水溶液中金属元素的激光诱导击穿光谱的检测分析

文章对竖直流动的CuSO₄和Pb(NO₃)₂水溶液样品表面的激光诱导击穿光谱的（简称LIBS）特性进行了观测分析。实验中采用的烧蚀激光波长为532 nm,脉冲宽度为10 ns,重复频率为10 Hz;LIBS信号的探测通过一色散相加型双光栅单色仪、Boxcar和PMT的组合来完成。通过对水溶液中金属元素的LIBS信号随时间和能量演化规律的分析,初步确定了系统 的最佳烧蚀能量和最佳探测延时。受样品表面附近空气击穿时氧元素信号的影响,实验对Cu和Pb各自的击穿位置进行了优化。在分析影响LIBS光谱探测因素的基础上,进一步优化了系统的工作条件和探测 参数。通过对不同浓度下LIBS信号的探测分析,初步确定了系统对Cu与Pb的最低检测浓度,分别约为31,50 ppm(μg·mL-1)。文章还对将LIBS技术运用到海水中重金属的实时在线检测的可 行性进行了讨论。     

Temporally and spectrally resolved analysis of a copper plasma plume produced by ultrafast laser ablation

We report an experimental analysis of the plasma plume produced during ultrafast laser ablation of a copper target, in high vacuum. The plasma plume optical emission is studied by using a hybrid time-gated imaging technique which allows obtaining simultaneous information on the spectral and spatial characteristics of the emitting species. We used both single and double pulse ablation scheme, observing their influence on the characteristics of the ablated atomic species.     

基于一种远程双脉冲激光诱导击穿光谱系统原位分析钢样成分

为了实现钢铁等金属熔炼过程中实时、在线监测元素组分含量,设计了一种远程双脉冲激光诱导击穿光谱(LIBS)分析系统,对远距离的样品进行非接触式远程测量、成分分析。首先利用固体标准钢样对系统进行了测试以及标定,为下一步利用此系统在线监测熔融钢液组分含量提供了基础。实验结果表明：激光远距离聚焦光斑在1 mm左右;双脉冲烧蚀比单脉冲烧蚀深度深很多;双脉冲最佳延时在不同距离下不一致;3.1 m处双脉冲增强效果比2.1 m处更好,其中Ti(Ⅰ)319.99 nm增强最显著为5.19倍;各种元素的标定曲线相关系数r都在0.99左右,重复精度(RSD)基本都小于5%,测量偏差(RMSE)都小于0.021%,2.1 m处的检出限相比3.1 m处更低,2.1 m处多数元素检出限小于500 ppm。     

Microdrilling of metals with an inexpensive and compact ultra-short-pulse fiber amplified microchip laser

We have investigated the ultra-fast microdrilling of metals using a compact and cheap fiber amplified passively Q-switched microchip laser. This laser system delivers 100-ps pulses with repetition rates higher than 100 kHz and pulse energies up to 80 μJ. The ablation process has been studied on metals with quite different thermal properties (copper, carbon steel and stainless steel). The dependence of the ablation depth per pulse on the pulse energy follows the same logarithmic scaling laws governing laser ablation with sub-picosecond pulses. Structures ablated with 100-ps laser pulses are accompanied only by a thin layer of melted material. Despite this, results with a high level of precision are obtained when using the laser trepanning technique. This simple and affordable laser system could be a valid alternative to nanosecond laser sources for micromachining applications.     

