激光诱导击穿光谱在金属材料在线分析方面的应用进展

激光诱导击穿光谱(LIBS)由于具有无需样品制备、分析速度快、可远距离在线遥测以及可进行元素的二维表面分布和深度分析等特点,引起光谱化学分析领域研究者的广泛关注。在冶金过程工艺控制领域,金属材料的在线分析以及元素多维信息的获取,对于实时监控金属材料的生产工艺及准确实现金属材料的快速分类方面具有重要的意义。与传统的分析方法相比较,LIBS技术因其众多优势已成为金属材料实时在线分析的最佳手段之一,而且已有多种商品化的仪器推出。论文首先对LIBS在线仪器装置进行介绍,然后对近些年LIBS在熔融金属在线分析、连铸钢坯鉴别、炉渣在线分析、金属材料分类识别、金属材料镀层分析等方面的发展现状及挑战进行论述,最后对LIBS在线分析进行展望。     

Electric-field induced fluctuations in laser generated plasma plume

The effect of an external electric field on laser-generated plasma has been studied. It is observed that the laser-generated plasma can be used for the ignition of a spark in the presence of a low voltage external electric field. An eight-fold emission intensity enhancement in Cu Ⅰ spectral lines are measured as compared to the signal intensity in the absence of an external electric field.The plasma parameters remain the same initially, up to a few microseconds after the generation of plasma, and this feature makes it more interesting for the quantitative analysis of any sample using laser induced breakdown spectroscopy(LIBS). In the presence of an external electric field,fluctuations(contraction and expansion) in the laser-generated plasma are observed which increase the plasma decay time and consequently result in enhanced signal intensity.     

一种两阶段变量选择的LIBS定量分析方法

使用机器学习方法结合激光诱导击穿光谱(Laser Induced Breakdown Spectroscopy,LIBS)进行定量分析,变量选择的结果直接影响最终的定标模型.现有的变量选择方法多存在需要先验知识、计算量庞大等问题,因此提出一种两阶段变量选择方法.第一阶段为排序阶段,以皮尔逊相关系数r为排序准则快速排除与...     

激光诱导击穿光谱技术研究的新进展

激光诱导击穿光谱技术（LIBS）是一种基于原子发射光谱学的物质组分分析技术。随着激光技术和光学检测技术的发展,激光诱导击穿光谱技术已经成为光谱学领域的研究热点。尤其是近几年,LIBS技术发展迅速,涌现出多种LIBS的激发和探测新技术。在光谱激发方面,出现了如飞秒激光及飞秒激光大气中长距离成丝诱导击穿光谱技术,双脉冲激光诱导击穿光谱技术等。在光谱探测方面,出现了时间分辨激光诱导击穿光谱技术,偏振分辨激光诱导击穿光谱技术等。本文将对这几种LIBS中所出现的新技术进行介绍并给出LIBS技术的发展趋势。     

激光诱导击穿光谱在冶金在线分析中的应用研究进展

化学成分在线直接测量是冶金分析长久以来的追求,也被誉为冶金分析面临的三大难题之一.激光诱导击穿光谱技术因其在无需复杂样品制备、直接快速、非接触等方面展现的独有技术优势,备受研究上的关注.文章综述了激光诱导击穿光谱在选矿、熔融金属在线检测方面的研究进展,总结了当前存在的主要问题,并对未来发展进行了展望.     

基于DP-LIBS铁合金中碳元素特征谱线的研究

采用双脉冲和单脉冲激光,对空气中标准铁合金样品中碳元素的激光诱导实验,研究两种方式下形成的光谱。双脉冲激光诱导击穿光谱采用两束激光,在第一束激光脉冲的基础上加入第二束高压激光脉冲,对等离子体进行二次激发。通过对比研究发现:双脉冲激发技术延长了原子特征辐射的有效时间,提高了获取信号的信噪比,增强了发射光谱的信号强度,提高了信号的稳定性。此外,通过分析影响双脉冲信号增强程度的因素,研究了脉冲宽度和延迟时间以及激发能级对光谱增强程度的影响。     

