激光诱导击穿光谱技术在气体检测中的研究综述

随着工业技术的发展,气体检测领域对在线检测仪器及检测技术的要求越来越高,气体成分在气体流动时会发生复杂变化,通常的检测手段傅里叶变换红外光谱技术(FTIR)、光腔衰荡技术(CRDS)、电化学传感等往往不能满足检测要求或仅对局部区域检测。激光诱导击穿光谱(LIBS)作为一种新兴的原子发射光谱分析技术,得到光谱分析领域研究者的广泛重视与研究。LIBS技术具备多元素同时检测、非侵入式、实时在线以及无需样品特殊制备等技术优势,已应用于固体、液体和气体的检测。在环境恶劣、干扰较大的气体制造及检测领域LIBS技术能够实时准确地进行检测。介绍了LIBS技术基本原理并描述等离子体物理特性的两个参数等离子体温度及等离子体电子数密度,针对LIBS技术在气体检测领域中的应用,从通过原子谱线强度比分析燃料的当量比、燃料混合气燃烧产物的气体组分、工业制造中作为保护气的氮气及稀有气体、温室气体和新能源气体的检测,以及与之相关的LIBS实验装置及实验方法的改进与优化等6个方面介绍了LIBS技术应用于气体检测领域的近些年国内外进展。对气体检测领域激光诱导击穿光谱研究的前景进行了展望。     

Influence of polarization of laser beam on emission intensity of femtosecond laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy(LIBS) is an important technique which is widely used to analyze element composition. In order to improve the sensitivity of LIBS, much effort has been made to enhance the spectral intensity of LIBS by proposing a number of methods. In addition, we find that laser polarization has great influence on the emission intensity of femtosecond LIBS. By comparing the emission intensity of femtosecond LIBS in the circular polarization with that in the linear polarization, the spectral intensity in the case of circular polarization is stronger than that in the case of linear polarization. Moreover, this phenomenon is more obvious as laser energy increases. The polarization plays an important role in LIBS signal intensity. Based on the observation, the enhanced mechanism of the laser polarization for the spectral intensity is discussed in this paper, which will be helpful in spectral analysis and component analysis.     

火星车载激光诱导击穿光谱仪(MarsCoDe)在轨定标样品选取研究

我国首次火星全球遥感与区域巡视探测任务已获批立项,首个火星探测器也即将前往火星。为满足火星物质成分分析的需求,我国研制了不同类型的火星物质成分分析仪器,其中包括火星表面成分探测仪（MarsCoDe）,应用了激光诱导击穿光谱技术（laser-induced breakdown spectroscopy,LIBS）。火星表面覆盖尘埃,探测仪器想要准确获取火星尘埃之下的物质成分,必须剥去尘埃或者进行破坏从而深入岩层取样。LIBS可以用激光烧蚀待测物体表面,获得深部物质光谱信息,在火星表面探测中具有其他仪器无法取代的优势。LIBS在火星探测中几乎适用于探测每一个元素,包括轻元素H,Li,Be,B,C,N,O等,帮助寻找有机物和含水地质过程的证据。由于LIBS在火星环境工作,等离子体的物理性质与地球上完全不同。为了确保火星车载LIBS返回数据的光谱质量,需要对LIBS在着陆后开展在轨定标。借助火星车的携带在轨定标样品,对探测数据进行在轨定标,确保返回数据的可靠性。定标样品的选择是一项十分重要的工作,存在仪器工程条件限制、定标样品类型的代表性、元素成分分布范围、样品稳定性等多种考虑因素,需满足科学任务的同时达到加工工艺要求。总结了国外已有的火星车载LIBS在轨定标的研究进展,重点分析了LIBS在轨定标样品选择依据、国外选择样品的优缺点,并总结经验提出了几点建议,为我国在轨定标工作提供参考。对火星探测数据的正确解译,对未来研究火星的起源、火星的长期地质演变过程等具有重要的科学意义。     

Trace elemental analysis by laser-induced breakdown spectroscopy—Biological applications

Laser-Induced Breakdown Spectroscopy (LIBS) is a sensitive optical technique capable of fast multi-elemental analysis of solid, gaseous and liquid samples. Since the late 1980s LIBS became visible in the analytical atomic spectroscopy scene; its applications having been developed continuously since then. In this paper, the use of LIBS for trace element determination in different matrices is reviewed. The main emphasis is on spatially resolved analysis of microbiological, plant and animal samples.     

