Calibration-free laser-induced breakdown spectroscopy for quantitative elemental analysis of materials

The application of calibration-free laser-induced breakdown spectroscopy (CF-LIBS) for quantitative analysis of materials, illustrated by CF-LIBS applied to a brass sample of known composition, is presented in this paper. The LIBS plasma is produced by a 355?nm pulsed Nd:YAG laser with a pulse duration of 6?ns focussed onto a brass sample in air at atmospheric pressure. The time-resolved atomic and ionic emission lines of Cu and Zn from the LIBS spectra recorded by an Echelle spectrograph coupled with a gated intensified charge coupled detector are used for the plasma characterization and the quantitative analysis of the sample. The time delay where the plasma is optically thin and is also in local thermodynamic equilibrium (LTE), necessary for the elemental analysis of samples from the LIBS spectra, is deduced. An algorithm relating the experimentally measured spectral intensity values with the basic physics of the plasma is developed. Using the algorithm, the Zn and Cu concentrations in the brass sample are determined. The analytical results obtained from the CF-LIBS technique agree well with the certified values of the elements in the sample, with an accuracy error <1%.     

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.     

Determination of Chloride Content in Different Types of Cement Using Laser-Induced Breakdown Spectroscopy

The characterization and accurate determination of the chloride content in cement/concrete is very important for the assessment of the durability and safety of a concrete structure. The available analytical techniques are relatively expensive and time consuming. In this study, a laser-induced breakdown spectroscopy (LIBS) system was used for determination of elemental composition in three different types of cement samples. The plasma was generated by focusing a pulsed Nd: YAG laser at 1064 nm on the cement samples. The concentrations of different elements of significance for structural stability in cement samples were determined. The evaluation of the potential and the capabilities of LIBS as a rapid tool for characterization of cement samples is discussed. The optimum LIBS setup and experimental conditions to detect and measure chloride in building materials are reported. The LIBS results were compared with the results obtained using a standard analytical technique such as inductively coupled plasma emission spectroscopy (ICP–ES). The limits of detection were determined, and calibration curves were measured. The results of this investigation indicate the reliability of LIBS to characterize different cement samples and to assess the chloride content in these cements.     

On the improvement of signal repeatability in laser-induced air plasmas

The relatively low repeatability of laser-induced breakdown spectroscopy (LIBS) severely hinders its wide commercialization. In the present work, we investigate the optimization of LIBS system for repeatability improvement for both signal generation (plasma evolution) and signal collection. Timeintegrated spectra and images were obtained under different laser energies and focal lengths to investigate the optimum configuration for stable plasmas and repeatable signals. Using our experimental setup, the optimum conditions were found to be a laser energy of 250 mJ and a focus length of 100 mm. A stable and homogeneous plasma with the largest hot core area in the optimum condition yielded the most stable LIBS signal. Time-resolved images showed that the rebounding processes through the air plasma evolution caused the relative standard deviation (RSD) to increase with laser energies of > 250 mJ. In addition, the emission collection was improved by using a concave spherical mirror. The line intensities doubled as their RSDs decreased by approximately 25%. When the signal generation and collection were optimized simultaneously, the pulse-to-pulse RSDs were reduced to approximately 3% for O(I), N(I), and H(I) lines, which are better than the RSDs reported for solid samples and showed great potential for LIBS quantitative analysis by gasifying the solid or liquid samples.     

LIBS-Raman光谱联合水下探测系统及初步试验

水下激光诱导击穿光谱技术(LIBS)和水下激光拉曼光谱技术(Raman)已在深海成功获得应用,这两种技术探测对象互补、器件类似,两者联合探测可更好的进行深海研究。针对此需求研发了一套LIBS-Raman光谱联合水下原位探测原理样机,整个系统集成于L790 mm×Φ270 mm的舱体内,在舱体前端有光学窗口和水密插头,舱体内部主要包括脉冲激光器、光谱仪、嵌入式计算机和供电转换装置,甲板控制终端通过水密电缆实现对系统的供电、控制和数据采集。该联合系统采用一台双波长脉冲激光器同时作为LIBS和拉曼光谱的激发光源,LIBS采用1 064 nm波长,拉曼光谱采用532 nm波长。双波长激光器发出的光束经分光镜分为两路,经过后向散射光路收集的两路信号分别进入两个小型光纤光谱仪进行分光探测,LIBS采用AvaSpec-ULS2048光谱仪,拉曼光谱采用QE 65000光谱仪。利用搭建的原理样机在青岛近海进行水下原位探测,在实验室开展了水中固体靶的探测,实验结果证明了LIBS-Raman联合光谱探测装置的可行性。下一步将优化系统并开展深海探测应用。     

