Quantitative Analysis of Cr in Milk Powder by Laser Induced Breakdown Spectroscopy( LIBS)

At present, heavy metal pollution in food occurs frequently, which requires a novel method for rapid detection. Laser induced breakdown spectroscopy （LIBS） is a new technique for rapid and environmental friendly detection, but it lacks high sensitivity and stability which restrict its development. In this study, Cr-polluted infant milk powder was used as experimental material to explore the feasibility of the application of LIBS technique in food safety detection. Aiming at improving the precision and accuracy of Cr detection by LIBS technique, LIBS spectra of samples were collected by a spectrometer with an intensified charge-cou- pled device （ICCD） using three gratings with different resolutions to comprehensively compare and analyze the stability, sensitivity and quantitative analysis accura- cy of LIBS detection. The results showed that average relative standard deviation （RSD） of LIBS spectral intensity was below 10%, indicating good stability. LIBS signals were collected by three gratings for quantitative analysis, and the results demonstrated that the linear correlation coefficient R2 of fitting curves was 0. 248 87, 0.903 12 and 0.992 81, respectively; the relative errors between actual and predicted concentrations were 38.23%, 8.84% and 7.43%, respectively, indicating that gratings with higher resolutions could lead to higher linear correlation coefficient and better detection accuracy. According to the results, high-resolu- tion spectrometer could significantly improve the accuracy of LIBS detection of Cr concentration in milk powder, suggesting that it is feasible to detect heavy metals in food by LIBS technique with the improvement of core device performance.

Self-Absorption Effects on Electron Temperature-Measurements Utilizing Laser Induced Breakdown Spectroscopy (LIBS)-Techniques

In the present work, we have studied the temporal evolution of aluminum alloy plasma produced by the fundamental (1064 nm) of a Q-switched Nd:YAG laser by placing the target material in air at atmospheric pressure. The four Al I-neutral lines at 308.21, 309.27, 394.40 and 369.15 nm as well as Al II-ionic lines at 281.61, 385.64 and 466.30 nm are used for the determination of the electron temperature Te using Saha-Boltzmann plot method. The neutral aluminum lines were found to suffer from optical thickness which manifested itself on the form of scattered points around the Saha-Boltzmann line. The isolated optically thin hydrogen Hα-line at 656.27 nm appeared in the spectra under the same experimental conditions was used to correct the Al I-lines which contained some optical thickness. The measurements were repeated at different delay times ranging from 1 to 5 μs. The comparison between the deduced electron temperatures from aluminum neutral lines before correction against the effect self-absorption to that after correction revealed a precise value in temperature. The results sure that, in case of the presence of self-absorption effect the temperature varies from (1.4067 - 1.2548 eV) as the delay time is varied from 0 to 5 μs. Whereas, in the case of repairing against the effect, it varies from (1.2826 - 0.8961 eV) for the same delay time variation.

Investigation of Laser Induced Breakdown Spectroscopy(LIBS)for the Differentiation of Nerve and Gland Tissue-A Possible Application for a Laser Surgery Feedback Control Mechanism

Laser surgery provides clean,fast and accurate modeling of tissue.However,the inability to determine what kind of tissue is being ablated at the bottom of the cut may lead to the iatrogenic damage of structures that were meant to be preserved.In this context,nerve preservation is one of the key challenges in any surgical procedure.One example is the treatment of parotid gland pathologies,where the facial nerve（N.VII） and its main branches run through and fan out inside the glands parenchyma.A feedback system that automatically stops the ablation to prevent nerve-tissue damage could greatly increase the applicability and safety of surgical laser systems.In the present study,Laser Induced Breakdown Spectroscopy（LIBS） is used to differentiate between nerve and gland tissue of an ex-vivo pig animal model.The LIBS results obtained in this preliminary experiment suggest that the measured spectra,containing atomic and molecular emissions,can be used to differentiate between the two tissue types.The measurements and differentiation were performed in open air and under normal stray light conditions.

Laser-Induced Breakdown Spectroscopy (LIBS) Applied in the Differentiation of <i>Arabica</i>and <i>Robusta</i>Coffee

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.

Rock and Soil Classification Using PLS-DA and SVM Combined with a Laser-Induced Breakdown Spectroscopy Library

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.

Quantitative analysis of impurities in aluminum alloys by laser-induced breakdown spectroscopy without internal calibration

To develop a fast and sensitive alloy elemental analysis method,a laser-induced breakdown spectroscopy(LIBS)system was established and used to carry out quantitative analysis of impurities in aluminum alloys in air at atmospheric pressure.A digital storage oscilloscope was used as signal recording instrument,instead of traditional gate integrator or Boxcar averager,to reduce the cost of the whole system.Linear calibration curves in the concentration range of 4×10-510-2 are built for Mg,Cr,Mn,Cu and Zn using absolute line intensity without internal calibrations.Limits of detection for these five elements in aluminum alloy are determined to be(2-90)×10-6.It is demonstrated that LIBS can provide quantitative trace elemental analysis in alloys even without internal calibration.This approach is easy to use in metallurgy industries and relative research fields.

