapid, stable and accurate quantification of different types of cement raw meal samples is promising.
基金This research is financial supported by the Natural National Science Foundation of China(Grant Nos.11874364,41877311,and 42005107)the National Key Research and Development Program of China(Grant No.2017YFC0805004)the CAS&Bengbu Technology Transfer Project(Grant No.ZKBB202102).
文摘Continuous-wave cavity ring-down spectroscopy(CW-CRDS)is an important technical means to monitor greenhouse gases in atmospheric environment.In this paper,a CW-CRDS system is built to meet the needs of atmospheric methane monitoring.The problem of mode matching is explained from the perspective of transverse mode and longitudinal mode,and the influence of laser injection efficiency on measurement precision is further analyzed.The results of cavity ring-down time measurement show that the measurement precision is higher when the laser is coupled with the fundamental mode.In the experiment,DFB laser is used to calibrate the system with standard methane concentration,and the measurement residual is less than±4×10^(-4)μs^(-1).The methane concentration in the air is monitored in real time for two days.The results show the consistency of the concentration changes over the two days,which further demonstrates the reliability of the system for the measurement of trace methane.By analyzing the influence of mode matching,it not only assists the adjustment of the optical path,but also further improves the sensitivity of the system measurement.
基金supported by National Natural Science Foundation of China (Grant No. 61505223)the project of China State Key Lab. of Power System (Grant No. SKLD18KM11)
文摘Calibration-free laser-induced breakdown spectroscopy can overcome the matrix effect and the huge application prospects of in situ and on-line measurement, so it has been studied and applied to many analytical samples by numerous researchers since it was first proposed in 1999.However, its accuracy is always lower than other analytical techniques and traditional quantitative analysis methods of laser-induced breakdown spectroscopy. The goal of this paper is to review the improvement of accuracy in the experimental setup and spectral analysis,especially after 2010, but not limited to it. The main contents include the accurate measurement of spectral intensity, the spatial and temporal window of local thermodynamic equilibrium and the accurate calculation of temperature and electron density. Due to the requirement of one or more standard samples, the combination of standard samples and CF-LIBS is discussed as a separate section. Finally, a simple conclusion is offered to relevant researchers who want to use CF-LIBS for quantitative analysis.
基金supported by the Young Scientists Fund of National Natural Science Foundation of China(No.12004388)the National High Technology Research and Development Program of China(No.2021YFB3202402)+1 种基金the Key Research and Development Plan of Anhui Province(No.202104i07020009)the Collaborative Innovation Program of Hefei Science Center,CAS(No.2021HSCCIP005)。
文摘The optimal spectral excitation and acquisition scheme is explored by studying the effect of the lensto-sample distance(LTSD)on the spatial homogeneity and emission spectra of flat-top laser converging spot induced plasma.The energy distribution characteristics before and after the convergence of the laser beam with quasi flat-top intensity profile used in this study are theoretically simulated and experimentally measured.For an aspheric converging mirror with a focal length of100 mm,the LTSD(106 mm≥LTSD≥96 mm)was changed by raising the stainless-steel sample height.The plasma images acquired by ICCD show that there is air breakdown when the sample is below the focal point,and a ring-like plasma is produced when the sample is above the focal point.When the sample is located near the focal point,the plasma shape resembles a hemisphere.Since the spectral acquisition region is confined to the plasma core and the image contains all the optical information of the plasma,it has a lower relative standard deviation(RSD)than the spectral lines.When the sample surface is slightly higher than the focal plane of the lens,the converging spot has a quasi flat-top distribution,the spatial distribution of the plasma is more uniform,and the spectral signal is more stable.Simultaneously,there is little difference between the RSD of the plasma image and the laser energy.In order to further improve the stability of the spectral signal,it is necessary to expand the spectral acquisition area.
