激光诱导击穿光谱技术及应用研究进展

激光诱导击穿光谱（LIBS）技术是一种基于原子发射光谱学的元素定性、定量检测手段。本文介绍了LIBS技术的原理、应用方式、检测元素种类及检测极限;综述了该项技术在固体、液体、气体组分检测方面的技术发展,以及在环境检测、食品安全、生物医药、材料、军事、太空领域的应用进展。最后,提出了高功率、高稳定的激光光源和准确的定量分析方法是LIBS技术目前所面临的问题和挑战。     

八字门滑坡滑带土壤的激光击穿光谱探测

利用搭建的一套激光击穿光谱测量土壤样品的实验系统,对三峡坝区香溪河段八字门滑坡滑带土壤进行了探测研究。在同一纬度不同海拔高度选取了5个地点采取了土壤样品,对5个样品进行了实验测量,得到了这些土壤样品的光谱图,并对其中的Mg,Al,Si,K等元素进行了定性和定量分析。结果表明,这些元素随着海拔的降低,其含量也逐渐降低。     

土壤中砷元素的激光诱导击穿光谱测量分析

利用Nd:YAG脉冲激光器作为光源,在实验室自然大气环境下诱导产生国家标准土壤的激光等离子体,选取砷的228.8 nm特征谱线作为分析线,测量并分析了砷元素的激光诱导击穿光谱特性。在相同含量和积分时间条件下,调节延迟时间,获取了砷元素的时间演化特性。确定砷元素的最佳延迟时间为1 s,积分时间为2 s。测定不同含量下,砷的特征谱线强度,给出砷元素的定标曲线,并计算得到砷元素的检测限为45 mg/kg。     

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.     

基于激光诱导击穿光谱技术定量分析食用明胶中的铬元素

利用激光诱导击穿光谱技术对食用明胶样品中的铬元素进行定量分析.采用Nd:YAG脉冲激光器三倍频输出的355 nm激光诱导击穿食用明胶产生激光等离子体,测量等离子发射光谱.实验数据表明:使用内标法定量分析食用明胶样品中铬元素浓度分别为10—200 ppm(1 ppm=10-6)时,铬元素含量与分析谱线(CrI:245.43 nm)强度之间具有很好的线性关系.分析了光谱探测延迟时间对明胶中铬元素激光诱导击穿光谱的影响,利用信号强度与信噪比获得了优化的光谱探测延迟时间实验参数.     

土壤重金属铬元素的激光诱导击穿光谱定量分析研究

利用Nd ∶YAG脉冲激光器(波长:1064 nm)作为光源,在实验室自然大气环境下诱导产生土壤激光等离子体,通过等离子体原子发射光谱法定量分析了国家标准土壤样品中元素Cr的含量.实验上研究了在最佳实验条件下土壤中Cr的LIBS分析谱线,测定了Cr元素的定标曲线.实验结果表明,Cr元素浓度在(60—400)×10^-6范围内,元素含量与光谱线强度之间有较好的线性关系;元素Cr浓度分析测量的相对标准偏差(RSD)为7.89%,定量分析结果与标准值的相对偏差为5.3%,Cr元素的检测限为1 关键词： 土壤污染 定量分析 激光诱导击穿光谱 定标曲线     

溶液中金属元素的激光诱导击穿光谱

利用激光击穿光谱的方法对水溶液样品中的金属元素进行定性和定量分析。分别采用竖直喷流（口径0.5 mm）和静止液面两种样品采样模式,针对不同质量浓度的Cd,Fe,Al和Pb元素进行了检测分析并得到了其定标曲线(线性拟合相关度基本在0.99以上),初步确定了４种元素在喷流模式下的检测限为0.206 5(Cd),0.147 6(Fe),0.061 9(Al)和0.200 9(Pb) g/L;静止液面模式下的检测限为0.050 1(Cd),0.023 9(Fe),0.014 8(Al)和0.006 9(Pb) g/L。实验所得的结果为检测工业废水中金属元素的含量提供了依据。     