微波辅助激光诱导击穿光谱增强大米中Cd发射强度的研究

食品安全问题已成为全世界关注的焦点,对食品中污染物的绿色检测方法有利于环境的可持续发展。以大米中重金属污染物Cd元素为研究对象,分别采用激光诱导击穿光谱(LIBS)和微波辅助激光诱导击穿光谱(MA-LIBS)对空白和实验室污染处理的大米样品进行检测,并选用Cd Ⅰ 228.802 nm为分析线,探讨目标元素分析谱线等离子体发射强度的增强效果。同时,采用阳极溶出伏安法获取大米中Cd元素的真实含量。研究结果表明,对于实验室配制的浓度范围在2.16~13.69 μg·g-1的大米样品,LIBS仅能检测出其中大米Cd真实含量为13.69 μg·g-1的样品;而在同一实验条件下,MA-LIBS能检测出所有污染后样品中的Cd元素信号,并且与LIBS方法相比,Cd元素谱线发射强度增强了9~27倍,检测灵敏度提高了6.34倍。结果表明,采用MA-LIBS能有效地增强大米中Cd元素等离子体的发射强度并提高其检测灵敏度。     

High stability breakdown of noble gases with femtosecond laser pulses

In the past, laser-induced breakdown spectroscopy (LIBS) signals have been reported to have a stability independent of the pulse length in solids. In this Letter, we perform the first stability study of femtosecond LIBS in gases (to our best knowledge) and show a significant improvement in signal stability over those achieved with longer pulses. Our study shows that ultrashort-pulse LIBS has an intrinsically higher stability in gas compared to nanosecond-pulse LIBS because of a deterministic ionization process at work in the femtosecond pulse. Relative standard deviations below 1% are demonstrated and are likely only limited by our laser output fluctuations. This enhanced emission stability may open up possibilities for a range of applications, from monitoring rapid gas dynamics to high-quality broadband light sources.     

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.     

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.     

真空环境熔融金属成分检测的激光诱导击穿光谱系统

激光诱导击穿光谱(LIBS)技术是应用于冶金在线分析最具前景的技术之一。为了研究真空和高温条件下LIBS光谱特性和物质成分定量分析方法,设计并搭建了可实现真空环境高温熔融金属LIBS光谱测量的实验系统。系统以调Q Nd: YAG脉冲激光器为光源,采用不同焦距透镜实现激光聚焦和信号光采集,并利用光谱仪进行光谱检测,真空获取和高温加热通过真空泵和中频感应电炉实现,感应加热线圈通过陶瓷封接引线法兰与真空系统进行整合。经过安装测试,搭建系统在未加热情况下真空度可达1×10-4Pa,加热温度可达到1 600 ℃,可实现真空环境下铁、铝等金属加热或熔融,并获得相应环境下的LIBS测量光谱。利用该系统进行真空和熔融条件下标准钢样品的LIBS实验,得到了固态钢样品LIBS光谱在不同真空度下的光谱对比,以及真空环境熔融态和固态钢样品光谱对比。通过对测得的LIBS光谱进行数据处理和理论分析,所得初步实验结果与现有研究结论相符合,表明该系统工作状况良好,可满足真空环境下的熔融金属成分分析研究的基本需求。     

