激光诱导击穿光谱在煤质检测中的应用现状

我国当前主要能源仍是煤炭资源,煤质快速检测有利于其清洁高效利用。激光诱导击穿光谱（Laser-Induced Breakdown Spectroscopy,LIBS）作为一种快速光谱检测技术,具有样品需求量小、制样简便、可多元素同时测量等优点,其在煤质快速检测中的应用潜力已得到广泛认可。本文从激光诱导击穿光谱仪器（实验室台式、在线式和便携式）的研发现状、激光诱导击穿光谱对煤质（金属元素、非金属元素和工业指标）的检测现状、煤质分析性能提升方法,以及激光诱导击穿光谱定量分析模型研究等方面介绍了近几年来LIBS技术在煤质检测中的应用现状及未来展望。     

支持向量机结台主成分分析辅助激光诱导击穿光谱技术识别鲜肉品种

为提高激光诱导击穿光谱技术(Laser-induced breakdown spectroscopy,LIBS)对鲜肉品种的识别率,采用支持向量机结合主成分分析算法辅助LIBS技术对鲜肉品种进行识别.对鲜肉切片用载玻片压平,采用LIBS技术对鲜肉组织(猪肉、牛肉和鸡肉)表面进行光谱数据的采集,每种鲜肉采集150幅光谱并进行随机排列,取前75幅光谱作为训练集建立模型,后75幅作为测试集测试建模结果.研究选取K、Ca、Na、Mg、Al、H、O等元素的49条归一化谱线数据进行主成分分析,并用所得数据建立支持向量机分类模型.结果表明,通过主成分分析降维,输入变量从49个优化减少到18个,模型建模速度从88.91 s降至55.52 s,提高了支持向量机的建模效率;并使预测集的平均识别率提高到89.11%.本研究为激光诱导击穿光谱技术在鲜肉品种快速分类领域提供了方法和数据参考.     

激光诱导击穿光谱:从实验平台到现场仪器

激光诱导击穿光谱(Laser-induced breakdown spectroscopy, LIBS)技术利用激光实现对分析样品的快速原位剥蚀和光谱激发,是一种具有广阔应用前景的分析手段,尤其是在现场、原位分析中优势明显,快速原位的分析特点符合未来分析仪器的发展方向.近年来基于该技术开展各类仪器研发的相关工作,引起广大研究者的极大关注.本文综述了激光诱导击穿光谱仪器中关键部件的组成及发展,从便携式、手持式及远程系统三个方面综述了各类现场应用仪器的研发进展,并对未来发展方向进行了展望.     

激光诱导荧光光谱分析进展

本文对激光诱导荧光光谱分析的研究现状和发展趋势进行了综述。着重介绍了激光诱导原子荧光光谱、激光诱导分子荧光光谱、激光低温光谱,时间分辨光谱和激光诱导荧光光谱与其它分析技术的联用研究。     

便携式远程激光诱导击穿光谱系统及其定量分析性能

因高温、辐射等极端环境限制，核领域亟需具备在线快速检测特性的分析仪器。基于小型风冷脉冲激光器与小型光纤光谱仪实现了远程激光诱导击穿光谱技术（LIBS）装置的小型化，对该便携式远程LIBS系统的定量分析性能进行了研究，实现了5 m外样品的元素遥测。在单脉冲激光能量100 mJ，脉冲延时1.0 μs的分析条件下，实现了白水晶、陶瓷及铝合金样品中Mn、Si、Al、Na、Ba、Ca及Cr元素的激发，验证了LIBS技术对材料组分和物料成分的远程探测能力，对铝合金样品的定量分析结果显示，该远程遥测系统对铝合金样品定量测量结果的最大相对平均偏差为12%，具备执行核领域快速分析场景下的半定量检测能力。     

激光诱导荧光光谱分析法研究：Ⅴ.Dy—TFA—TOPO—Tween—20的荧光特性及应用

激光诱导荧光光谱在确定与证实光谱的归属和能量传递研究以及提高检测灵敏度方面,具有很大的潜力。前人有关稀土配合物的激光诱导荧光分析虽能提高测定灵敏度,但很少涉及发光机理和能量传递方面的研究。     

