Coffee is one of the most consumed and commercialized crops in the world, which is why there is a potential risk to find arabica coffee (an expensive variety) adulterated with robusta coffee (a cheaper variety). The c...Coffee is one of the most consumed and commercialized crops in the world, which is why there is a potential risk to find arabica coffee (an expensive variety) adulterated with robusta coffee (a cheaper variety). The currently used technique for certifying coffee, High Performance Liquid Chromatography (HPLC), requires the sample to be subjected to a chemical treatment prior to analysis;in addition, the equipment is bulky and can not be moved easily. Laser Induced Breakdown Spectroscopy (LIBS) is a technique which does not require that samples be subjected to a chemical pretreatment, and equipment is small and portable, this can save valuable time in coffee trading. The purpose of this research was to demonstrate that LIBS can be applied to solve various problems related with the coffee authentication. Green coffee pills with different concentrations of arabica and robusta varieties were analyzed by LIBS, the results were used in the construction of calibration curves for the detection of the degree of simulated adulteration in coffee. It was found that the relative intensities of Ca (392.4 nm), Sr (407.1 nm), N (500.5 nm) and Na (588.7 nm), as well as the intensity ratios of Ca II (392.4 nm)/N I (500.5 nm), Sr I (407.1 nm)/N I (500.5 nm)and N I (500.5 nm)/Na I (588.7 nm) can be used for this purpose. It is concluded that the differentiation of coffee and the detection of its adulteration is possible with the use of LIBS. Further, with the use of an Artificial Neural Network (ANN) of type Multilayer Perceptron, it was possible to correctly classify the spectra of arabica and robusta roasted coffee.展开更多
Scrap metals are typically covered with surface contaminants,such as paint,dust,and rust,which can significantly affect the emission spectrum during laser-induced breakdown spectroscopy(LIBS)based sorting.In this stud...Scrap metals are typically covered with surface contaminants,such as paint,dust,and rust,which can significantly affect the emission spectrum during laser-induced breakdown spectroscopy(LIBS)based sorting.In this study,the effects of paint layers on metal surfaces during LIBS classification were investigated.LIBS spectra were collected from metal surfaces painted with black and white paints by ablation with a nanosecond pulsed laser(wavelength=1064 nm,pulse width=7 ns).For the black-painted samples,the LIBS spectra showed a broad background emission,emission lines unrelated to the target metals,large shot-to-shot variation,and a relatively low signal intensity of the target metal,causing poor classification accuracy even at high shot numbers.Cleaning the black paint layer by ablating over a wide area prior to LIBS analysis resulted in high classification accuracy with fewer shot numbers.A method to determine the number of cleaning shots necessary to obtain high classification accuracy and high throughput is proposed on the basis of the change in LIBS signal intensity during cleaning shots.For the white-painted samples,the paint peeled off the metal surface after the first shot,and strong LIBS signals were measured after the following shot,which were attributed to the nanoparticles generated by the ablation of the paint,allowing an accurate classification after only two shots.The results demonstrate that different approaches must be employed depending on the paint color to achieve high classification accuracy with fewer shot numbers.展开更多
Laser-induced breakdown spectroscopy （LIBS） has become a powerful technology in geological applications. The correct identification of rocks and soils is critical to many geological projects. In this study, LIBS dat...Laser-induced breakdown spectroscopy （LIBS） has become a powerful technology in geological applications. The correct identification of rocks and soils is critical to many geological projects. In this study, LIBS database software with a user-friendly and intuitive interface is developed based on Windows, consisting of a database module and a sample identification module. The database module includes a basic database containing LIBS persistent lines for elements and a dedicated geological database containing LIBS emission lines for several rock and soil reference standards. The module allows easy use of the data. A sample identification module based on partial least squares discriminant analysis （PLS-DA） or support vector machine （SVM） algorithms enables users to classify groups of unknown spectra. The developed system was used to classify rock and soil data sets in a dedicated database and the results demonstrate that the system is capable of fast and accurate classification of rocks and soils, and is thus useful for the detection of geological materials.展开更多
Laser-induced breakdown spectroscopy(LIBS) is a useful technique for accurate sorting of metal scrap by chemical composition analysis.In this work,a method for intensity-ratiobased LIBS classification of stainless ste...Laser-induced breakdown spectroscopy(LIBS) is a useful technique for accurate sorting of metal scrap by chemical composition analysis.In this work,a method for intensity-ratiobased LIBS classification of stainless steel applicable to highly fluctuating LIBS signal conditions is proposed.The spectral line pairs for intensity ratio calculation are selected according to elemental concentration and upper levels of emission lines.It is demonstrated that the classification accuracy can be significantly improved from that of full-spectra principal component analysis or intensity-based analysis.The proposed method is considered to be suited to an industrial scrap sorting system that requires minimal maintenance and low system price.展开更多
