基于双脉冲LIBS结合偏最小二乘回归的稀土元素定量分析

激光诱导击穿光谱(LIBS)是一种以激光为激发源的等离子体发射光谱分析技术,已有将其用于稀土元素的定量分析研究,但由于稀土矿基体差异大、元素含量低,定量分析灵敏度和准确度仍有待提高。通过使用单激光分束构造双脉冲LIBS系统,并结合偏最小二乘回归(PLSR)算法实现对稀土矿石样品中的稀土元素La、Dy、Yb和Y的定量分析。结果表明,双脉冲LIBS结合PLSR可建立更加稳定的定标模型,与常规基本定标法相比,La、Dy、Yb和Y元素的相对均方根预测误差(RMSEP)从0.0061 %、0.0037%、0.0045%、0.0280 %降低至0.0044%、0.0016%、0.0029%、0.0134%,平均相对预测误差(AREP)从10.88%、15.27%、6.42%、17.20%降低至6.67%、3.62%、4.10%、7.98%。因此,双脉冲LIBS结合PLSR方法可以有效地提高LIBS对稀土矿石中稀土元素的定量分析能力。     

基于LIBS的GdFe合金材料快速检测技术研究

为了明晰LIBS（激光诱导击穿光谱）技术检测稀土合金材料的光谱特点,进一步开发基于LIBS的快速检测方法,推动LIBS技术在稀土领域的应用。本文利用激光诱导击穿光谱仪对GdFe合金材料的激发光谱,结合信号强度及背景噪音,研究确定了最佳设置参数。分别考察激光器和光谱仪的参数设置对光谱的影响,根据激发光谱中相关谱线的变化趋势,探讨GdFe合金材料的LIBS检测方法。实验发现,GdFe合金样品与激光孔(Laser aperture)的距离(Z值)、激光能量和积分时间是影响 LIBS光谱信号强度和背景噪音的关键参数。因金属和合金样品表面常覆盖氧化层,考察了脉冲激光的预剥蚀次数对光谱稳定性的影响,研究得出,在双脉冲均为164 mJ激光能量的激发下,预剥蚀1次可保证光谱效果。同时研究了两个激光器同时激发和延迟激发对GdFe合金光谱成因的影响,发现单脉冲激发与双脉冲同时激发所得光谱的信号强度并非两束脉冲单独激发的累加信号。通过光谱分析,确定了Z值0.8 mm、两个激光器的脉冲能量164 mJ、积分时间12 μs、脉冲延时时间0 μs,GdFe合金材料的光谱效果最佳,可为GdFe合金材料的LIBS检测方法建立提供参考,拓展LIBS技术在稀土领域的应用,为稀土合金产品的快速检测技术发展提供基础研究数据。     

激光诱导击穿光谱(LIBS)法微损快速检测党参中Pb

中药材重金属元素快速检测对污染监控及人们健康具有重要意义。激光诱导击穿光谱技术(Laser Induced Breakdown Spectroscopy, LIBS)属于一种快速检测方法,研磨压片等预处理方法相对样品消解已有所简化,但破坏了样品的物理性质,且不能满足中药材大宗品种、大批量检测需求。若进一步简化样品预处理,将更加凸显LIBS快速检测的优势。本文建立了激光诱导击穿光谱技术(LIBS)快速微损检测中药材样品重金属元素定标方法。线性相关系数R2为0.7764,建立的微损定标曲线线性可用于切片党参LIBS快速检测,对待测党参切片样品检测平均相对误差为3.74%,与电感耦合等离子体质谱法(ICP-MS)对比,相关系数R2为0.7957,验证了LIBS技术微损检测的可行性。制备的党参参考定标样品可多次重复用于待测样定标和仪器标定等。实验对待测党参样品仅进行切片处理,避免了研磨、压片等预处理,更加充分地体现LIBS快速检测的优势,为LIBS技术应用于中药材重金属元素快检等领域提供了一种新方法。     

基于黑体辐射提高自由定标激光诱导击穿光谱(CF-LIBS)定量精度的方法

自由定标激光诱导击穿光谱(Calibration-Free LIBS,CF-LIBS)技术是定量分析行业发展的主要趋势之一。该技术可直接基于局部热力学平衡等离子体模型,通过LIBS光谱数据和谱线参数计算出等离子体参数和各元素含量。且无需使用标准样品建立定标曲线,该技术不受基体效应的影响,非常适合实时、在线和多元素同时分析。但由光学厚而引起的自吸收效应是影响定量分析的重要因素。通过对比实验光谱数据与黑体辐射强度,研究等离子体温度,提高光学系统收集效率,抑制自吸收效应对CF-LIBS定量结果的影响。经过黑体辐射校正后,基体元素Fe的测定含量从88.700%提升到94.575%,相对误差(RE)从8.072%降低到1.984%。微量元素Cr、Mo和V的测定含量分别从0.635%、0.096%和0.023%降低至0.698%、0.143%和0.022%,相对误差(RE)从13.723%、45.455%和21.053%降低至5.163%、18.75%和15.789%。整体的平均绝对误差(MAE)从1.994%降低至0.497%。玻尔兹曼图拟合回归曲线有了更高的线性度。拟合系数R²     