金纳米与磁场作用下LIBS检测灵敏度改善研究

针对激光诱导击穿光谱技术（LIBS）中等离子体的发射光谱增强问题,提出一种磁场增强LIBS与纳米颗粒增强LIBS（NELIBS）相结合的方法。采用热蒸发法在样品表面沉积一层直径20 nm的金纳米颗粒。利用波长为1 064 nm,最大能量为200 mJ的Nd∶YAG脉冲激光器在室温,一个标准大气压下对纯铜和黄铜进行诱导击穿。调整激光能量为30~110 mJ,分别使用传统LIBS、磁场增强LIBS、NELIBS以及两种方法结合对纯铜进行激光诱导击穿,得到特征谱线(Cu Ⅰ 521.8 nm)的强度增强因子和信噪比,并对其增强机理进行分析。在相同环境下使用四种方式对黄铜和纯铜进行诱导击穿以探测样品中的微量元素。当在样品表面沉淀金纳米颗粒或者将沉淀有金纳米颗粒的样品放在磁场中进行诱导击穿时,发现纯铜样品的光谱中存在Mg元素的特征谱线Mg Ⅱ 279.569 nm,黄铜样品的光谱中存在Si元素的特征谱线 Si Ⅰ 251.611 nm。实验结果表明：单独施加磁场约束或增加纳米金颗粒均可以有效增强等离子体光谱强度,但增强效果弱于两种方法结合,磁场约束对光谱的增强效果弱于NELIBS的增强效果。当结合NELIBS与磁场约束LIBS时,谱线增强因子最高可达14.3(Cu Ⅰ 521.8 nm),相比于磁场增强LIBS和NELIBS,最大增强因子分别提高了28%和59%。四种情况中当激光脉冲能量逐渐增大时,等离子体向外膨胀的强度增大,磁场产生的洛伦兹力束缚等离子的能力相对减弱,同时纳米金颗粒对等离子体发射光谱的增强作用被削弱,谱线强度降低,等离子体的增强因子逐渐减小后趋于稳定。通过NELIBS与磁场约束LIBS结合方式,不仅可以有效提高等离子体的发射谱线强度,改善光谱信号信噪比,而且传统LIBS方法中由于谱线强度低、背景噪声大而无法探测的微量元素可以被探测到,LIBS技术对微量元素的探测能力得到显著提高,微量元素的探测下限变得更低。NELIBS与磁场约束LIBS结合的方法具有更高的灵敏度和准确度,为激光诱导击穿光谱技术的谱线增强方法提供了新的思路,在该领域具有广阔的应用前景。     

Spectroscopic analysis using a hybrid LIBS-Raman system

A novel setup, combining two spectroscopic techniques, laser induced breakdown spectroscopy (LIBS) and Raman spectroscopy in a hybrid unit, is described. The work presented herein is part of a broader project that aims to demonstrate the applicability of the hybrid LIBS-Raman unit as an analytical tool for the investigation of samples and objects of cultural heritage. The system utilizes a nanosecond pulsed Nd:YAG laser (532 nm) for both LIBS and Raman analysis. In the Raman mode, a low intensity beam from the laser probes the sample surface and the scattering signal is collected into a grating spectrograph coupled to an intensified charge-coupled device (ICCD) detector, which records the Raman spectrum. In the LIBS mode a single high intensity pulse from the laser irradiates the sample surface and the time- and spectrally-resolved emission from the resulting laser ablation plume yields the LIBS spectrum. The use of a non-gated CCD detector was found to produce similar quality data (in terms of S/N ratio and fluorescence background) in the Raman mode, while in the LIBS mode spectral features were clearly broader but did not prevent identification of prominent atomic emission lines. Several model pigment samples were examined and the data obtained show the ability of the hybrid unit to record both Raman and LIBS spectra from the same point on the sample, a clear advantage over the use of different analytical setups. PACS 39.30.+w; 82.80.Dx; 82.80.Gk; 52.38.Mf     

缅甸翡翠中铁元素的激光诱导击穿光谱定量检测

采用激光诱导击穿光谱(LIBS)技术定量分析缅甸翡翠中Fe元素的浓度。选择Fe元素的275.57 nm光谱线作为定量分析谱线,选取Si元素的288.17 nm光谱线作为内标谱线,选取12个缅甸翡翠样品作为研究对象,以其中9个样品绘制了传统定标法和内定标法的Fe元素定标曲线,并将定标曲线用于3个检验样品的Fe含量的实际预测。实验结果表明,采用传统定标方法时,定标样品光谱强度的相对标准偏差(RSD)在1.4%～8.3%之间,所建立的Fe元素浓度含量定标曲线的拟合相关系数R2为0.979,使用该方法建立的定标曲线对3个检验样品中Fe元素含量进行测定,最大相对误差为10.6%;而采用内定标法时,定标样品光谱强度的比值(I_Fe/I_Si)的相对标准偏差(RSD)在0.9%～5.7%之间,Fe的拟合相关系数R2达到0.989,样品中Fe元素的测定相对误差均可降低到7%以下。结果证明,利用内定标法定量分析翡翠中Fe的含量比传统定标法相对误差更小,采用LIBS技术结合内定标法更适于缅甸翡翠样品中Fe元素定量分析。     

Measurements of plasma temperature and electron density in laser-induced copper plasma by time-resolved spectroscopy of neutral atom and ion emissions

Plasma produced by a 355 nm pulsed Nd:YAG laser with a pulse duration of 6 ns focussed onto a copper solid sample in air at atmospheric pressure is studied spectroscopically. The temperature and electron density characterizing the plasma are measured by time-resolved spectroscopy of neutral atom and ion line emissions in the time window of 300–2000 ns. An echelle spectrograph coupled with a gated intensified charge coupled detector is used to record the plasma emissions. The temperature is obtained using the Boltzmann plot method and the electron density is determined using the Saha-Boltzmann equation method. Both parameters are studied as a function of delay time with respect to the onset of the laser pulse. The results are discussed. The time window where the plasma is optically thin and is also in local thermodynamic equilibrium (LTE), necessary for the laser-induced breakdown spectroscopy (LIBS) analysis of samples, is deduced from the temporal evolution of the intensity ratio of two Cu I lines. It is found to be 700–1000 ns.     