Double-pulse laser-induced breakdown spectroscopy for trace element analysis in sintered iron oxide ceramics

Double-pulse laser-induced breakdown spectroscopy (LIBS) is an emerging technique for accurate compositional analysis of many different materials. We present a systematic study of collinear double-pulse LIBS for analysis of the trace and side elements boron, manganese, copper, aluminum, titanium, silicon, chromium, nickel, potassium, and calcium in sintered iron oxide targets. The samples were ablated in air by single-pulse and double-pulse Nd:YAG laser radiation (6 ns pulse duration, laser wavelength of 532 nm) and spectra were recorded with an Echelle spectrometer equipped with an ICCD camera. We investigated the evolution of atomic and ionic line emission intensities for different interpulse delay times between the laser pulses (from 100 ns to 50 μs) and gate delays after the second laser pulse. We also varied the energy partition between the first and second laser pulse and the size of the irradiated spot at the sample surface. For the trace and side elements, we observed double-pulse LIBS signals that were enhanced as compared to single-pulse measurements depending on the interpulse delay time, the energy partition between the pulses, and the spot size. For the elements boron, copper, aluminum, titanium, chromium, potassium, and calcium limits of detection below 10 ppm were achieved.     

铅的单脉冲LIBS定量光谱检测与比较

单脉冲激光诱导击穿光谱技术(single-shot,LIBS)是一种在国际上被广泛使用的物质及元素检测技术,具有快速、准确、无需样品制备等诸多优点.为了满足单脉冲LIBS的实验要求,实验用激光器的选取是非常重要的,它直接关系到诱导激光的强度以及脉冲宽度的大小,而这些又对实验结果产生深刻的影响.因此,选取正确的激光器,是单脉冲LIBS成功的关键.正是基于这个目的,比较了不同波长、不同激光能量的激光脉冲作用下,纯铅发射光谱的定量变化,对于单脉冲LIBS中激光器的选取有着很好的借鉴意义.     

An improved approach for hydrogen analysis in metal samples using single laser-induced gas plasma and target plasma at helium atmospheric pressure

We report in this paper the results of an experimental study on hydrogen analysis of solid samples in high pressure helium ambient gas employing the basic scheme of laser induced breakdown spectroscopy (LIBS). It is shown that the metastable excited state of helium atom can be utilized to induce delayed excitation of the ablated hydrogen atoms, and thereby avoid the Stark broadening effect as well as overcoming the undesirable mismatch effect, which are responsible for inefficient excitation respectively. It is further demonstrated that for samples of high boiling-point materials such as zircaloy, successful hydrogen analysis can be achieved by a newly introduced double excitation technique employing single laser realized in a modified configuration of the conventional LIBS method. PACS 51-52     

金属特性对激光诱导击穿光谱最佳实验参数的影响

采用波长为532nm的单脉冲激光诱导两种金属样品铜和锌，产生等离子光谱，固定激光能量40mJ、门宽100ns、光谱仪入射狭缝0.1mm、ICCD增益100等参数，研究金属样品物理化学特性对汇聚透镜焦点到样品表面距离、ICCD采集延迟等最优化实验参数的影响.实验中分别选取铜样品Cu（I）521.82nm和锌样品Zn（I）481.053nm谱线作为LIBS信号，实验测定的透镜焦点在距样品表面不同距离处的LIBS信号强度，结果表明铜和锌样品的聚焦透镜焦点分别在样品表面内距表面的距离为5mm和5.5mm时得到光谱信号强度最大；铜和锌的ICCD探测延时分别为1300ns和1100ns时等离子体光谱信号的信噪比最大并具有可观测的强度，依据铜和锌样品物理化学特性的差异对实验结果进行了合理的分析与讨论，为后续研究金属样品LIBS技术的基底效应、纳米结构增强激光诱导击穿光谱机理提供数据参考.     

钾元素单脉冲和双脉冲激光诱导击穿光谱研究

基于自行研制的新型液体射流的激光诱导击穿光谱(LIBS)实验装置,研究了实验条件(如积分延时、脉冲间隔、激光能量等)对K元素单脉冲LIBS和双脉冲LIBS等离子发射的影响.实验得知相对单脉冲激光激发,双脉冲激光激发可以显著提高等离子体发射谱线强度,增加谱线强度的衰减时间,提高LIBS数据的稳定性.通过最佳实验条件下K766.49nm谱线强度随溶液浓度的分析,得到该实验系统中,双脉冲激光激发时K元素的检测灵敏度和检测限约是单脉冲激光激发时的37倍.实验结果为双脉冲LIBS技术应用于水体金属的检测提供了一定依据.     