Although laser-induced breakdown spectroscopy(LIBS),as a fast on-line analysis technology,has great potential and competitiveness in the analysis of chemical composition and proximate analysis results of coal in therm...Although laser-induced breakdown spectroscopy(LIBS),as a fast on-line analysis technology,has great potential and competitiveness in the analysis of chemical composition and proximate analysis results of coal in thermal power plants,the measurement repeatability of LIBS needs to be further improved due to the difficulty in controlling the stability of the generated plasmas at present.In this paper,we propose a novel x-ray fluorescence(XRF) assisted LIBS method for high repeatability analysis of coal quality,which not only inherits the ability of LIBS to directly analyze organic elements such as C and H in coal,but also uses XRF to make up for the lack of stability of LIBS in determining other inorganic ash-forming elements.With the combination of elemental lines in LIBS and XRF spectra,the principal component analysis and the partial least squares are used to establish the prediction model and perform multi-elemental and proximate analysis of coal.Quantitative analysis results show that the relative standard deviation(RSD) of C is 0.15%,the RSDs of other elements are less than 4%,and the standard deviations of calorific value,ash content,sulfur content and volatile matter are 0.11 MJ kg,0.17%,0.79% and 0.41%respectively,indicating that the method has good repeatability in determination of coal quality.This work is helpful to accelerate the development of LIBS in the field of rapid measurement of coal entering the power plant and on-line monitoring of coal entering the furnace.展开更多
As an important non-ferrous metal structural material most used in industry and production,aluminum(Al) alloy shows its great value in the national economy and industrial manufacturing.How to classify Al alloy rapidly...As an important non-ferrous metal structural material most used in industry and production,aluminum(Al) alloy shows its great value in the national economy and industrial manufacturing.How to classify Al alloy rapidly and accurately is a significant, popular and meaningful task.Classification methods based on laser-induced breakdown spectroscopy(LIBS) have been reported in recent years. Although LIBS is an advanced detection technology, it is necessary to combine it with some algorithm to reach the goal of rapid and accurate classification. As an important machine learning method, the random forest(RF) algorithm plays a great role in pattern recognition and material classification. This paper introduces a rapid classification method of Al alloy based on LIBS and the RF algorithm. The results show that the best accuracy that can be reached using this method to classify Al alloy samples is 98.59%, the average of which is 98.45%. It also reveals through the relationship laws that the accuracy varies with the number of trees in the RF and the size of the training sample set in the RF. According to the laws, researchers can find out the optimized parameters in the RF algorithm in order to achieve,as expected, a good result. These results prove that LIBS with the RF algorithm can exactly classify Al alloy effectively, precisely and rapidly with high accuracy, which obviously has significant practical value.展开更多
Laser-induced breakdown spectroscopy（LIBS） is a versatile tool for both qualitative and quantitative analysis.In this paper,LIBS combined with principal component analysis（PCA） and support vector machine（SVM） is...Laser-induced breakdown spectroscopy（LIBS） is a versatile tool for both qualitative and quantitative analysis.In this paper,LIBS combined with principal component analysis（PCA） and support vector machine（SVM） is applied to rock analysis.Fourteen emission lines including Fe,Mg,Ca,Al,Si,and Ti are selected as analysis lines.A good accuracy（91.38% for the real rock） is achieved by using SVM to analyze the spectroscopic peak area data which are processed by PCA.It can not only reduce the noise and dimensionality which contributes to improving the efficiency of the program,but also solve the problem of linear inseparability by combining PCA and SVM.By this method,the ability of LIBS to classify rock is validated.展开更多
The use of laser-induced breakdown spectroscopy(LIBS) for the analysis of heavy metals in water samples is investigated. Some factors such as splashing, surface ripples, extinction of emitted intensity, and a shorter ...The use of laser-induced breakdown spectroscopy(LIBS) for the analysis of heavy metals in water samples is investigated. Some factors such as splashing, surface ripples, extinction of emitted intensity, and a shorter plasma lifetime will influence the results if the water sample is directly measured. In order to avoid these disadvantages and the ‘coffee-ring effect', hydrophilic graphite flakes with annular grooves were used for the first time to enrich and concentrate heavy metals in water samples before being analyzed by LIBS. The proposed method and procedure have been evaluated to concentrate and analyze cadmium, chromium, copper, nickel, lead,and zinc in a water sample. The correlation coefficients were all above 0.99. The detection limits of 0.029, 0.087, 0.012, 0.083, 0.125, and 0.049 mgl^(-1) for Cd, Cr, Cu, Ni, Pb, and Zn,respectively, were obtained in samples prepared in a laboratory. With this structure, the heavy metals homogeneously distribute in the annular groove and the relative standard deviations are all below 6%. This method is very convenient and suitable for online in situ analysis of heavy metals.展开更多