新型便携式激光诱导击穿光谱系统综述

本文主要综述了国内外便携式激光诱导击穿光谱(LIBS)系统的研究进展和应用情况。目前该系统主要针对金属元素进行检测,对非金属等轻元素的定量分析需要较大能量的激光激发,但受限于激光器和光谱仪等组件体积的影响,研发便携式、高精度LIBS系统有较高难度。本文针对全元素检测便携设备的研发,利用限域和高压放电脉冲得到了增强的LIBS信号,降低了激光能量,从物理机理上给出了便携式LIBS设备研发的新方向。     

水中镉含量的激光诱导击穿光谱高灵敏快速检测

为了对水中的痕量镉进行高灵敏快速检测,实验采用一种未受污染的薄木片作为基底来吸收水样品,将其晾干后再用激光诱导击穿光谱（LIBS）技术对其进行分析,克服了用LIBS技术直接分析水样品时灵敏度低和稳定性差等问题。实验中选择214.44 nm的镉离子线作为分析线以提高光谱检测的灵敏度,建立了用于定量分析的校正曲线,镉的检出限达到55 μg/L,重复测量的信号相对标准偏差小于5%,单次测量的时间短于5 min。     

用激光诱导击穿光谱测量铝合金的激光烧蚀阈值

采用正交几何配置的双波长双脉冲激光烧蚀-激光诱导击穿光谱技术准确测量了铝合金样品的激光烧蚀阈值。在烧蚀激光波长为532 nm、脉宽为12 ns并采用焦距为2 cm的非球面透镜强聚焦的条件下,得到铝合金的激光能量烧蚀阈值为48 J,等效的能量密度烧蚀阈值为9.8 J/cm2。该技术是一种新的激光烧蚀阈值的光谱测量手段,与传统的测量技术相比,具有高灵敏、准确、快捷和便利的特点,可以用于不同材料的激光烧蚀阈值的准确测量。     

用激光感生击穿光谱对大气进行定量分析

研究将激光感生击穿光谱技术用于元素定量分析的可行性。利用Nd∶YAG激光器发出的激光与一个大气压下的空气相互作用产生激光等离子体，等离子体的光经单色仪分光后转化为电信号进入计算机，存储了600～800nm的等离子体光谱数据。利用自由定标模型对等离子体进行了分析。在延迟时间8μs、采样门宽0.4μs时，利用二维波尔兹曼平面得到了大气等离子体处于局部热平衡时的温度（1.62×10K）。在假设空气全部由N和O组成的条件下由自由定标模型得到了空气中氧的含量（20.75%）和氮的含量（79.25%）。试验结果与实际吻合得很好。实验证实了用激光感生击穿光谱对大气进行定量分析是可行的，为大气污染监测研究和试验工作奠定了基础。     

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.     

The high dependence of polarization resolved laser-induced breakdown spectroscopy on experimental conditions

It is shown that the continuum emission produced by an Al alloy ablated by femtosecond laser pulses is much more polarized than the characteristic lines of elements. A Glan-Thomson polarizer is used in the laser-induced breakdown spectroscopy experiment to investigate the polarization effect. The use of the polarizer at its minimal transmission increases the signal-to-noise ratio. The effects of angle of detection, focal position, and pulse energy on the signal-to-noise ratio are also studied.     

水中镉含量的激光诱导击穿光谱高灵敏快速检测

 为了对水中的痕量镉进行高灵敏快速检测,实验采用一种未受污染的薄木片作为基底来吸收水样品,将其晾干后再用激光诱导击穿光谱（LIBS）技术对其进行分析,克服了用LIBS技术直接分析水样品时灵敏度低和稳定性差等问题。实验中选择214.44 nm的镉离子线作为分析线以提高光谱检测的灵敏度,建立了用于定量分析的校正曲线,镉的检出限达到55 μg/L,重复测量的信号相对标准偏差小于5%,单次测量的时间短于5 min。     