Laser-induced breakdown spectroscopy: A versatile tool for monitoring traces in materials

Laser-induced breakdown spectroscopy (LIBS) is an emerging technique for simultaneous multi-elemental analysis of solids, liquids and gases with minute or no sample preparation and thus revolutionized the area of on-line analysis technologies. The foundation for LIBS is a solid state, short-pulsed laser that is focused on a sample to generate a high-temperature plasma, and the emitted radiation from the excited atomic and ionic fragments produced within the plasma is characteristic of the elemental composition of the sample that can be detected and analyzed using a suitable optical spectrograph. In the present paper, the applicability of LIBS for different solid samples having homogeneous (silver ornament, aluminum plate) or heterogeneous composition (soil) using nanosecond laser pulses is discussed. Nanosecond pulse laser makes plasma at the sample surface even at very low pulse energies and also allows for precise ablation of the substrate material with little damage to the surrounding area. We have also studied the penetration of different heavy metals inside the soil surface.      

钾元素单脉冲和双脉冲激光诱导击穿光谱研究

基于自行研制的新型液体射流的激光诱导击穿光谱(LIBS)实验装置,研究了实验条件(如积分延时、脉冲间隔、激光能量等)对K元素单脉冲LIBS和双脉冲LIBS等离子发射的影响.实验得知相对单脉冲激光激发,双脉冲激光激发可以显著提高等离子体发射谱线强度,增加谱线强度的衰减时间,提高LIBS数据的稳定性.通过最佳实验条件下K766.49nm谱线强度随溶液浓度的分析,得到该实验系统中,双脉冲激光激发时K元素的检测灵敏度和检测限约是单脉冲激光激发时的37倍.实验结果为双脉冲LIBS技术应用于水体金属的检测提供了一定依据.     

用大芯径石英玻璃光纤传输兆瓦级高能激光脉冲及其在双波长LA-LIBS技术中的应用

为了解决单脉冲激光诱导击穿光谱(LIBS)技术在元素分析时空间分辨本领与分析灵敏度之间的矛盾,本文利用一台双波长输出的Nd∶YAG激光器开展了双波长激光剥离-激光诱导击穿光谱(LA-LIBS)技术的研究。其中532 nm的二倍频激光用于剥离样品;1 064 nm的基频激光通过大芯径石英玻璃光纤传输并实现一定的延时后用于击穿被剥离的样品。两束激光采用正交几何配置以实现高空间分辨高灵敏的元素分析。实验研究了1 064 nm激光到光纤的耦合、光纤输出后的准直以及再聚焦时的一些关键技术问题。研究并得出了四种不同光纤对激光能量的传输能力。选择利用芯径为800 μm,数值孔径为0.39、长50 m的石英玻璃光纤成功传输了15 mJ的调Q激光脉冲并实现了250 ns的延时。并在此基础上开展了铜合金样品的双波长LA-LIBS分析,实验验证了基于一台Nd∶YAG激光器开展双波长LA-LIBS研究的可行性。该技术只需要一台激光器就可以完成相应的光谱分析,具有系统结构简单,便于小型化等优点,适合对不同样品开展原位的高空间分辨高灵敏的元素显微分析。     