A diode-pumped solid-state laser （DPSSL） with a high energetic stability and long service life is applied to ablate the steel samples instead of traditional Nd：YAG laser pumped by a xenon lamp, and several factors,...A diode-pumped solid-state laser （DPSSL） with a high energetic stability and long service life is applied to ablate the steel samples instead of traditional Nd：YAG laser pumped by a xenon lamp, and several factors, such as laser pulse energy, repetition rate and argon flow rate, that influence laser-induced breakdown spectroscopy （LIBS） analytical performance are investigated in detail. Under the optimal experiment conditions, the relative standard deviations for C, Si, Mn, Ni, Cr and Cu are 3.3%-8.9%, 0.9%-2.8%, 1.2%-4.1%, 1.7%-3.0%, 1.1%-3.4% and 2.5%-8.5%, respectively, with the corresponding relative errors of 1.1%-7.9%, 1.0%-6.3%, 0.4%-3.9%, 1.5%-6.3%, 1.2%-4.0% and 1.2%-6.4%. Compared with the results of the traditional spark discharge optical emission spectrometry technique, the analytical performance of LIBS is just a little inferior due to the less stable laser-induced plasma and smaller amount of ablated sample by the laser. However, the precision, detection limits and accuracy of LIBS obtained in our present work were sufficient to meet the requirements for process analysis. These technical performances of higher stability of output energy and longer service life for DPSSL, in comparison to the Q-switch laser pumped by xeon lamp, qualify it well for the real time online analysis for different industrial applications.展开更多
Laser-induced breakdown spectroscopy(LIBS) is regarded as a promising technique for realtime sorting of scrap metals due to its capability of fast multi-elemental and in-air analysis. This work reports a method for si...Laser-induced breakdown spectroscopy(LIBS) is regarded as a promising technique for realtime sorting of scrap metals due to its capability of fast multi-elemental and in-air analysis. This work reports a method for signal processing which ensures high accuracy and high speed during similar metal sorting by LIBS. Similar metals such as aluminum alloys or stainless steel are characterized by nearly the same constituent elements with slight variations in elemental concentration depending on metal type. In the proposed method, the original data matrix is substantially reduced for fast processing by selecting new input variables(spectral lines) using the information for the constituent elements of similar metals. Specifically, principal component analysis(PCA) of full-spectra LIBS data was performed and then, based on the loading plots, the input variables of greater significance were selected in the order of higher weights for each constituent element. The results for the classification test with aluminum alloy, copper alloy,stainless steel and cast steel showed that the classification accuracy of the proposed method was nearly the same as that of full-spectra PCA, but the computation time was reduced by a factor of 20 or more. The results demonstrated that incorporating the information for constituent elements can significantly accelerate classification speed without loss of accuracy.展开更多
Laser-induced breakdown spectroscopy （LIBS） has been used to detect atomic species in various enviromnents. The quantitative analysis （C, H, O, N and S） of representative coal samples are being carried out with LI...Laser-induced breakdown spectroscopy （LIBS） has been used to detect atomic species in various enviromnents. The quantitative analysis （C, H, O, N and S） of representative coal samples are being carried out with LIBS, and the effects of particle size are analyzed. A powerful pulse Nd：YAG laser is focused on the coal sample at atmosphere pressure, and the emission spectra from laser-induced plasmas are measured by time-resolved spectroscopy, and the intensity of analyzed spectral lines is obtained through observing the laser plasma with a delay time of 0.4 #s. The experimental results show that the slope of calibration curve is nearly 1 when the concentration of the analyzed element is relatively low, and the slope of curve is nearly 0.5 when the concentration of C is higher than other elements. In addition, using the calibration-free model without self-absorption effect, the results show that the decreasing of particle size leads to an increase of the plasma temperature.展开更多
The influence of the energy of femtosecond laser pulses on the intensity of Fe I （371.99 nm） emission line and the continuous spectrum of the plasma generated on the surface of Fe^3＋ water solution by a Ti： sapphi...The influence of the energy of femtosecond laser pulses on the intensity of Fe I （371.99 nm） emission line and the continuous spectrum of the plasma generated on the surface of Fe^3＋ water solution by a Ti： sapphire laser radiation with pulse duration 〈45 fs and energies up to 7 mJ is determined. A calibration curve was obtained for Fe3＋ concentration range from 0.5 g/L to the limit of detection in water solution, and its saturation was detected for concentrations above 0.25 g/L, which is ascribed to self-absorption. The 3σ- limit of detection obtained for Fe in water solution is 2.6 mg/L in the case of 7 mJ laser pulse energy. It is found that an increase of laser pulse energy insignificantly affects on LOD in the time-resolved LIBS and leads to a slight improvement of the limit of detection.展开更多
A mobile fiber-optic laser-induced breakdown spectrometer(FO-LIBS) prototype was developed to rapidly detect a large quantity of steel material online and quantitatively analyze the trace elements in a large-diameter ...A mobile fiber-optic laser-induced breakdown spectrometer(FO-LIBS) prototype was developed to rapidly detect a large quantity of steel material online and quantitatively analyze the trace elements in a large-diameter steel tube.Twenty-four standard samples and a polynomial fitting method were used to establish calibration curve models.The R^2 factors of the calibration curves were all above 0.99,except for Cu,indicating the elements’ strong self-absorption effect.Five special steel materials were rapidly detected in the steel mill.The average absolute errors of Mn,Cr,Ni,V,Cu,and Mo in the special steel materials were 0.039,0.440,0.033,0.057,0.003,and0.07 wt%,respectively,and their average relative errors fluctuated from 2.9% to 15.7%.The results demonstrated that the performance of this mobile FO-LIBS prototype can be compared with that of most conventional LIBS systems,but the more robust and flexible characteristics of the FO-LIBS prototype provide a feasible approach for promoting LIBS from the laboratory to the industry.展开更多