飞秒-纳秒双脉冲激光诱导击穿光谱(LIBS)技术对合金的定量分析

激光诱导击穿光谱(Laser-induced breakdown spectroscopy, LIBS)技术几乎不受聚变环境中的强磁场影响，是一种最有希望实现托卡马克装置中面向等离子体材料(Plasma facing materials, PFMs)原位在线诊断的技术，已被用于多个托卡马克PFMs壁诊断。然而，LIBS技术对PFMs表面元素的探测限、定量分析以及PFMs的服役状态判定依旧面临很大挑战。采用同轴飞秒-纳秒激光协同技术，建立了飞秒-纳秒双脉冲激光诱导击穿光谱(fs-ns-DP-LIBS)技术，通过高峰值功率、低激光能量的飞秒激光诱导等离子体，再用纳秒激光增强常规单脉冲LIBS技术信号发射强度，进而提升常规单脉冲LIBS的探测灵敏度，同时结合6种合金标准样品，采用fs-ns-DP-LIBS技术对样品中的主要元素进行了定量分析，并进一步结合机器学习方法对6种合金进行种类判别。结果显示：在纳秒单脉冲和飞秒单脉冲LIBS检测中，Ni、Fe和Mo在400～800 nm波段没有观察到明显特征峰，仅观察到Cr的特征峰；在飞秒-纳秒脉冲间2μs延时，NiⅠ498.02 nm、FeⅠ517....     

激光诱导击穿光谱(LIBS)法微损快速检测党参中Pb

中药材重金属元素快速检测对污染监控及人们健康具有重要意义。激光诱导击穿光谱技术(Laser Induced Breakdown Spectroscopy, LIBS)属于一种快速检测方法,研磨压片等预处理方法相对样品消解已有所简化,但破坏了样品的物理性质,且不能满足中药材大宗品种、大批量检测需求。若进一步简化样品预处理,将更加凸显LIBS快速检测的优势。本文建立了激光诱导击穿光谱技术(LIBS)快速微损检测中药材样品重金属元素定标方法。线性相关系数R2为0.7764,建立的微损定标曲线线性可用于切片党参LIBS快速检测,对待测党参切片样品检测平均相对误差为3.74%,与电感耦合等离子体质谱法(ICP-MS)对比,相关系数R2为0.7957,验证了LIBS技术微损检测的可行性。制备的党参参考定标样品可多次重复用于待测样定标和仪器标定等。实验对待测党参样品仅进行切片处理,避免了研磨、压片等预处理,更加充分地体现LIBS快速检测的优势,为LIBS技术应用于中药材重金属元素快检等领域提供了一种新方法。     

化学计量学在激光诱导击穿光谱分析中的研究进展

激光诱导击穿光谱作为一种新兴的元素分析技术,具有实时在线、非接触、多元素同时检测等优点,是光谱分析领域内的一种前沿性分析手段.然而,如何从复杂大量的激光诱导击穿光谱数据提取有用信息,提高其定性、定量分析准确度是激光诱导击穿光谱技术目前面临的难题.化学计量学作为多学科交叉的化学分支学科,在数据处理、信号解析和模式识别等方面具有优势,能够解决传统化学研究方法难以解决的一些复杂问题.本文从光谱数据预处理、定性和定量分析三方面综述了近年来化学计量学方法在激光诱导击穿光谱中的研究进展.     

高分辨激光诱导击穿光谱技术用于碳质页岩光谱特征分析

碳质页岩是一种重要的非常规油气源岩,包含丰富的页岩气储存信息。在地质油气勘探领域,识别物性相近的碳质页岩是地质学的难题之一。为快速准确判别碳质页岩特性,本研究利用激光诱导击穿光谱( LIBS)技术对碳质页岩的光谱进行特征分析。以1064 nm纳秒脉冲激光作为激发光源,采用高分辨中阶梯光栅光谱仪配合ICCD搭建高分辨光学系统,利用LIBS装置分析四川盆地某井2396~3428 m不同深度处的5个典型碳质页岩样品,共获取碳质页岩中主量元素Si,Al,Fe,Ca,Mg,K和微量元素Cu,Cr,Ni,Sr,Mn,Ti,Rb等22种元素的350条发射谱线。基于高分辨LIBS系统采集的丰富谱线信息,采用主成分分析( PCA)法提取光谱贡献率最大的主成分得分二维图,识别不同类别碳质页岩样品,实现定性分析。结果表明,高分辨LIBS实验装置不仅可用于碳质页岩主量元素Si,Al,Fe,Ca,Mg,K等谱线分析,同时对微量元素如Ni,Cr,Mn,Sr等也具有很好的灵敏性。此外,LIBS技术与主成分分析( PCA)法结合可以更好地用于碳质页岩定性分析领域,提供科学的碳质页岩岩性判断数据和快速的分类手段,为页岩气开采和评估提供强有力的工具。     