激光诱导击穿光谱法测定铅泥废渣中的铅含量

铅泥废渣样品经105℃烘干3h,并研磨至通过0.075mm筛。称取此样品与石墨按1∶4~1∶29的质量比混合,两者的总质量为3.00g,充分混匀后压制成直径为30 mm,厚度为3mm的圆片,采用激光诱导击穿光谱法(LIBS)测定其中铅含量。选择铅的灵敏谱线405.78nm为分析线,仪器的采样门宽和延迟时间依次选为5.5,4.0μs。铅的拟合线性关系在10 000μg·g~(-1)以下,方法的检出限为345.2μg·g~(-1)。对同一样品用电感耦合等离子体原子发射光谱法测定其中铅含量并与LIBS结果进行比较。结果表明:两种方法的结果之间存在一定误差,当铅从约9 000μg·g~(-1)降低至约1 500μg·g~(-1)时,其相对误差从约1.3%增加至约15%,平均相对误差为6.80%。     

双脉冲激光诱导击穿光谱结合多元定标法定量分析大豆油中的铅

应用双脉冲激光诱导击穿光谱(DP-LIBS)对大豆油中的铅(Pb)含量进行检测。配制9个大豆油样品,采用一定规格圆柱形桐木对样品中Pb进行富集,然后通过Ava-Spec二通道高精度光谱仪采集其LIBS光谱信号。根据样品的LIBS谱线图和美国国家标准技术研究所(NIST)原子光谱数据库,确定选用CaⅡ393.284 nm,CaⅡ396.752 nm,NⅡ399.399 nm和PbⅠ405.685 nm的特征谱线强度作为自变量,得到Pb含量的多元线性回归定量分析模型,并通过方差分析和t检验验证分析模型的可行性。结果表明,采用Pb元素直接定标法得到的平均相对误差约为16%,拟合度R2为0.981 8;采用多元线性回归模型得到的平均相对误差为7.25%,拟合度R2为0.997 1,3个检验样品的相对误差均在合理范围内。采用多元校正分析模型可以充分利用光谱中的有效信息,降低基体效应的影响,从而提高LIBS分析的准确性。     

激光诱导击穿光谱对U元素的定量分析

铀矿是核领域最重要的矿产资源之一,快速、有效勘探铀矿资源能促进核领域平稳、健康发展。激光诱导击穿光谱(LIBS)技术具备多目标元素现场快速检测的优点,能实现铀矿资源准确、快速的现场分析。本工作基于LIBS技术对铀矿中U元素进行了定量分析,对比了偏最小二乘(PLS)和随机森林(RF)两种机器学习算法的定量效果。结果显示,RF模型的定量线性相关系数为0.996,对三个验证集的相对误差分别是22.33%、12.79%和12.04%;PLS模型的定量线性相关系数为0.997,对三个验证集的相对误差分别是4.33%、6.63%和6.85%。对比结果表明,本研究中的PLS模型定量准确度更高,同RF算法相比,PLS算法更适用于铀矿中U的LIBS定量分析。     

光谱滤波法提高激光诱导击穿光谱对蔬菜中元素Pb的检测精度

激光诱导击穿光谱(Laser induced breakdown spectroscopy, LIBS)原始光谱中包含较多噪声信号, 为探究不同滤波方法对LIBS光谱预处理的影响, 本研究以实验室Pb污染处理的蔬菜为研究对象, 采集波长范围在400.45~410.98 nm的LIBS谱线信息, 分别利用相邻平均(Adjacent averaging)、Savitzky-Golay(S-G)滤波器、快速傅里叶变换(Fast Fourier transformation, FFT)对采集的LIBS光谱进行平滑、去噪, 并结合偏最小二乘法(PLS)定量分析模型对光谱处理效果进行评价.结果表明, S-G平滑效果最优, 当S-G滤波器窗口宽度为15, 拟合阶次为3时, PLS定量模型效果最佳, 其验证集均方根误差(RMSEP)为0.26、平均相对误差(ARE)为3.7%.结果表明, 选择适合的滤波方法有助于提高LIBS光谱质量以及检测模型的精度.     