Laser-induced breakdown spectroscopy （LIBS） has attracted many academic and industrial interests world-wide due to its unique advantages, such as little or no sample preparation requirement, in-situ/online and multi...Laser-induced breakdown spectroscopy （LIBS） has attracted many academic and industrial interests world-wide due to its unique advantages, such as little or no sample preparation requirement, in-situ/online and multi-elemental analysis, and remote sensing etc., and it has been regarded as a ＂future super star＂ for chemical analysis for many years . In China,展开更多
Aluminum samples have been analyzed by femtosecond polarization-resolved laser-induced breakdown spectroscopy （fs-PRLIBS）. We compare the obtained spectra with those obtained from nanosecond PRLIBS （ns-PRLIBS）. Th...Aluminum samples have been analyzed by femtosecond polarization-resolved laser-induced breakdown spectroscopy （fs-PRLIBS）. We compare the obtained spectra with those obtained from nanosecond PRLIBS （ns-PRLIBS）. The main specific features of fs-PRLIBS are that a lower plasma temperature leads to a low level of continuum and no species are detected from the ambient gas. Furthermore, signals obtained by fs-PRLIBS show a higher stability than those of ns-PRLIBS. However, more elements are detected in the ns-PRLIBS spectra.展开更多
Determination of the chemical composition of cement and ratio values of clinker plays an important role in cement plants as part of the optimal process control and product quality evaluation. In the present paper, a l...Determination of the chemical composition of cement and ratio values of clinker plays an important role in cement plants as part of the optimal process control and product quality evaluation. In the present paper, a laboratory laser-induced breakdown spectroscopy （LIBS） apparatus mainly comprising a sealed optical module and an analysis chamber has been designed for possible application in cement plants for on-site quality analysis of cement. Emphasis is placed on the structure and operation of the LIBS apparatus, the sealed optical path, the temperature controlled spectrometer, the sample holder, the proper calibration model established for minimizing the matrix effects, and a correction method proposed for overcoming the ＇drift＇ obstacle. Good agreement has been found between the laboratory measurement results from the LIBS method and those from the traditional method. The absolute measurement errors presented here for oxides analysis are within 0.5%, while those of ratio values are in the range of 0.02 to 0.05. According to the obtained results, this laboratory LIBS apparatus is capable of performing reliable and accurate, composition and proximate analysis of cement and is suitable for application in cement plants.展开更多
Severe matrix effects and high signal uncertainty are two key bottlenecks for the quantitative performance and wide applications of laser-induced breakdown spectroscopy(LIBS).Based on the understanding that the superp...Severe matrix effects and high signal uncertainty are two key bottlenecks for the quantitative performance and wide applications of laser-induced breakdown spectroscopy(LIBS).Based on the understanding that the superposition of both matrix effects and signal uncertainty directly affects plasma parameters and further influences spectral intensity and LIBS quantification performance,a data selection method based on plasma temperature matching(DSPTM)was proposed to reduce both matrix effects and signal uncertainty.By selecting spectra with smaller plasma temperature differences for all samples,the proposed method was able to build up the quantification model to rely more on spectra with smaller matrix effects and signal uncertainty,therefore improving final quantification performance.When applied to quantitative analysis of the zinc content in brass alloys,it was found that both accuracy and precision were improved using either a univariate model or multiple linear regression(MLR).More specifically,for the univariate model,the root-mean-square error of prediction(RMSEP),the determination coefficients(R^(2))and relative standard derivation(RSD)were improved from 3.30%,0.864 and 18.8%to 1.06%,0.986 and 13.5%,respectively;while for MLR,RMSEP,R^(2)and RSD were improved from 3.22%,0.871 and 26.2%to 1.07%,0.986 and 17.4%,respectively.These results prove that DSPTM can be used as an effective method to reduce matrix effects and improve repeatability by selecting reliable data.展开更多
文摘Coffee is one of the most consumed and commercialized crops in the world, which is why there is a potential risk to find arabica coffee (an expensive variety) adulterated with robusta coffee (a cheaper variety). The currently used technique for certifying coffee, High Performance Liquid Chromatography (HPLC), requires the sample to be subjected to a chemical treatment prior to analysis;in addition, the equipment is bulky and can not be moved easily. Laser Induced Breakdown Spectroscopy (LIBS) is a technique which does not require that samples be subjected to a chemical pretreatment, and equipment is small and portable, this can save valuable time in coffee trading. The purpose of this research was to demonstrate that LIBS can be applied to solve various problems related with the coffee authentication. Green coffee pills with different concentrations of arabica and robusta varieties were analyzed by LIBS, the results were used in the construction of calibration curves for the detection of the degree of simulated adulteration in coffee. It was found that the relative intensities of Ca (392.4 nm), Sr (407.1 nm), N (500.5 nm) and Na (588.7 nm), as well as the intensity ratios of Ca II (392.4 nm)/N I (500.5 nm), Sr I (407.1 nm)/N I (500.5 nm)and N I (500.5 nm)/Na I (588.7 nm) can be used for this purpose. It is concluded that the differentiation of coffee and the detection of its adulteration is possible with the use of LIBS. Further, with the use of an Artificial Neural Network (ANN) of type Multilayer Perceptron, it was possible to correctly classify the spectra of arabica and robusta roasted coffee.