Laser-induced Fluorescence Spectroscopy of Uranium Monofluoride

The laser-induced fluorescence excitation spectra of uranium monofluoride have been recorded in the range of 17000\begin{document}$ - $\end{document} 19000 cm\begin{document}$^{-1} $\end{document} using two-dimensional spectroscopy. High resolution dispersed fluorescence spectra and time-resolved fluorescence spectroscopy were also recorded. Three rotationally resolved bands were intensively analyzed, and all bands were found to be derived from the ground state X(1)4.5 with a rotational constant of 0.23421 cm\begin{document}$^{-1} $\end{document}. The low-lying electronic states were observed near 435 and 651 cm\begin{document}$^{-1} $\end{document} in the dispersed fluorescence spectra, which were assigned as \begin{document}$ \Omega' $\end{document}=3.5 and 2.5, respectively. The vibrational constants for the X(1)4.5 and X(1)3.5 states were calculated. The branching ratios of the dispersed fluorescence spectra for the [18.62]3.5, [17.72]4.5, and [17.65]4.5 states were reported. Radiative lifetime of 332(9) ns, 825(49) ns, and 433(15) ns for the [18.62]3.5, [17.72]4.5, and [17.65]4.5 states were obtained by fitting the time-resolved fluorescence spectroscopy, respectively. Transition dipole moments were performed using the branching ratios and the radiative lifetimes.     

Laser-induced Fluorescence Spectroscopy of NiO between 510 and 650 nm

Laser-induced fluorescence excitation spectra of NiO have been recorded in the wavelength region of 510-650 nm under supersonic molecular beam conditions. More than fifty bands have been observed and rotationally analyzed to determine the molecular constants. The excited states exhibit highly irregular variations in terms of isotopic shifts, vibrational intervals, and rotational constants. Twenty-six bands attributed to [Ω=0, 1]-X3∑o transitions have been tentatively grouped into five vibrational progressions. Furthermore, dispersed fluorescence and lifetimes of the strong bands have also been measured.     

Laser-induced Fluorescence Spectroscopy of NiS: Identification of a Low-lying Electronic State

Laser-induced fluorescence excitation spectra of jet-cooled NiS molecules were recorded in the energy range of 12200-13550 cm^-1. Four vibronic bands with rotational structure have been observed and assigned to the [12.4]³∑₀^- -X³∑₀^- transition progression. The relevant rotational constants, significant isotopic shifts, and (equilibrium) molecular parameters have been determined. In addition, the lifetimes of the observed bands have also been measured.     

Laser-induced fluorescence detection of lead atoms in a laser-induced plasma: An experimental analytical optimization study

The combination of the laser-induced breakdown spectroscopy (LIBS) and laser-induced fluorescence (LIF) techniques was investigated to improve the limit of detection (LoD) of trace elements in solid matrices. The influence of the main experimental parameters on the LIF signal, namely the ablation fluence, the excitation energy, and the inter-pulse delay, was studied experimentally and a discussion of the results was presented. For illustrative purpose we considered detection of lead in brass samples. The plasma was produced by a Q-switched Nd:YAG laser and then re-excited by a nanosecond Optical Parametric Oscillator (OPO) laser. The experiments were performed in air at atmospheric pressure. We found out that the optimal conditions were obtained for our experimental set-up using relatively weak ablation fluence of 2–3 J/cm² and an inter-pulse delay of about 5–10 μs. Also, a few tens of microjoules was typically required to maximize the LIF signal. Using the LIBS–LIFS technique, a single-shot LoD for lead of about 1.5 part per million (ppm) was obtained while a value of 0.2 ppm was obtained after accumulating over 100 shots. These values represent an improvement of about two orders of magnitude with respect to LIBS.     

Laser-induced Fluorescence Excitation Spectrum of NiS in 15500-17200 cm^-1

The laser-induced fluorescence excitation spectrum of jet-cooled NiS molecule has been recorded in the energy range of 15500 17200 cm-1. Fifteen bands have been assigned as three transition progressions：[15.65]^3Ⅱ1（v′=0-4）-X^3∑0^-（v″=0）,[15.69]^3∑0^-（v′=0-4）-X^3∑0^-（v″=0）,and [15.81]^3Ⅱ1（v′=0-4）-X^3∑0^-（v″=0）.Spectroscopic constants for the three newly identified electronically excited states have been determined for the first time. In addition,the lifetimes for most observed vibronic bands have also been measured.     