便携式远程激光诱导击穿光谱系统及其定量分析性能

因高温、辐射等极端环境限制，核领域亟需具备在线快速检测特性的分析仪器。基于小型风冷脉冲激光器与小型光纤光谱仪实现了远程激光诱导击穿光谱技术（LIBS）装置的小型化，对该便携式远程LIBS系统的定量分析性能进行了研究，实现了5 m外样品的元素遥测。在单脉冲激光能量100 mJ，脉冲延时1.0 μs的分析条件下，实现了白水晶、陶瓷及铝合金样品中Mn、Si、Al、Na、Ba、Ca及Cr元素的激发，验证了LIBS技术对材料组分和物料成分的远程探测能力，对铝合金样品的定量分析结果显示，该远程遥测系统对铝合金样品定量测量结果的最大相对平均偏差为12%，具备执行核领域快速分析场景下的半定量检测能力。     

支持向量机结台主成分分析辅助激光诱导击穿光谱技术识别鲜肉品种

为提高激光诱导击穿光谱技术(Laser-induced breakdown spectroscopy,LIBS)对鲜肉品种的识别率,采用支持向量机结合主成分分析算法辅助LIBS技术对鲜肉品种进行识别.对鲜肉切片用载玻片压平,采用LIBS技术对鲜肉组织(猪肉、牛肉和鸡肉)表面进行光谱数据的采集,每种鲜肉采集150幅光谱并进行随机排列,取前75幅光谱作为训练集建立模型,后75幅作为测试集测试建模结果.研究选取K、Ca、Na、Mg、Al、H、O等元素的49条归一化谱线数据进行主成分分析,并用所得数据建立支持向量机分类模型.结果表明,通过主成分分析降维,输入变量从49个优化减少到18个,模型建模速度从88.91 s降至55.52 s,提高了支持向量机的建模效率;并使预测集的平均识别率提高到89.11%.本研究为激光诱导击穿光谱技术在鲜肉品种快速分类领域提供了方法和数据参考.     

Determination of chromium in the surface nano-layer covering the Zn-based anti corrosion coating of steel sheets using a laser-induced breakdown spectrometry

A method was proposed for the determination of Cr in a thin surface nanolayer deposited on top of a micrometrical Zn-based anticorrosive coating of steel sheets using laser-induced breakdown spectrometry (LIBS). Optimization of the LIBS parameters was performed with respect to the statistical parameters of regression, these being the coefficient of determination (R ²), akaike information criterion and mean-squared prediction error. These were calculated for curves describing the relationship between the Cr surface concentration and the intensity of LIBS signal. The most critical parameter of analysis appears to be the focal spot diameter. When its value was 200 μm and corresponding energy density (fluence) had value of 413.8 J/cm², the intensity–concentration relationship revealed a negative slope. This phenomenon was caused by the difference in total ablated volume for samples with a different content of Cr in the surface layer. This phenomenon was not observed for higher values of the focal spot diameter (400 and 500 μm) and lower values of fluence (103.5 and 66.2 J/cm²). A range of calibration obtained under optimal conditions (focal spot diameter of 400 μm; single pulse mode, laser pulse energy of 130 mJ) was 11–21 mg/m² and the limit of detection was 0.7 mg/m². The recovery values calculated from the results of the proposed LIBS method and the standard ED XRF method ranged from 99.2 to 101%.     

Pulse chirp effects in ultrafast laser-induced breakdown spectroscopy

When compared to many other sensitive methods for material detection, such as inductively coupled mass spectroscopy and thermal ionization mass spectroscopy, laser-induced breakdown spectroscopy (LIBS) typically exhibits a lower signal-to-noise ratio (SNR), resulting in higher detection limits. Increasing the SNR of LIBS would improve the ability to characterize the sample composition with increased accuracy and speed and reduce the amount of material needed to perform analysis. We have been investigating the effect of simple ultrashort laser pulse shaping on the SNR of LIBS. Our goal is to control the dynamics of the ionization and recombination processes in the laser-produced plasma to favorably affect the SNR associated with the line emission from the plasma. Pulse shaping is performed using an acousto-optic programmable dispersive filter. An adaptive learning algorithm is being developed to automate the pulse shape optimization process for maximization of LIBS SNR in nuclear security-relevant material characterization scenarios. We report a 27 % increase of the SNR for non-gated LIBS measurements of uranium by utilizing simple pulse shaping limited exclusively to excess quadratic spectral phase of the laser pulse.     