Laser-induced breakdown spectroscopy in China

Laser-induced breakdown spectroscopy （LIBS） has been regarded as a future superstar for chemical analysis for years due to its unique features such as little or no sample preparation, remote sensing, and fast and multi-element analysis. Chinese LIBS comnmnity is one of the most dynamically developing communities in the World. The aim of the work is to inspect what have been done in China for LIBS development and, based on the understanding of the overall status, to identify the challenges and opportunities for the future development. In this paper, the scientific contributions from Chinese LIBS comlnunity are reviewed for the following four aspects： fimdamentals, instrumentation, data processing and modeling, and applications; and the driving force of LIBS development in China is analyzed, the critical issues for successful LIBS application are discussed, and in our opinion, the potential direction to improve the technology and to realize large scale commercialization in China is proposed.     

基于激光诱导击穿光谱技术的土壤泥浆中Pb元素检测

激光诱导击穿光谱(LIBS)作为一种新兴的元素分析技术,具有实时在线、非接触、多元素同时探测等渚多优点.将LIBS技术引入土壤泥浆重金属污染的检测分析,力图发展一种针对泥浆重金属污染监测的原位传感技术.实验选择Pb作为探测元素,Mn为内标元素;采用重复频率10 Hz的Nd:YAG调Q激光器的二倍频(532 nm)输出作为激发光源,OCD收集信号,对实验室配制的不同浓度Pb泥浆样品的LIBS信号进行了探测分析.获得了各种浓度下Pb泥浆样品在Pb 405.78 nm和Mn 403.07 nm处的原子线强度比IPb/IMn及其随浓度变化的规律.结果显示IPb/IMn与样品的含铅浓度有着很好的线性关系,线性拟合相关系数R2达到0.994 9.初步证实了采用内标法对土壤泥浆中重金属Pb进行LIBS检测分析的可行性.文章还对泥浆重金属LIBS检测的影响因素进行了讨论.     

基于EEMD-MRA方法的LIBS信号处理研究

LIBS技术优点众多,但由于光谱噪声干扰和基体效应等因素,影响了分析的准确度^[1]; EEMD方法能清晰的将LIBS信号中的不同特征成分自适应的分解开来。MRA方法能够补偿元素信号之间的互干扰,可进一步提高LIBS信号的准确性。通过自行搭建的测试系统获得了标准样品的原始信号,使用EEMD-MRA方法进行处理后,元素浓度曲线的决定系数R²得到了极大的提高,大大的提高数据的准确性,为LIBS信号的处理提供了一种全新的方式。     

激光诱导击穿光谱技术在土壤元素检测中的应用

激光诱导击穿光谱(laser-induced breakdown spectroscopy,LIBS)是一种原子发射光谱,具有对样本简单(或不需要)预处理,多元素同步、远距离测量,适用性广等独特优势。因此,LIBS分析技术被看作是未来化学分析和快速绿色分析技术领域的新兴技术。目前,土壤污染(重金属、有机污染等)检测与防治已成为现代农业和农业可持续发展关注和研究的热点问题。介绍了常见LIBS系统的结构组成以及工作原理,综述了LIBS技术对土壤中大量营养元素,重金属元素和土壤相关其他物质的研究现状和主要进展,提出了LIBS检测技术在土壤元素等方面的研究方向和发展趋势。     