基于多谱线内标法的不规则铜合金样品中 Pb元素成分检测研究

原位分析和在线检测是激光诱导击穿光谱(LIBS)技术的一大优势,但是,在野外环境中,人们无法对样品进行统一预处理,面对各种形态的待测样品如何保证LIBS的检测精度是函待解决的一大难题。提出一种多谱线内定标的方法来解决上述问题,即通过求解多条分析谱线的强度和与内标元素谱线的强度比值来建立定标曲线,进而降低光谱信号波动带来的误差,提高线性相关性和检测精度。实验中以铅黄铜合金样品为例,采用LIBS对厚度不一（最大变化值为±2 mm）的铅黄铜样品中的Pb元素进行了定量检测研究,并分别采用传统定标法和多谱线内定标法对这种不规则样品进行校正和建立定标曲线。实验发现,对于不规则样品,传统定标法的检测精度大大降低,定标曲线没有明显的线性关系。当采用单条谱线的内定标方法时,定标曲线线性相关度大大提高,校正决定系数达到0.724 89。而采用多条谱线内标方法（考虑多条分析谱线的相对强度总和）计算发现,当选取5条Pb谱线（Pb 261.42 nm,Pb 280.20 nm,Pb 368.35 nm,Pb 405.78 nm和Pb 520.14 nm）进行计算时,定标曲线线性拟合度达到0.984 6,由此可见该方法消除了样品不规则所带来的光谱强度波动误差,显著提高了测量精度。虽然继续增加分析谱线数目可以进一步提升线性相关度,但是也会增加计算的复杂度,所以选择合适的分析谱线是十分重要的。此外,通过多谱线内标法也能一定程度上消除基体效应和光谱干扰等影响,是一种简单有效且具备普适性的数据处理方法。当然,该方法也存在一定的局限性（如样品成分分布极不均匀、样品表面极不规则致使激光能量低于击穿阈值等）,不过通过调整和优化检测装置方案（例如增大激光能量、增大聚焦光斑、采用长焦距聚焦透镜等）可以更好的发挥该方法的优势。该研究内容可以为LIBS原位检测和在线检测的应用提供一种新思路。     

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.     

Biomedical and environmental applicationsof laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) is an emerging analytical technique with numerous advantages such as rapidity, multi-elemental analysis, minimal sample preparation, minimal destruction, low cost and versatility of being applied to a wide range of materials. In this paper, we report the preliminary observations we obtained using LIBS for clinical and environmental samples. Elemental analysis has been done qualitatively in human teeth samples which show encouraging results. It has also been demonstrated in this paper that LIBS can be very well utilized in field applications such as plastic waste sorting and recycling.     

Influence of Laser Wavelength on Laser-induced Breakdown Spectroscopy Applied to Semi-Quantitative Analysis of Trace-Elements in a Plant Sample

Laser-induced breakdown spectroscopy （LIBS） as a powerful analytical technique is applied to analyze trace- elements in fresh plant samples. We investigate the LIBS spectra of fresh holly leaves and observe more than 430 lines emitted from 25 elements and molecules in the region 230-438nm. The influence of laser wavelength on LIBS applied to semi-quantitative analysis of trace-element contents in plant samples is studied. The results show that the UV laser has lower relative standard deviations and better repeatability for semi-quantitative analysis of trace-element contents in plant samples. This work may be helpful for improving the quantitative analysis power of LIBS applied to plant samples.     

Artificial neural networks applied to the classification of hair samples according to pigment and sex using non-invasive analytical techniques

In this study, we investigated the possibility of using an artificial neural network (ANN) to classify human hair samples according to pigment (original or bleached hair) and sex (female or male) from numerical data obtained by wavelength dispersive X-ray fluorescence (WDXRF) and by laser-induced breakdown spectroscopy (LIBS). The results were promising, showing that the developed ANNs are able to classify the pigment and donor sex of hair samples with 100% and 89.5% accuracy, respectively, in the test set using WDXRF data. For the LIBS data in the test set, 100% of the pigment classifications were correct, and 78.9% of the donor sex classifications were correct.