Parametric study of a fiber-optic laser-induced breakdown spectroscopy probe for analysis of aluminum alloys

In the present work we demonstrate a fiber-optic laser-induced breakdown spectroscopy (FO LIBS) system for delivering laser energy to a sample surface to produce a spark as well as to collect the resulting radiation from the laser-induced spark. In order to improve the signal/background (S/B) ratio, various experimental parameters, such as laser energy, gate delay and width, detector gain, lenses of different focal lengths and sample surface, were tested. In order to provide high reliability and repeatability in the analysis, we also measured plasma parameters, such as electron density and plasma temperature, and determined their influence on the measurement results. The performance of FO LIBS was also compared with that of a LIBS system that does not use a fiber to transmit the laser beam. LIBS spectra with a good S/B were recorded at 2-μs gate delay and width. LIBS spectra of six different Al alloy samples were recorded to obtain calibration data. We were able to obtain linear calibration data for numerous elements (Cr, Zn, Fe, Ni, Mn, Mg and Cu). A linear calibration curve for LIBS intensity ratio vs. concentration ratio reduces the effect of physical variables (i.e. shot-to-shot power fluctuation, sample-to-surface distance, and physical properties of the samples). Our results reveal that this system may be useful in designing a high-temperature LIBS probe for measuring the elemental composition of Al melt.     

Laser-Induced Breakdown Spectroscopy in open-path configuration for the analysis of distant objects

A review of recent results on stand-off Laser-Induced Breakdown Spectroscopy (LIBS) analysis and applications is presented. Stand-off LIBS was suggested for elemental analysis of materials located in environments where any physical access was not possible but optical access could be envisaged. This review only refers to the use of the open-path LIBS configuration in which the laser beam and the returning plasma light are transmitted through the atmosphere. It does not present the results obtained with a transportation of the laser pulses to the target through an optical fiber. Open-path stand-off LIBS has mainly been used with nanosecond laser pulses for solid sample analysis at distances of tens of meters. Liquid samples have also been analyzed at distances of a few meters. The distances achievable depend on many parameters including the laser characteristics (pulse energy and power, beam divergence, spatial profile) and the optical system used to focus the pulses at a distance. A large variety of laser focusing systems have been employed for stand-off analysis comprising refracting or reflecting telescope. Efficient collection of the plasma light is also needed to obtain analytically useful signals. For stand-off LIBS analysis, a lens or a mirror is required to increase the solid angle over which the plasma light can be collected. The light collection device can be either at an angle from the laser beam path or collinear with the optical axis of the system used to focus the laser pulses on the target surface. These different configurations have been used depending on the application such as rapid sorting of metal samples, identification of material in nuclear industry, process control and monitoring in metallurgical industry, applications in future planetary missions, detection of environmental contamination or cleaning of objects of cultural heritage. Recent stand-off analyses of metal samples have been reported using femtosecond laser pulses to extend LIBS capabilities to very long distances. The high-power densities achievable with these laser pulses can also induce self-guided filaments in the atmosphere which produce LIBS excitation of a sample. The first results obtained with remote filament-induced breakdown spectroscopy predict sample analysis at kilometer ranges.     

Simple cylindrical ion mirror with three elements

A new cylindrical ion mirror has been designed to create an electric field that is non-linear or curved along the flight path axis for general-purpose time-of-flight mass spectrometers. The inclusion of one or two grids is found to improve the radial field homogeneity especially around the aperture. Only three cylindrical electrodes are used in the design. Changing the electrode dimensions and voltages affects the electric field distribution. Once the electrode dimensions are fixed, there are only two adjustable parameters for achieving optimum nonlinear electric field shape. Resolving powers of 7,000 and 16,100 have been achieved with kinetic energy variations of 34 and 10.5%, respectively. Simulations show that the electric field homogeneity in the radial direction enables the use of ion beam diameters up to 15 mm with only modest loss of resolving power. Increasing the mirror diameter could further increase the practical ion beam diameter. This article details the electric field distribution within the cylindrical mirror in both axial and radial directions. The voltages of the middle and rear electrodes affect the resolving power and the kinetic energy range over which focus can be achieved. The predicted arrival time spread for a single m/z value is narrower than that caused by the turn-around time of ions in a gas-phase ion source. In this case, the broad energy range over which good focus is achieved enables the use of higher extraction fields for turn-around time reduction.     