Recent progress on the application of LIBS for metallurgical online analysis in China

Recent progress on the application of laser-induced breakdown spectroscopy (LIBS) for metallurgical analysis particularly achieved by Chinese research community is briefly reviewed in this article. The content is mainly focused on the progress in experimental research and calibration methods toward LIBS applications for metallurgical online analysis over the past few years. Different experiment setups such as single-pulse and double-pulses LIBS schematics are introduced. Various calibration methods for different metallic samples are presented. Quantitative results reported in the literature and obtained in the analysis of various samples with different calibration methods are summarized. At the last section of this article, the difficulties of LIBS application for molten metal analysis in a furnace are discussed.     

Detection of explosives with laser-induced breakdown spectroscopy

Our recent work on the detection of explosives by laser-induced breakdown spectroscopy (LIBS) is reviewed in this paper. We have studied the physical mechanism of laser-induced plasma of an organic explosive, TNT. The LIBS spectra of TNT under single-photon excitation are simulated using MATLAB. The variations of the atomic emission lines intensities of carbon, hydrogen, oxygen, and nitrogen versus the plasma temperature are simulated too. We also investigate the time-resolved LIBS spectra of a common inorganic explosive, black powder, in two kinds of surrounding atmospheres, air and argon, and find that the maximum value of the O atomic emission line SBR of black powder occurs at a gate delay of 596 ns. Another focus of our work is on using chemometic methods such as principle component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) to distinguish the organic explosives from organic materials such as plastics. A PLS-DA model for classification is built. TNT and seven types of plastics are chosen as samples to test the model. The experimental results demonstrate that LIBS coupled with the chemometric techniques has the capacity to discriminate organic explosive from plastics.     

Development in the application of laser-induced breakdown spectroscopy in recent years: A review

Laser-induced breakdown spectroscopy (LIBS) has been widely studied due to its unique advantages such as remote sensing, real-time multi-elemental detection and none-to-little damage. With the efforts of researchers around the world, LIBS has been developed by leaps and bounds. Moreover, in recent years, more and more Chinese LIBS researchers have put tremendous energy in promoting LIBS applications. It is worth mentioning that the application of LIBS in a specific field has its special application background and technical difficulties, therefore it may develop in different stages. A review summarizing the current development status of LIBS in various fields would be helpful for the development of LIBS technology as well as its applications especially for Chinese LIBS community since most of the researchers in this field work in application. In the present work, we summarized the research status and latest progress of main research groups in coal, metallurgy, and water, etc. Based on the current research status, the challenges and opportunities of LIBS were evaluated, and suggestions were made to further promote LIBS applications.     

Laser-Induced Breakdown Spectroscopy: An Approach to Detect Adulteration in Turmeric

In the present paper, four turmeric samples, A, B, C, and D, were analyzed using the laser-induced breakdown spectroscopic (LIBS) technique. Laser-induced breakdown spectra of A, B, and C give the spectral lines of elements such as carbon, sodium, potassium, magnesium, calcium, iron, and molecular bands of CN, whereas spectral signatures of the toxic elements lead and chromium are also present in sample D, demonstrating the adulteration in it. Principal component analysis of the LIBS data of the turmeric samples has been used for instant discrimination. The plots and principal components provide clusters belonging to two groups, enabling laser-induced breakdown spectroscopic data along with principal component analysis to be used as an instant monitoring tool.     