Double pulse UV laser induced breakdown spectroscopy of stainless steel

Results of experimental investigations of 304 austenitic stainless steel (ASS) ultraviolet spectral range by single and double pulse laser induced breakdown spectroscopy (LIBS) at atmospheric pressure are reported. Various parameters, such as laser energy, placement of the laser beam focus with respect to the surface of illumi-nation, and collinear double laser pulse delay were used as variables. This study contributes to a better under-standing of the LIBS plasma dynamics by observing the temporal evolution of various emission lines. Temperature measurements were made by the Boltzmann diagram method using singly ionized Fe lines, and electron densities were found from Stark broadening. The temporal behaviors of these parameters were also estimated. It was found that the electron temperature for double pulses is higher than that for single pulse of the same total energy. For double pulse LIBS, the iron line emission intensities are enhanced and the analytical performance is improved. For instance, the intensity of iron line Fe I 275.01 nm was a factor of about 300 times higher if a double pulse of 2 × 20 mJ was used instead of a single pulse of 40 mJ when focusing the beam 4.7 mm behind the target surface. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 79, No. 5, pp. 654–660, 2006.     

Comparative Study of Two Methods of Orthogonal Double-Pulse Laser-Induced Breakdown Spectroscopy of Aluminum

Double-pulse laser induced breakdown spectroscopy (DP-LIBS) of aluminum sample is studied experimentally in orthogonal configuration in air. In this configuration, two schemes of reheating and pre-ablation are examined and the results are compared with single pulse one. The effect of delay time between two laser pulses on emission line intensities of plasma is investigated. Some of the parameters that have been involved in different mechanism of signal enhancement such as plasma temperature, sample heating effects, atmospheric effects, and modification of the ablation dynamics are more discussed. Investigation of the effect of laser pulse energy on emission line intensities in single pulse LIBS experiment demonstrate that because of saturation effects the intensities will not increase necessarily by increasing the laser pulse energy. Moreover, the results show that the electron temperature and rate of mass removal in orthogonal configuration of DP-LIBS is higher than that of single pulse with the same total energy. It is suggested that for correct comparison between single and double pulse results, the optimum pulse energy in single pulse should be considered. Overall, our results demonstrate that under optimized conditions the signal enhancement is much more in pre-ablation configuration than re-heating configuration.     

Optical transmission and reflection of aluminum film irradiated by nanosecond laser beam and experimental studying of phase-explosion

In this paper we present evidence for a phase explosion during the laser-induced ablation process by studying the optical reflectivity of the ablated plume. The ablation was produced by irradiating thin film aluminum coated on a quartz substrate with a single pulse laser beam in ambient air. The laser pulse was provided by the second harmonic of a Q-switched Nd:YAG laser with ∼10 ns pulse duration. The transmission of a low power He–Ne laser beam through the hot ablated material plume and its reflection (from the front surface, and rear surface of aluminum film) were also monitored during the duration of the ablation event. The results show that the front surface reflectivity is enhanced at an early time of ablation which is described as strong evidence for the creation of a phase explosion in this process.     

LIBS used as a diagnostic tool during the laser cleaning of ancient marble from Mediterranean areas

The use of laser ablation for cleaning stone is a tried-and-tested method for preserving outdoor artwork surfaces exposed to environmental stresses. However, it is of interest to spectroscopically characterize the sample surface before and during the laser ablation in order to implement automatic control of the cleaning process. To this aim, we have undertaken systematic LIBS analysis on various clean and dirty surfaces of marble fragments collected from ancient quarries in Mediterranean areas, without the characteristic patina that comes from the protective layers usually deposited on the final artwork. The effectiveness of the cleaning process was then monitored by following the disappearance from the LIBS spectra of the encrustation elements during successive laser shots. The LIBS analysis of the clean surfaces of the samples examined confirmed that main bulk composition is based on calcium and magnesium carbonates, with the addition of strontium and, to a minor extent, of manganese and copper substituents. On the other hand, the encrustations were rich in sodium, aluminum, iron, silicon, titanium, lithium, manganese, and chromium, probably coming from sand/soil deposition and, only to a minor extent, from atmospheric pollution. Although SEM imaging and SEM-EDX analyses performed on the same samples at different resolutions showed remarkable surface inhomogeneities from the crustal region deep into the bulk material, the work demonstrates the possibility of a quantitative, minimally invasive, LIBS stratigraphy. The results from the technique are suitable for monitoring cleaning processes by determining appropriate elemental markers present on the surface at trace level (of the order of 100 ppm). PACS 52.25.Kn; 7.60.Rd; 32.30.Jc; 42.62.Fi     