Comparison of Calibration Curve Method and Partial Least Square Method in the Laser Induced Breakdown Spectroscopy Quantitative Analysis

The Laser Induced Breakdown Spectroscopy (LIBS) is a fast, non-contact, no sample preparation analytic technology;it is very suitable for on-line analysis of alloy composition. In the copper smelting industry, analysis and control of the copper alloy concentration affect the quality of the products greatly, so LIBS is an efficient quantitative analysis tech- nology in the copper smelting industry. But for the lead brass, the components of Pb, Al and Ni elements are very low and the atomic emission lines are easily submerged under copper complex characteristic spectral lines because of the matrix effects. So it is difficult to get the online quantitative result of these important elements. In this paper, both the partial least squares (PLS) method and the calibration curve (CC) method are used to quantitatively analyze the laser induced breakdown spectroscopy data which is obtained from the standard lead brass alloy samples. Both the major and trace elements were quantitatively analyzed. By comparing the two results of the different calibration method, some useful results were obtained: both for major and trace elements, the PLS method was better than the CC method in quantitative analysis. And the regression coefficient of PLS method is compared with the original spectral data with background interference to explain the advantage of the PLS method in the LIBS quantitative analysis. Results proved that the PLS method used in laser induced breakdown spectroscopy was suitable for simultaneous quantitative analysis of different content elements in copper smelting industry.

LIBS结合图像筛选方法提高钢铁中Cu、Cr、Mn元素检测稳定性研究

优质特种钢材和低端粗钢之间的性能差异主要受其构成元素种类及其成分含量的影响,因此,如何快速准确地对物质成分进行定性及定量分析对钢铁产品的质量评估至关重要。针对传统方法难以实现对钢铁合金成分的快速准确检测的难题,采用激光诱导击穿光谱(LIBS)结合等离子体图像信息的方法,通过快速地对不同元素的特征光谱强度与激发生成的等离子体图像进行采集,分析两者之间的相关性,并通过提取的图像特征信息的异常值剔除了部分无效光谱数据,进而实现了对钢铁成分的高精度分析。通过分析延迟时间和激光能量等不同实验条件对元素特征光谱强度及其对应等离子体图像的影响规律,不仅证明了等离子体图像与光谱之间存在相关性,还利用等离子体图像特征信息的局部最优值确定了最优延迟时间、激光能量分别为1000 ns与50 mJ,并根据图像特征的平均阈值来筛选无效光谱数据。结果表明,图像筛选优化数据后,各元素谱线校准模型的决定系数(R^(2))分别从原始数据的0.978、0.986、0.957、0.935提升至0.995、0.997、0.968、0.957,且其定标曲线对未知样品元素的预测浓度相对标准偏差(RSD)下降为原始数据预测浓度RSD的50%左右。由此可知采用LIBS结合图像筛选方法可以减少定量分析的误差,提高预测结果精确度。

激光诱导击穿光谱(LIBS)分析虚拟仿真实验

虚拟仿真实验作为大型仪器分析实验教学模式的新兴趋势,有效地将虚拟仿真技术与实物仪器教学相结合,最大限度地提升了学生对于大型仪器分析的综合应用能力。本文以激光诱导击穿光谱(LIBS)虚拟仿真实验系统为例,完整地模拟了LIBS系统的样品处理、光谱采集、定性分析和定量分析等实际实验场景,通过虚实结合实验教学模式对实验过程进行实时跟踪与综合考评。该实验有助于提高学生自主探究能力和创新意识,培养具有独立思考与实践能力的拔尖人才。