基金supported by the R&D Center for Valuable Recycling (Global-Top R&D Program)of the Ministry of Environment (No.2016002250003)。
文摘Scrap metals are typically covered with surface contaminants,such as paint,dust,and rust,which can significantly affect the emission spectrum during laser-induced breakdown spectroscopy(LIBS)based sorting.In this study,the effects of paint layers on metal surfaces during LIBS classification were investigated.LIBS spectra were collected from metal surfaces painted with black and white paints by ablation with a nanosecond pulsed laser(wavelength=1064 nm,pulse width=7 ns).For the black-painted samples,the LIBS spectra showed a broad background emission,emission lines unrelated to the target metals,large shot-to-shot variation,and a relatively low signal intensity of the target metal,causing poor classification accuracy even at high shot numbers.Cleaning the black paint layer by ablating over a wide area prior to LIBS analysis resulted in high classification accuracy with fewer shot numbers.A method to determine the number of cleaning shots necessary to obtain high classification accuracy and high throughput is proposed on the basis of the change in LIBS signal intensity during cleaning shots.For the white-painted samples,the paint peeled off the metal surface after the first shot,and strong LIBS signals were measured after the following shot,which were attributed to the nanoparticles generated by the ablation of the paint,allowing an accurate classification after only two shots.The results demonstrate that different approaches must be employed depending on the paint color to achieve high classification accuracy with fewer shot numbers.
基金supported by National Major Scientific Instruments and Equipment Development Special Funds,China(No.2011YQ030113)
文摘Laser-induced breakdown spectroscopy （LIBS） has become a powerful technology in geological applications. The correct identification of rocks and soils is critical to many geological projects. In this study, LIBS database software with a user-friendly and intuitive interface is developed based on Windows, consisting of a database module and a sample identification module. The database module includes a basic database containing LIBS persistent lines for elements and a dedicated geological database containing LIBS emission lines for several rock and soil reference standards. The module allows easy use of the data. A sample identification module based on partial least squares discriminant analysis （PLS-DA） or support vector machine （SVM） algorithms enables users to classify groups of unknown spectra. The developed system was used to classify rock and soil data sets in a dedicated database and the results demonstrate that the system is capable of fast and accurate classification of rocks and soils, and is thus useful for the detection of geological materials.
基金supported by the R&D Center for Valuable Recycling(Global-Top R&BD Program)of the Ministry of Environment.(Project No.2016002250003)partially supported by Korea Institute for Advancement of Technology(KIAT)grant funded by the Korea Government(MOTIE)(P0008763,The Competency Development Program for Industry Specialist)。
文摘Laser-induced breakdown spectroscopy(LIBS) is a useful technique for accurate sorting of metal scrap by chemical composition analysis.In this work,a method for intensity-ratiobased LIBS classification of stainless steel applicable to highly fluctuating LIBS signal conditions is proposed.The spectral line pairs for intensity ratio calculation are selected according to elemental concentration and upper levels of emission lines.It is demonstrated that the classification accuracy can be significantly improved from that of full-spectra principal component analysis or intensity-based analysis.The proposed method is considered to be suited to an industrial scrap sorting system that requires minimal maintenance and low system price.