Laser-induced breakdown spectroscopy of solid aerosols produced by optical catapulting

Laser-induced breakdown spectroscopy of particles ejected by optical catapulting is discussed for the first time. For this purpose, materials deposited on a substrate were ejected and transported from the surface in the form of a solid aerosol by optical catapulting using a neodymium-doped yttrium aluminum garnet (Nd:YAG) laser at 1064 nm. A Q-switched Nd:YAG laser at 532 nm was used for chemical characterization of the particles by laser-induced breakdown spectroscopy. Both lasers were synchronized in order to perform suitable spectral detection. The optical catapulting was optimized and evaluated using aluminum silicate particles, nickel spheres, and quartz and stainless steel particles. Experimental parameters such as the interpulse delay time, the sampling distance, the laser fluence, the sampling rate and the particle size have been studied. A correlation between these parameters and the particle size is reported and discussed.     

Laser-induced breakdown spectroscopy of carbon in helium and nitrogen at high pressure

This work is devoted to the study of the gas pressure effect on the laser-induced breakdown spectroscopy signal intensity of carbon. Experiments are performed, using a 1064 nm Nd:YAG laser, with carbon solid samples placed inside a high pressure chamber filled with helium or nitrogen, the gas pressure varying from 1 to 80 atm. The signal intensity of the carbon line (247.86 nm) decreases with increasing pressure. As the plasma size strongly decreases with pressure, two collection optical setups are used, showing different raw results. To take into account the plasma size evolution with pressure, calculated corrections are applied to the collected light intensity. Carbon line emission is measured and corrected as a function of pressure in both gases. At 1 atm, the emission line is found to be greater in helium than in nitrogen by a factor of approximately 3, whereas the intensities in the two gases become close to each other at 80 atm.     

Laser-induced Fluorescence Spectroscopy of NiCl in 12900-15000 cm-1

Laser-induced fluorescence excitation spectra of jet-cooled NiCl molecules were recorded in the energy range of 12900-15000 cm^-1. Six vibronic bands with rotational structure have been observed and assigned to the [13.0]²П^3/2(v'=0-5)-X²П^3/2(v"=0) transition progres-sion. The relevant rotational constants, significant isotopic shifts, and (equilibrium) molecu-lar parameters have been determined. In addition, the lifetimes of the observed bands have also been measured.     

超声射流冷却丁二酮的激光诱导荧光激发谱

在超声射流条件下获得了丁二酮在４３２－４５１ｎｍ波段的激光诱导荧光激发谱。在前人标识为０＾００带谱峰的红端观察到３个很弱的谱峰分别位于０,８７,９７ｃｍ＾－１处（以２２１８２ｃｍ＾－１为０ｃｍ＾－１）。在８７和９７ｃｍ＾－１附近精细扫描,观测到８７和９７ｃｍ＾－１谱峰的联道分裂分别为１．０５观和１．６８ｃｍ＾－１,与理论计算的分裂值符合得很好人 而确定了Ｓ１←Ｓ０跃迁０＾００带的位置在２２１８２ｃ     

Laser-induced breakdown spectroscopy analysis of minerals: Carbonates and silicates

Laser-induced breakdown spectroscopy (LIBS) provides an alternative chemical analytical technique that obviates the issues of sample preparation and sample destruction common to most laboratory-based analytical methods. This contribution explores the capability of LIBS analysis to identify carbonate and silicate minerals rapidly and accurately. Fifty-two mineral samples (18 carbonates, 9 pyroxenes and pyroxenoids, 6 amphiboles, 8 phyllosilicates, and 11 feldspars) were analyzed by LIBS. Two composite broadband spectra (averages of 10 shots each) were calculated for each sample to produce two databases each containing the composite LIBS spectra for the same 52 mineral samples. By using correlation coefficients resulting from the regression of the intensities of pairs of LIBS spectra, all 52 minerals were correctly identified in the database. If the LIBS spectra of each sample were compared to a database containing the other 51 minerals, 65% were identified as a mineral of similar composition from the same mineral family. The remaining minerals were misidentified for two reasons: 1) the mineral had high concentrations of an element not present in the database; and 2) the mineral was identified as a mineral with similar elemental composition from a different family. For instance, the Ca–Mg carbonate dolomite was misidentified as the Ca–Mg silicate diopside. This pilot study suggests that LIBS has promise in mineral identification and in situ analysis of minerals that record geological processes.