基于凸优化的激光诱导击穿光谱基线校正方法

在激光诱导击穿光谱定量分析中,基线是LIBS光谱信号的重要组成部分,由于受到实验参数设置及实验环境变化等影响,导致等离子体的发射谱线呈现不同程度的基线漂移现象,因此基线校正是光谱分析的重要环节。现有算法如多项式拟合通常需要设定关键参数,不具备自适应性。由于激光诱导产生的等离子体光谱信号的特征峰具有明显的独立性和稀疏性,以及基线具有低通特性,因此在凸优化约束框架下,提出了非参数化基线校正模型。同时,利用高效率的迭代算法来保证结果的收敛性。首先对23个高合金钢样本的光谱信号进行基线校正,然后以合金钢样本中的铬(Cr)元素为分析对象,并选取11条分析线进行定量分析。分别采用PLS和SVM定量模型进行训练和预测,并且与传统方法相比较,证明了所提出方法可以提高定量分析精度。     

人工神经网络在激光诱导击穿光谱数据分析中的应用进展

激光诱导击穿光谱(LIBS)具有实时、远程、多元素同时分析的优点,近年来在工业在线分析领域逐渐受到关注,发挥着重要作用。但基于发射光谱本身的特性,LIBS存在光谱噪声、基线漂移、自吸收和重叠峰等现象;又由于环境变化、激光能量波动、基体效应、样品表面形貌等因素,造成光谱稳定性和重现性差。这些问题导致光谱信息与定性、定量分析之间呈非线性关系,限制了分析灵敏度和准确度。随着LIBS器件稳定性的逐渐改善,LIBS光谱数据分析方法日新月异,人工神经网络(ANN)能跟踪和识别非线性特性,自适应学习LIBS光谱特征,筛除干扰信息,在LIBS数据分析领域的应用得到飞速发展。介绍了LIBS原理、仪器结构和工作流程以及在LIBS光谱分析领域常见的神经网络模型,总结出2015年—2020年LIBS结合常见的ANN模型在地质、合金、有机聚合物、煤炭、土壤及生物等领域的具体应用,指出ANN在数据分析领域的超强能力可有效改进LIBS分析精度,提升光谱数据利用率,降低光谱采集环境要求。针对仍然有待突破的技术难点,展望了ANN在LIBS光谱深度信息挖掘、便携式专用型设备开发、技术联用等方面的发展前景。LIBS日趋成熟...     

激光诱导等离子体光谱法检测合金钢组分的实验研究

激光诱导击穿光谱技术(LIBS)具有无需样品制备,原位快速分析,可进行实时控制的特点使其在钢铁冶炼控制中具有巨大的实际应用价值。本文以波长为1 064 nm的Nd∶YAG调Q固体激光器为激发光源,CCD为探测器,高合金钢GBW01605—01609系列为样品,在建立的LIBS实验装置上研究激光与合金钢之间的相互作用。系统地研究了观测距离、激光能量对高合金钢样品中激光诱导击穿谱特性的影响,并分析了LIBS信号的时间分辨特性,确定了将LIBS用于合金钢微量元素定量分析时的最佳实验条件。     

Effects of experimental parameters on elemental analysis of coal by laser-induced breakdown spectroscopy

The purpose of this work is to improve the precision of the elemental analysis of coal using laser-induced breakdown spectroscopy (LIBS). The LIBS technique has the ability to allow simultaneous elemental analysis and on-line determination, so it could be used in the elemental analysis of coal. Organic components such as C, H, O, N and inorganic components such as Ca, Mg, Fe, Al, Si, Ti, Na, and K of coal have been identified. The precision of the LIBS technique depends strongly on the experimental conditions, and the choice of experimental parameters should be aimed at optimizing the repeatability of the measurements. The dependences of the relative standard deviation (RSD) of the LIBS measurements on the experimental parameters including the sample preparation parameters, lens-to-sample distance, sample operation mode, and ambient gas have been investigated. The results indicate that the precision of LIBS measurements for the coal sample can be improved by using the optimum experimental parameters.     