用激光诱导击穿光谱技术定量分析油漆中的有害重金属

很多轻工业产品需要用到油性油漆,其中的重金属元素的含量是否超标将会直接影响到产品质量及其安全性.因此发展轻工产品中重金属含量的快速检测技术,对促进国民经济的发展和保障消费者生命安全具有重要的意义.我们利用激光诱导击穿光谱技术实现了对油漆中有害重金属含量的快速定性和定量分析.通过观测激光等离子体中重金属原子辐射强度可以定性测量重金属含量的大体水平.然后,在相同检测条件下,将已知浓度的标准样品作为参考,制定出各元素的校正曲线,使用外标法,就能够实现定量分析.对Pb、Cr、Cd三种有害重金属元素,目前检出限分别达到9、3.5和23ppm的水平,分析相对误差小于10%,单次测量时间短于2分钟.汞的结果不太理想,检测灵敏度相对偏低,与其原子辐射寿命较短有关.我们将采取脉冲放电延长汞原子辐射弛豫时间的措施来改进汞元素的分析灵敏度,使其达到较高水平.     

Effect of parameters on Si plasma emission in collinear double-pulse laser-induced breakdown spectroscopy

Collinear dual-pulse laser-induced breakdown spectroscopy was carried out on Si crystal by using a pair of nanosecond Nd:YAG laser sources emitting at 1064 nm. The spectral intensities and signalto-noise ratios of selected Si atomic and ionic lines were used to evaluate the optical emission. The optical emission intensity was recorded while varying the interpulse delay time and energy ratio of the two pulsed lasers. The effects of the data acquisition delay time on the line intensity and signal-to-noise ratio have been investigated as well. Based on the results, the optimal interpulse delay time, energy ratio of the two pulsed lasers, and data acquisition delay time for achieving the maximum atomic and ionic line intensities were found for generation of Si plasma with the collinear dual-pulse laser approach. The dominant mechanism for the observed line intensity variation was also discussed. In addition, the plasma temperature and electron number density at different gate delay times and different interpulse delay times were derived. A significant influence of plasma shielding on the electron temperature and electron number density at shorter interpulse delay times was observed.     

基于激光诱导击穿光谱技术的铝合金成分定量分析

利用Nd:YAG激光器输出的532nm激光束对位于空气中的标准变形铝合金样品进行烧蚀产生了激光诱导等离子体.对测量的230—440nm波长范围的光谱进行了谱线标定,同时基于自由定标方法对样品成分进行了定量分析,确定了样品中的元素含量.分析结果与标准值具有较好的一致性.     

应用激光诱导击穿光谱检测土壤中的铅

应用激光诱导击穿光谱技术对模拟土壤中Pb进行快速定量分析。该模拟土壤由PbCl₂,CaCO₃,SiO₂,KBr化学纯试剂制备而成。通过实验得到信噪比随延时的增大呈先增后减的变化规律。利用实验光谱图建立了Pb含量的定标曲线。定量分析研究得到：该方法用于Pb含量定量分析的平均相对误差为8.33%,最低检测限为89μg/g。实验结果验证了激光诱导击穿光谱技术用于土壤中Pb含量测量的能力。     

激光诱导击穿光谱应用于三种水果样品微量元素的分析

激光诱导击穿光谱(LIBS)在植物样品上面的应用是一个较新的课题. 为将LIBS技术能实际应用于与食品安全相关的领域,实验中对三种真空冻干水果样品进行了初步LIBS实验研究,鉴别了其LIBS光谱,并选取典型光谱线,运用统计学方法分析比较了三种水果中Ca,Na,K,Fe,Al,Mg六种元素含量的差别. 实验结果表明,苹果中Na的含量最高,Ca的含量最低,三种水果样品中的K,Fe,Mg等元素含量也都有差异. 实验结果还表明LIBS技术是一种检测、对比植物样品中微量元素含量的有效手段. 关键词： 激光诱导击穿光谱 等离子体 植物样品 微量元素