基金supported by National Energy R&D Center of Petroleum Refining Technology of China(RIPP,SINOPEC)National Key Research and Development Program of China(No.2017YFA0304203)+5 种基金Changjiang Scholars and Innovative Research Team in University of Ministry of Education of China(No.IRT_17R70)National Natural Science Foundation of China(Nos.61975103,61875108,61775125 and 11434007)Industrial Application Innovation Project(No.627010407)Scientific and Technological Innovation Project of Shanxi Gemeng US-China Clean Energy R&D Center Co.,Ltd111 Project(D18001)Fund for Shanxi‘1331KSC’。
文摘Although laser-induced breakdown spectroscopy(LIBS),as a fast on-line analysis technology,has great potential and competitiveness in the analysis of chemical composition and proximate analysis results of coal in thermal power plants,the measurement repeatability of LIBS needs to be further improved due to the difficulty in controlling the stability of the generated plasmas at present.In this paper,we propose a novel x-ray fluorescence(XRF) assisted LIBS method for high repeatability analysis of coal quality,which not only inherits the ability of LIBS to directly analyze organic elements such as C and H in coal,but also uses XRF to make up for the lack of stability of LIBS in determining other inorganic ash-forming elements.With the combination of elemental lines in LIBS and XRF spectra,the principal component analysis and the partial least squares are used to establish the prediction model and perform multi-elemental and proximate analysis of coal.Quantitative analysis results show that the relative standard deviation(RSD) of C is 0.15%,the RSDs of other elements are less than 4%,and the standard deviations of calorific value,ash content,sulfur content and volatile matter are 0.11 MJ kg,0.17%,0.79% and 0.41%respectively,indicating that the method has good repeatability in determination of coal quality.This work is helpful to accelerate the development of LIBS in the field of rapid measurement of coal entering the power plant and on-line monitoring of coal entering the furnace.
基金supported by National High Technology Research and Development Program of China (863 Program. No. 2013AA102402)
文摘As an important non-ferrous metal structural material most used in industry and production,aluminum(Al) alloy shows its great value in the national economy and industrial manufacturing.How to classify Al alloy rapidly and accurately is a significant, popular and meaningful task.Classification methods based on laser-induced breakdown spectroscopy(LIBS) have been reported in recent years. Although LIBS is an advanced detection technology, it is necessary to combine it with some algorithm to reach the goal of rapid and accurate classification. As an important machine learning method, the random forest(RF) algorithm plays a great role in pattern recognition and material classification. This paper introduces a rapid classification method of Al alloy based on LIBS and the RF algorithm. The results show that the best accuracy that can be reached using this method to classify Al alloy samples is 98.59%, the average of which is 98.45%. It also reveals through the relationship laws that the accuracy varies with the number of trees in the RF and the size of the training sample set in the RF. According to the laws, researchers can find out the optimized parameters in the RF algorithm in order to achieve,as expected, a good result. These results prove that LIBS with the RF algorithm can exactly classify Al alloy effectively, precisely and rapidly with high accuracy, which obviously has significant practical value.
基金Project supported by the National Natural Science Foundation of China(Grant No.11075184)the Knowledge Innovation Program of the Chinese Academy of Sciences(CAS)(Grant No.Y03RC21124)the CAS President’s International Fellowship Initiative Foundation(Grant No.2015VMA007)
文摘Laser-induced breakdown spectroscopy（LIBS） is a versatile tool for both qualitative and quantitative analysis.In this paper,LIBS combined with principal component analysis（PCA） and support vector machine（SVM） is applied to rock analysis.Fourteen emission lines including Fe,Mg,Ca,Al,Si,and Ti are selected as analysis lines.A good accuracy（91.38% for the real rock） is achieved by using SVM to analyze the spectroscopic peak area data which are processed by PCA.It can not only reduce the noise and dimensionality which contributes to improving the efficiency of the program,but also solve the problem of linear inseparability by combining PCA and SVM.By this method,the ability of LIBS to classify rock is validated.
基金supported by National Natural Science Foundation of China (No. 21735005)the Science and Technology Program of Anhui Province (No. 1501041119)+1 种基金the Science and Technology Major Special Program of Anhui Province (No. 15CZZ04125)National Key Research and Development Plan of China (No. 2016YFD0800902-2)
文摘The use of laser-induced breakdown spectroscopy(LIBS) for the analysis of heavy metals in water samples is investigated. Some factors such as splashing, surface ripples, extinction of emitted intensity, and a shorter plasma lifetime will influence the results if the water sample is directly measured. In order to avoid these disadvantages and the ‘coffee-ring effect', hydrophilic graphite flakes with annular grooves were used for the first time to enrich and concentrate heavy metals in water samples before being analyzed by LIBS. The proposed method and procedure have been evaluated to concentrate and analyze cadmium, chromium, copper, nickel, lead,and zinc in a water sample. The correlation coefficients were all above 0.99. The detection limits of 0.029, 0.087, 0.012, 0.083, 0.125, and 0.049 mgl^(-1) for Cd, Cr, Cu, Ni, Pb, and Zn,respectively, were obtained in samples prepared in a laboratory. With this structure, the heavy metals homogeneously distribute in the annular groove and the relative standard deviations are all below 6%. This method is very convenient and suitable for online in situ analysis of heavy metals.