飞秒双脉冲激光照射金属薄膜的热行为

通过双温方程对飞秒单脉冲与双脉冲照射金薄膜进行了计算模拟分析,得到了金靶的电子温度和晶格温度随着时间空间的变化。在同样激光能量密度下,单脉冲与双脉冲使得金膜温度的变化表明双脉冲使得更多的激光能量渗透到靶材内部,这些能量可以使得烧蚀深度更深,有利于提高激光烧蚀靶材的效率。计算结果显示随着激光能量密度的增加熔化面深度逐渐增加,单脉冲与双脉冲熔化面深度的变化明显不同。在激光能量密度高于损伤阈值附近,单脉冲的烧蚀深度大于双脉冲的烧蚀深度,随着激光能量密度增加,双脉冲的烧蚀深度将大于单脉冲的烧蚀深度。     

Molecular dynamics simulations of cluster distribution from femtosecond laser ablation in aluminum

Femtosecond laser ablation and plume evolution of aluminum is investigated for various inhomogeneous laser pulses. For the simulations of the atoms the molecular dynamics code IMD is used. The ablated gas-phase is scanned by a cluster algorithm (DBSCAN), from which we gain a cluster size distribution of the ablated material. Per single pulse, only a small portion of the total volume evaporates into the gas phase. Therefore??to have reasonable statistics??we have to deal with huge samples (6×10⁷?atoms). The ablation threshold is determined by comparing the depth of the holes to the applied fluence. Angular and velocity distributions of the plume are compared to experiments.     

Comparison between geometrically focused pulses versus filaments in femtosecond laser ablation of steel and titanium alloys

Kerr self-focusing of high-power ultrashort laser pulses in atmosphere may result in a structure or structures of high intensity that can propagate over long distances with little divergence. Filamentation has garnered significant interest in the nonlinear optics community due to its unique properties. Salient features of filaments include a central region of intense laser power (greater than the ionization threshold of the propagation medium) and a low temperature plasma column that lasts up to nanoseconds in duration after the passage of the laser pulse. Steel and titanium samples are ablated by filaments and by sharply focused sub-picosecond laser pulses. We then performed metrology on the samples to compare the ablation features in addition to modeling of the plasma ablation process. Ablation with filaments leads to a wider range of material responses as compared to ablation with sharply focused pulse. This results in potential complications for applications of filament ablation that depends on the rate of material removal and spectroscopic analysis.     

铀元素的激光诱导击穿光谱测量分析

为促进LIBS技术在微量重金属元素检测以及核污染检测领域的应用,提高检测灵敏度和准确性,采用了激光双脉冲LIBS技术和光电双脉冲LIBS技术,分别对土壤和二氧化硅中的铀元素进行分析。首先,对激光脉冲能量、电压和采集延时等参数进行优化,提高铀元素特征谱线的强度和信噪比;然后在优化实验参数条件下,对含不同浓度铀元素的土壤样品和二氧化硅样品进行激发;选取UII 367.01 nm、 UII 454.36 nm两条铀元素的特征谱线作为分析线,通过铀元素浓度与特征谱线强度的线性关系,建立定标曲线。双脉冲激光激发条件为：激光脉冲1作为预脉冲,主要参数为1 064 nm, 90 mJ, 9.2 ns,激光脉冲2作为再加热脉冲,主要参数为355 nm, 50 mJ, 8 ns,两个脉冲的时间间隔800 ns,光谱采集相对第二个脉冲延时1μs,得到铀元素在土壤和二氧化硅两种样品中的浓度检测下限分别为572和110 mg·kg^-1,拟合优度值R²分别为0.958和0.999。在光电双脉冲激发条件下,激光脉冲作为预脉冲,主要参数为355 nm, 50 mJ, 8 ...