An improved approach for hydrogen analysis in metal samples using single laser-induced gas plasma and target plasma at helium atmospheric pressure

We report in this paper the results of an experimental study on hydrogen analysis of solid samples in high pressure helium ambient gas employing the basic scheme of laser induced breakdown spectroscopy (LIBS). It is shown that the metastable excited state of helium atom can be utilized to induce delayed excitation of the ablated hydrogen atoms, and thereby avoid the Stark broadening effect as well as overcoming the undesirable mismatch effect, which are responsible for inefficient excitation respectively. It is further demonstrated that for samples of high boiling-point materials such as zircaloy, successful hydrogen analysis can be achieved by a newly introduced double excitation technique employing single laser realized in a modified configuration of the conventional LIBS method. PACS 51-52     

The validity of commercial LIBS for quantitative analysis of brass alloy — comparison of WDXRF and AAS

Commercial low-cost laser induced breakdown spectroscopy (LIBS) has been successfully employed for the quantitative analysis of a Cu-based alloy using a Nd:YAG laser at 1064 nm. The main aim of the present investigation is to explore the benefits of a commercial low-cost LIBS setup. It was recognized that some trace elements such as Al and S could not be detected by LIBS even with a high-resolution spectrometer. The main difficulties in quantifying Cu as a basic component of a brass alloy are related to the self-absorption of Cu spectral lines, with the effect complicated at Cu concentrations higher than 65%. However, few Cu lines such as that at 330.795 nm would be helpful to use due to their lower susceptibility to self-absorption. LIBS, flame atomic absorption spectrometry (FAAS), and wavelength dispersive X-ray fluorescence (WDXRF) were compared for the detection of major and trace metals in the Cu-based alloy. In the case of WDXRF, the brass samples were identified by using a standardless quantitative analysis program depending on a fundamental parameter approach. The quantitative analysis results were acceptable for most of the major and minor elements of the brass sample. Therefore, commercial low cost LIBS would be useful for quantitative analysis of most elements in different types of alloys.     

In-depth micro-spectrochemical analysis of archaeological Egyptian pottery shards

Old Egyptian pottery samples have been in-depth microchemically analyzed using laser induced breakdown spectroscopy (LIBS), energy dispersive X-ray (EDX), and X-ray diffraction (XRD) techniques. Samples from two different ancient Islamic eras, Mamluk (1250–1517 AD), Fatimid (969–1169 AD) in addition to samples from the Roman period (30 BC–395 AD) were investigated. LIBS provided the analytical data necessary to study in micrometric steps the depth profiling of various elements in each sample. Common elements such as silicon, calcium, and aluminum relevant to the originally manufactured and processed clay, showed up in all the investigated samples. EDX and XRD techniques that have been used in the present work provided important chemical insight about the structure of the samples. The obtained analytical results demonstrated the possibility of using LIBS technique in performing in situ spectrochemical analysis of archaeological pottery. This leads to fast in-depth spatial characterization of the samples in the micron range with nearly invisible surface destructive effects. There is no doubt that this can help in restoration and conservation of such precious objects.     

Assessment of LIBS for Spectrochemical Analysis: A Review

Abstract

This review assesses the applications of laser-induced breakdown spectroscopy (LIBS) for the analysis of a variety of samples, including biomaterials (teeth, nail, hair, gallstones, and kidney stones, etc.), food materials (fruits and vegetables, milk, salt, nutritional supplements, etc.), medicinal plants, industrial waste, liquid samples, etc. In addition, for the first time the identification of cholesterol and pigment stones was performed on the basis of atomic lines of different elements and molecular bands of C₂ molecules present in the LIBS spectra of gallstones. Chemometric techniques such as principal component analysis (PCA) was also applied to LIBS data for rapid identification/classification of different gallstone samples. LIBS analysis of toxic/heavy elements present in vegetables (spinach, tomato) and rice is also presented in this review. It was observed that vegetables grown near industrial areas are rich in several toxic metals like Pb and Cr. The wastewater samples from different industries were also analyzed by recording their spectra using a liquid jet. These results clearly demonstrate the ability of LIBS technique as an instant monitoring device to detect heavy metals present in liquid samples. Finally, this review shows that LIBS is a versatile analytical technique with unlimited applications.