Depth profiling of tungsten coating layer on CuCrZr alloy using LIBS approach

Laser induced breakdown spectroscopy (LIBS) was employed to find the depth profile of W-coated CuCrZr alloy. Cathodic arc deposition method was applied to produce tungsten coating on the CuCrZr alloy. The LIBS measurements were carried out by using a Nd:YAG laser at its fundamental wavelength (1064 nm) with various fluences. The spectral intensity emitted from laser induced plasma of the coating material was investigated for both elemental and depth-profile analyses in terms of linear correlation coefficient. Other surface characterization techniques (scanning electron microscopy and energy dispersive X-ray) were also used to determine morphology and elemental composition. It is observed that nonuniform radial energy distribution of Gaussian laser beam caused gradual decay of spectral lines of the coating and rise of substrate lines. The results indicate that the spectral intensity from W coating was higher than that from the bulk material at same laser fluence. The high-resolution in-depth profile was achieved at low fluence. This study demonstrates that LIBS is a promising technique for the depth-profiling analysis of W coating of EAST-like material and can be used to determine the material erosion and impurity deposition on plasma facing components.     

Detection of zinc and lead in water using evaporative preconcentration and single-particle laser-induced breakdown spectroscopy

A novel laser-induced breakdown spectroscopy (LIBS)-based measurement method for metals in water is demonstrated. In the presented technology a small amount of sodium chloride is dissolved in the sample solution before spraying the sample into a tubular oven. After water removal monodisperse dry NaCl aerosol particles are formed where trace metals are present as additives. A single-particle LIBS analysis is then triggered with a scattering based particle detection system. Benefits are the highly increased metal concentration in the LIBS focal volume and the static NaCl-matrix which can be exploited in the signal processing procedure. Emitted light from the emerged plasma plume is collected with wide angle optics and dispersed with a grating spectrometer. In an aqueous solution, the respective limits of detection for zinc and lead were 0.3 ppm and 0.1 ppm using a relatively low 14 mJ laser pulse energy. Zn/Na peak intensity ratio calibration curve for zinc concentration was also determined and LIBS signal dependence on laser pulse energy was investigated.     

Laser-induced breakdown spectroscopy—From research to industry,new frontiers for process control

This paper presents R&D activities to explore new laser parameter ranges in pulse energy, time and space for laser-induced breakdown spectroscopy. The collinear double pulse effect, which is well studied for pulses of typically several 100 mJ energy can also be observed for laser pulses having a pulse energy two orders of magnitude lower. In this case, maximum line emission intensity occurs at interpulse separations of a few 100 ns. Temporal pulse tailoring to improve the performance of LIBS is only a first step. A comprehensive approach includes spatial pulse shaping to generate craters with predefined shape or to improve spatial averaging for the analysis of inhomogeneous samples. High performance components for LIBS systems such as spectrometers, electronics and sample stands are required to enable industrial applications. Latest developments offer wide-band single spectra acquisition with a high spectral resolution at a measuring frequency of up to 500 Hz. The next generation of multi-channel integrator electronics for Paschen–Runge spectrometers equipped with PMT detectors will further push the measuring speed to up to 5 kHz, thus opening a new area of high-speed LIBS microanalysis. Novel LIBS devices for various industrial applications presented include analysis of metallic process control samples with scale layers, on-site analysis of slag samples in secondary metallurgy, high-speed identification of Al scrap, mix-up detection of pipe fittings as well as recent work towards in-process identification of hot coils in a rolling mill.     

Insights in the laser induced breakdown spectroscopy signal generation underwater using dual pulse excitation — Part II: Plasma emission intensity as a function of interpulse delay

Influence of time delay between two laser pulses on the LIBS (laser induced breakdown spectroscopy) signal inside liquids was investigated and the results are compared with data from literature. Plasma was produced by laser ablation (LA) of aluminum inside water and its emission after the second laser pulse was characterized by spectrally and time resolved detection. Light propagation through the vapor bubble formed by the first laser pulse was studied by measurements of beam scattering and transmission. Optical absorption by the evolving bubble is not significant, but its growth is accompanied by lowering of its refraction index n_b with respect to surrounding liquid; this effect increases defocusing both of the incident beam and of the out-coming plasma radiation. Collection efficiency of the secondary plasma emission rapidly degrades with the cavity growth, but close to its full expansion the LIBS signal partially recovers through Snell's reflections at the liquid–vapor interface, which produce a bright spot close to the bubble center. Such a light redistribution allows detecting of the emission from external plasma volume, otherwise deflected out of the collection system. Except for strong line transitions from the main sample constituents, self-absorbed inside the high-pressure cavity, we observed the highest LIBS signal when sending the second pulse well before the bubble is fully expanded. Transitions of the pressure wave through the focal volume, formed by the first laser pulse and reflected from the cell's walls and sample back-plane, enhances the LIBS signal importantly. The measured lifetime of the secondary plasma rapidly decreases with the bubble expansion. Here, we also discuss the optimization of the optical collection system and some analytical aspects of double-pulse (DP) LIBS inside liquids.