无监督数据挖掘辅助激光诱导击穿光谱用于铜冶炼光谱结构解析

在有色冶炼领域,元素成分检测是保证冶炼质量的重要一环。目前国内有色冶炼企业多采用X射线荧光光谱法进行检测,该方法需要样品制备,造成冶炼状态无法实时反馈,严重影响冶炼过程优化。研究了无监督数据挖掘算法辅助激光诱导击穿光谱技术用于铜冶炼光谱结构解析。实验中,首先选择4种铜冶炼物料作为实验样品,然后利用激光诱导击穿光谱技术(LIBS)激发样品获得18750个光谱数据,通过盲源分离技术对所有光谱进行分析,最终提取得到3个特征光谱。进一步研究发现,3个特征光谱与Cu、Fe、Ca元素光谱有一一对应关系。在此基础上,提出了LIBS光谱的定量化评价指标,量化结果表明分解模型对18750个光谱都能达到很高的评分,说明铜冶炼光谱能够良好地被3个特征光谱重构,即铜冶炼光谱存在显著的光谱结构。以上结论在实际应用中具有重要研究价值,可用于光谱快速评价、异常光谱剔除、光谱信号提纯、元素谱线选取、样品定性/半定量分析等,为LIBS技术应用于在线铜冶炼成分分析奠定基础。     

Detection of K in soil using time-resolved laser-induced breakdown spectroscopy based on convolutional neural networks

One of the technical bottlenecks of traditional laser-induced breakdown spectroscopy (LIBS) is the difficulty in quantitative detection caused by the matrix effect. To troubleshoot this problem, this paper investigated a combination of time-resolved LIBS and convolutional neural networks (CNNs) to improve K determination in soil. The time-resolved LIBS contained the information of both wavelength and time dimension. The spectra of wavelength dimension showed the characteristic emission lines of elements, and those of time dimension presented the plasma decay trend. The one-dimensional data of LIBS intensity from the emission line at 766.49 nm were extracted and correlated with the K concentration, showing a poor correlation of R²_c=0.0967, which is caused by the matrix effect of heterogeneous soil. For the wavelength dimension, the two-dimensional data of traditional integrated LIBS were extracted and analyzed by an artificial neural network (ANN), showing R²_v=0.6318 and the root mean square error of validation (RMSEV)=0.6234. For the time dimension, the two-dimensional data of time-decay LIBS were extracted and analyzed by ANN, showing R²_v=0.7366 and RMSEV=0.7855. These higher determination coefficients reveal that both the non-K emission lines of wavelength dimension and the spectral decay of time dimension could assist in quantitative detection of K. However, due to limited calibration samples, the two-dimensional models presented over-fitting. The three-dimensional data of time-resolved LIBS were analyzed by CNNs, which extracted and integrated the information of both the wavelength and time dimension, showing the R²_v=0.9968 and RMSEV=0.0785. CNN analysis of time-resolved LIBS is capable of improving the determination of K in soil.     

磁场环境下铝电解熔融铝液成分激光诱导击穿光谱原位测量分析

铝电解车间具有高温、强磁、多粉尘等环境特点,当前生产过程中熔融原铝的成分检测主要是人工取样然后离线分析,化验过程及结果具有较大的滞后性,故将激光诱导击穿光谱(LIBS)技术应用于铝电解车间铝液成分原位、实时测量具有重要意义。实验采用Nd:YAG脉冲激光器,多通道光纤光谱仪和电感耦合器件(CCD)探测器组成的激光诱导击穿光谱测量系统对电流为400kA电解槽中熔融铝液的主要成分铁、硅进行了探测,对原铝中部分元素的特征谱线进行了归属分析。考察了激光能量在磁场环境下的衰减变化及谱线梯度变迁规律,结果表明,距离电解槽边缘约2m处激光能量衰减达最大。分析了磁场对测试系统的影响,并建立了定标曲线,铁和硅两种元素按照内标法建立的定标曲线拟合度分别为93.50%和97.10%,采用该模型进行了测试实验,并用国标GB/T 7999—2015中光电直读发射光谱(OES)测试的相关指标验证测试结果的重复性与允许差。实验证明,LIBS技术在电解铝行业在线检测方面具有较好的应用前景,但是测试的稳定性与重复性也是面临的一个重要问题。     

Effect of distances between lens and sample surface on laser-induced breakdown spectroscopy with spatial confinement

Spatial confinement can significantly enhance the spectral intensity of laser-induced plasma in air.It is attributed to the compression of plasma plume by the reflected shockwave.In addition,optical emission spectroscopy of laser-induced plasma can also be affected by the distance between lens and sample surface.In order to obtain the optimized spectral intensity,the distance must be considered.In this work,spatially confined laser-induced silicon plasma by using a Nd:YAG nanosecond laser at different distances between lens and sample surface was investigated.The laser energies were 12 mJ,16 mJ,20 mJ,and 24 mJ.All experiments were carried out in an atmospheric environment.The results indicated that the intensity of Si (I) 390.55 nm line firstly rose and then dropped with the increase of lens-to-sample distance.Moreover,the spectral peak intensity with spatial confinement was higher than that without spatial confinement.The enhancement ratio was approximately 2 when laser energy was 24 mJ.