基于高频激光除漆的LIBS监测平台设计与应用研究

基于激光诱导击穿光谱(LIBS)技术的飞机漆层清洗监测,需要对峰值功率密度范围进行限定,以确保等离子体激发和漆层清洗的稳定性。然而,对于广泛使用的高频(kHz级)脉冲激光除漆技术,其峰值功率密度相对偏低,除漆过程中等离子体激发受到限制;且高频激光烧蚀材料产生的强连续背景光谱干扰了等离子体光谱采集。论文依据蒙皮功能漆层可控清洗需求,基于LabVIEW嵌入式开发系统的控制软件编写及激光清洗、光谱采集、控制与显示模块的集成,设计了一款适用于高频激光除漆的LIBS监测平台。选取2024-T3铝合金双漆层试样作为研究对象,采集波长介于360~700nm范围内的漆层/基体体系光谱(面漆层:Tc;底漆层:Pr;基体:As)。采用平滑滤波,基线校正和归一化对原始光谱进行预处理,并选取12条特征谱线进行主成分分析(PCA),其降维数据作为线性判别分析(LDA)的输入变量,以此建立PCA-LDA判别模型。最后将所建模型导入LIBS监测平台,通过试验验证了高频激光除漆LIBS监测平台的分类准确性。结果表明:仅以累积方差解释率大于85%作为主成分选取原则,不能满足除漆过程LDA的分类需要;通过优化LDA的主成分个数,最终选取前9个主成分作为LDA的输入,显著提升了LIBS平台的检测准确率,此时基于LIBS光谱的PCA-LDA模型分类准确率达92.5%。由此可见,设计的高频激光除漆LIBS监测平台能够完成漆层/基体体系不同结构层的材料识别,从而实现了高频脉冲激光可控除漆的有效监测。

基于LIBS数据流盘的飞机蒙皮激光除漆在线监测判据研究

等离子体产生及演化过程易受基体效应、环境噪声、脉冲能量抖动等影响,导致光谱数据具有不稳定性,从而难以保证以单条谱线为依据建立的监测判据的有效性。以连续多幅LIBS光谱为对象,并结合统计学方法建立的监测判据,可有效提升基于LIBS技术的除漆效果监测精度。论文基于搭建的高频纳秒红外脉冲激光除漆LIBS在线监测平台,实时采集了除漆过程的连续多幅LIBS光谱。光谱数据经基线矫正、归一化预处理后,依据面漆、底漆、铝合金基体光谱特征峰差异,并结合材料成分信息,选定BaⅠ(712.55 nm)、CrⅠ(357.48 nm)、CrⅠ(425.43 nm)、TiⅠ(427.45 nm)、CuⅡ(309.76 nm)、CuⅠ(484.22 nm)6条谱线作为特征谱线并监测除漆效果。研究不同除漆效果中6条特征谱线强度变化规律,建立不同除漆效果与所选特征谱线强度变化区间的映射关系。提取每幅谱线的上述6条特征谱线强度作为一组数据单元、将连续10幅谱线的数据单元作为一组数据集,除漆过程中随时间变化的每10组迭代数据集称为数据流盘。对数据流盘中的数据单元、数据集进行分析,结合置信区间,实时判定除漆区域除漆效果,获得基于数据流盘的监测判据。结果表明:该判据可有效监测仍在面漆、面漆完全去除、仍在底漆、底漆完全去除、基体损伤5类除漆效果。依据SRM手册对漆层去除效果的要求,选择面漆完全去除、基体损伤两类除漆效果展示了验证过程,三维微观形貌分析结果与LIBS数据流盘监测判据所得除漆效果结论一致。其中,面漆去除后三维微观形貌分析表明,面漆完全去除精度达1.2μm,有效验证了基于LIBS数据流盘监测判据的适用性及稳定性。

Heavy Metal Detection in Soils by Laser Induced Breakdown Spectroscopy Using Hemispherical Spatial Confinement

Spatial confinement has great potential for Laser Induced Breakdown Spectroscopy （LIBS） instruments after it has been proven that it has the ability to enhance the LIBS signal strength and repeatability. In order to achieve in-situ measurement of heavy metals in farmland soils by LIBS, a hemispherical spatial confinement device is designed and used to collect plasma spectra, in which the optical fibers directly collect the breakdown spectroscopy of the soil samples. This device could effectively increase the stability of the spectrum intensity of soil. It also has other advantages, such as ease of installation, and its small and compact size. The relationship between the spectrum intensity and the laser pulse energy is studied for this device. It is found that the breakdown threshold is 160 cm-2, and when the laser fluence increases to 250 J/cm2, the spectrum intensity reaches its maximum. Four different kinds of laser pulse energy were set up and in each case the limits of detection of Cd, Cu, Ni, Pb and Zn were calculated. The results show that when the laser pulse fluence was 2.12 GW/cm2, we obtained the smallest limits of detection of these heavy metals, which are all under 10 mg/kg. This device can satisfy the needs of heavy metal in-situ detection, and in the next step it will be integrated into a portable LIBS instrument.

Improvement of quantitative analysis of molybdenum element using PLS-based approaches for laser-induced breakdown spectroscopy in various pressure environments

An experimental setup has been designed and realized in order to optimize the characteristics of laser-induced breakdown spectroscopy system working in various pressure environments. An approach combined the normalization methods with the partial least squares(PLS) method are developed for quantitative analysis of molybdenum(Mo) element in the multi-component alloy,which is the first wall material in the Experimental Advanced Superconducting Tokamak. In this study, the different spectral normalization methods(total spectral area normalization,background normalization, and reference line normalization) are investigated for reducing the uncertainty and improving the accuracy of spectral measurement. The results indicates that the approach of PLS based on inter-element interference is significantly better than the conventional PLS methods as well as the univariate linear methods in the various pressure for molybdenum element analysis.