基金supported by the Development Fund of National Autonomous Demonstration Innovation Zone of Shandong Peninsula(Grant No.ZCQ17104)the National Key Research and Development Program of China(Grant No.2017YFB0305400)‘double hundred plan’ Yantai talent funding project
文摘A diode-pumped solid-state laser （DPSSL） with a high energetic stability and long service life is applied to ablate the steel samples instead of traditional Nd：YAG laser pumped by a xenon lamp, and several factors, such as laser pulse energy, repetition rate and argon flow rate, that influence laser-induced breakdown spectroscopy （LIBS） analytical performance are investigated in detail. Under the optimal experiment conditions, the relative standard deviations for C, Si, Mn, Ni, Cr and Cu are 3.3%-8.9%, 0.9%-2.8%, 1.2%-4.1%, 1.7%-3.0%, 1.1%-3.4% and 2.5%-8.5%, respectively, with the corresponding relative errors of 1.1%-7.9%, 1.0%-6.3%, 0.4%-3.9%, 1.5%-6.3%, 1.2%-4.0% and 1.2%-6.4%. Compared with the results of the traditional spark discharge optical emission spectrometry technique, the analytical performance of LIBS is just a little inferior due to the less stable laser-induced plasma and smaller amount of ablated sample by the laser. However, the precision, detection limits and accuracy of LIBS obtained in our present work were sufficient to meet the requirements for process analysis. These technical performances of higher stability of output energy and longer service life for DPSSL, in comparison to the Q-switch laser pumped by xeon lamp, qualify it well for the real time online analysis for different industrial applications.
基金supported by the R&D Center for Valuable Recycling (Global-Top R&BD Program) of the Ministry of Environment. (Project No. 2016002250003)
文摘Laser-induced breakdown spectroscopy(LIBS) is regarded as a promising technique for realtime sorting of scrap metals due to its capability of fast multi-elemental and in-air analysis. This work reports a method for signal processing which ensures high accuracy and high speed during similar metal sorting by LIBS. Similar metals such as aluminum alloys or stainless steel are characterized by nearly the same constituent elements with slight variations in elemental concentration depending on metal type. In the proposed method, the original data matrix is substantially reduced for fast processing by selecting new input variables(spectral lines) using the information for the constituent elements of similar metals. Specifically, principal component analysis(PCA) of full-spectra LIBS data was performed and then, based on the loading plots, the input variables of greater significance were selected in the order of higher weights for each constituent element. The results for the classification test with aluminum alloy, copper alloy,stainless steel and cast steel showed that the classification accuracy of the proposed method was nearly the same as that of full-spectra PCA, but the computation time was reduced by a factor of 20 or more. The results demonstrated that incorporating the information for constituent elements can significantly accelerate classification speed without loss of accuracy.
基金The project supported by Specialized Research Fund for the Doctoral Program of Higher Education (No. 20020487013) and bythe Key Program for International Cooperation of Science and Technology of China (No. 2001 CB711203)
文摘Laser-induced breakdown spectroscopy （LIBS） has been used to detect atomic species in various enviromnents. The quantitative analysis （C, H, O, N and S） of representative coal samples are being carried out with LIBS, and the effects of particle size are analyzed. A powerful pulse Nd：YAG laser is focused on the coal sample at atmosphere pressure, and the emission spectra from laser-induced plasmas are measured by time-resolved spectroscopy, and the intensity of analyzed spectral lines is obtained through observing the laser plasma with a delay time of 0.4 #s. The experimental results show that the slope of calibration curve is nearly 1 when the concentration of the analyzed element is relatively low, and the slope of curve is nearly 0.5 when the concentration of C is higher than other elements. In addition, using the calibration-free model without self-absorption effect, the results show that the decreasing of particle size leads to an increase of the plasma temperature.
基金supported by the Russian Science Foundation(agreement#14-50-00034)(measurements of limit of detection)Russian Foundation for Basic Research(NK 15-32-20878/15)obtained in the frame of "Organization of Scientific Research"in the Far Eastern Federal University supported by Ministry of Education and Science of Russian Federation
文摘The influence of the energy of femtosecond laser pulses on the intensity of Fe I （371.99 nm） emission line and the continuous spectrum of the plasma generated on the surface of Fe^3＋ water solution by a Ti： sapphire laser radiation with pulse duration 〈45 fs and energies up to 7 mJ is determined. A calibration curve was obtained for Fe3＋ concentration range from 0.5 g/L to the limit of detection in water solution, and its saturation was detected for concentrations above 0.25 g/L, which is ascribed to self-absorption. The 3σ- limit of detection obtained for Fe in water solution is 2.6 mg/L in the case of 7 mJ laser pulse energy. It is found that an increase of laser pulse energy insignificantly affects on LOD in the time-resolved LIBS and leads to a slight improvement of the limit of detection.