Quantitative analysis of C, Si, Mn, Ni, Cr and Cu in low-alloy steel under ambient conditions via laser-induced breakdown spectroscopy

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.

Spectral Enhancement of Laser-Induced Breakdown Spectroscopy in External Magnetic Field

In this paper the spectral enhancement of laser-induced breakdown spectroscopy （LIBS） for copper plasma in the presence of a magnetic field is investigated and the temporal- and spatial-resolved plasma emission spectra are analyzed. Experimental results show that the copper plasma atomic and ion spectra have been enhanced in the presence of the external magnetic field. In addition, the Cu I 521.82 nm spectral intensity evolution with delay time appears to have a double peak around the delay time of 2 μs, but that of Cu II 507.57 nm has a sharp decrease because of the electron-atom three body recombination process. The plasma temperature with magnetic confinement is lower than that of the case in the absence of magnetic fields. Finally, the spectral enhancement mechanisms of laser induced breakdown spectroscopy with magnetic confinement are analyzed.

A rapid classification method of aluminum alloy based on laser-induced breakdown spectroscopy and random forest algorithm

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.

Simultaneous Measurements of Coal Ash Composition by Laser-induced Breakdown Spectroscopy in Different Optical Collection

针对燃煤组分分布不均匀的特性，研究不同收光模式对激光诱导击穿光谱技术同步测量灰成分的影响。选用具有不同灰成分含量梯度的燃煤样品作为检测对象，对比分析同向收光和侧向收光下灰成分组成元素谱线信号探测的强度和稳定性及SiO2、Al2O3、Fe2O3、CaO、MgO和TiO2含量定量分析的精确度。研究结果表明，相同实验条件下同向收光模式的光谱信号稳定性和定量分析精确度更好，检验样品中各灰成分的预测值和参考值之间的拟合度均在0．986以上。而侧向收光模式下探测到的光谱信号强度更强，光谱探测下限可以达到190nm。

电化学富集-激光诱导击穿光谱(LIBS)法测定水中铀元素

为改善激光诱导击穿光谱技术(Laser-Induced Breakdown Spectroscopy,LIBS)检测液体样品时遇到的液体飞溅、等离子体猝灭和稳定性差的问题,结合电化学富集方法,以KCl为电解质,石墨棒为阴极,开展了水中铀(U)元素的LIBS检测研究。选择UⅡ367.007 nm、UⅡ409.013 nm作为分析对象进行定量分析,着重研究了富集电压、KCl质量浓度、激光脉冲能量、激发方式等对铀元素特征谱线强度的影响规律,并通过扫描电子显微镜(SEM)及能谱分析(EDS)对石墨棒表面吸附元素的空间分布进行了分析。结果表明,最佳富集电压为1.6 V,适当的电解质KCl质量浓度可以提高铀元素的富集效率和富集均匀性,提高激光脉冲能量与采用光电双脉冲激发方式能增强铀元素特征谱线的强度并提高信噪比。在光电双脉冲激发下,对水中铀元素进行了定量分析,获得UⅡ367.007 nm、UⅡ409.013 nm的检测下限分别为25.89和15.00μg/L,相关系数均大于0.98。方法可为水体中放射性核素含量调查、生活饮用水铀污染现状以及核工业含铀废水监测等场景提供技术支持。

Laser-induced breakdown spectroscopy applied to the characterization of rock by support vector machine combined with principal component analysis

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.

Laser Induced Breakdown Spectroscopy for Comparative Quantitative Analysis of Betel Leaves from Pakistan

Laser induced breakdown Spectroscopy(LIBS)was applied for the elemental analysis and exposure of the heavy metals in betel leaves in air.Pulsed Nd∶YAG(1064 nm)in conjunction with a suitable detector(LIBS 2000+,Ocean Optics,Inc)having the optical resolution of 0.06 nm was used to record the emission spectra from 220 to 720 nm.Elements like Al,Ba,Ca,Cr,Cu,P,Fe,K,Mg,Mn,Na,P,S,Sr,and Zn were found to present in the samples.The relative abundances of the observed elements were calculated through standard calibration curve method,integrated intensity ratio method,and weight percentage LIBS approach.LIBS findings were validated by comparing its results with the results obtained using a typical analytical technique of Inductively Coupled plasma-optical emission spectroscopy(ICP-OES).Limit of detection(LOD)of the LIBS system was also estimated for heavy metals.The experience gain through this work implies that LIBS could be highly applicable for testing the quality and purity of food products.