基金supported by National Natural Science Foundation of China(Nos.61705064,11647122)the Natural Science Foundation of Hubei Province(Nos.2018CFB773,2018CFB672)the Project of the Hubei Provincial Department of Education(No.T201617)。
文摘A mobile fiber-optic laser-induced breakdown spectrometer(FO-LIBS) prototype was developed to rapidly detect a large quantity of steel material online and quantitatively analyze the trace elements in a large-diameter steel tube.Twenty-four standard samples and a polynomial fitting method were used to establish calibration curve models.The R^2 factors of the calibration curves were all above 0.99,except for Cu,indicating the elements’ strong self-absorption effect.Five special steel materials were rapidly detected in the steel mill.The average absolute errors of Mn,Cr,Ni,V,Cu,and Mo in the special steel materials were 0.039,0.440,0.033,0.057,0.003,and0.07 wt%,respectively,and their average relative errors fluctuated from 2.9% to 15.7%.The results demonstrated that the performance of this mobile FO-LIBS prototype can be compared with that of most conventional LIBS systems,but the more robust and flexible characteristics of the FO-LIBS prototype provide a feasible approach for promoting LIBS from the laboratory to the industry.
文摘Laser-induced breakdown spectroscopy （LIBS） has attracted many academic and industrial interests world-wide due to its unique advantages, such as little or no sample preparation requirement, in-situ/online and multi-elemental analysis, and remote sensing etc., and it has been regarded as a ＂future super star＂ for chemical analysis for many years . In China,
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 11211120156, 11274053, 11074027, 61178022, and 60978014)the Science and Technology Department of Jilin Province, China (Grant Nos. 20100521, 20100168, and 20111812)the SRF for ROCS, SEM
文摘Aluminum samples have been analyzed by femtosecond polarization-resolved laser-induced breakdown spectroscopy （fs-PRLIBS）. We compare the obtained spectra with those obtained from nanosecond PRLIBS （ns-PRLIBS）. The main specific features of fs-PRLIBS are that a lower plasma temperature leads to a low level of continuum and no species are detected from the ambient gas. Furthermore, signals obtained by fs-PRLIBS show a higher stability than those of ns-PRLIBS. However, more elements are detected in the ns-PRLIBS spectra.
基金supported by National Natural Science Foundation of China(Nos.61127017,61378047,61205216,61178009,61108030,61475093,and 61275213)the National Key Technology R&D Program of China(No.2013BAC14B01)+2 种基金the 973 Program of China(No.2012CB921603)the Shanxi Natural Science Foundation,China(Nos.2013021004-1,2012021022-1)the Shanxi Scholarship Council of China(Nos.2013-011 and 2013-01)
文摘Determination of the chemical composition of cement and ratio values of clinker plays an important role in cement plants as part of the optimal process control and product quality evaluation. In the present paper, a laboratory laser-induced breakdown spectroscopy （LIBS） apparatus mainly comprising a sealed optical module and an analysis chamber has been designed for possible application in cement plants for on-site quality analysis of cement. Emphasis is placed on the structure and operation of the LIBS apparatus, the sealed optical path, the temperature controlled spectrometer, the sample holder, the proper calibration model established for minimizing the matrix effects, and a correction method proposed for overcoming the ＇drift＇ obstacle. Good agreement has been found between the laboratory measurement results from the LIBS method and those from the traditional method. The absolute measurement errors presented here for oxides analysis are within 0.5%, while those of ratio values are in the range of 0.02 to 0.05. According to the obtained results, this laboratory LIBS apparatus is capable of performing reliable and accurate, composition and proximate analysis of cement and is suitable for application in cement plants.
基金financial support from the Scientific Research Program for Young Talents of China National Nuclear Corporation(2020)National Natural Science Foundation of China(Nos.51906124 and 62205172)+1 种基金Shanxi Province Science and Technology Department(No.20201101013)Guoneng Bengbu Power Generation Co.,Ltd(No.20212000001)。
文摘Severe matrix effects and high signal uncertainty are two key bottlenecks for the quantitative performance and wide applications of laser-induced breakdown spectroscopy(LIBS).Based on the understanding that the superposition of both matrix effects and signal uncertainty directly affects plasma parameters and further influences spectral intensity and LIBS quantification performance,a data selection method based on plasma temperature matching(DSPTM)was proposed to reduce both matrix effects and signal uncertainty.By selecting spectra with smaller plasma temperature differences for all samples,the proposed method was able to build up the quantification model to rely more on spectra with smaller matrix effects and signal uncertainty,therefore improving final quantification performance.When applied to quantitative analysis of the zinc content in brass alloys,it was found that both accuracy and precision were improved using either a univariate model or multiple linear regression(MLR).More specifically,for the univariate model,the root-mean-square error of prediction(RMSEP),the determination coefficients(R^(2))and relative standard derivation(RSD)were improved from 3.30%,0.864 and 18.8%to 1.06%,0.986 and 13.5%,respectively;while for MLR,RMSEP,R^(2)and RSD were improved from 3.22%,0.871 and 26.2%to 1.07%,0.986 and 17.4%,respectively.These results prove that DSPTM can be used as an effective method to reduce matrix effects and improve repeatability by selecting reliable data.
