再加热双脉冲与单脉冲激光诱导Fe等离子体发射光谱实验对比研究

使用单脉冲和再加热双脉冲激光对位于空气中的钢样进行烧蚀激发等离子体,对两种方式产生的光谱进行研究。再加热双脉冲激光诱导击穿光谱采用两束激光,一束烧蚀样品激发等离子体,另外一束激光对产生的等离子进行加热。通过对比发现:采用再加热双脉冲激发样品,增强了发射光谱的信号,增大了等离子体的连续光谱,提高了信号的稳定性,十次测量信号的相对标准偏差从5.0%降低到2.0%。另外,还对影响双脉冲信号增强程度的因素进行了分析,研究了光谱的增强程度随两脉冲间隔和采集延时的变化;激发上能级对光谱增强程度的影响,上能级越高增强程度越大。     

单脉冲和再加热正交双脉冲激光诱导击穿光谱对比研究

为了提高激光诱导击穿光谱技术(LIBS)的检测灵敏度和辐射光谱特性,采用再加热正交双脉冲结构对样品中的4种元素Fe,Pb,Ca和Mg以及含有不同浓度重金属元素Cr的土壤样品进行分析。研究了4条特征谱线FeⅠ：404.581 nm,PbⅠ：405.78 nm,CaⅠ：422.67 nm和MgⅠ：518.361 nm的光谱强度和信背比随两激光脉冲之间时间间隔的变化关系,获得了两激光脉冲之间最佳的时间间隔为1.0 μs。在单脉冲和双脉冲条件下,得到了4条特征谱线FeⅠ：404.581 nm,PbⅠ：405.78 nm,CaⅠ：422.67 nm和MgⅠ：518.361 nm光谱强度的增强倍数分别为2.23,2.31,2.42和2.10;分析了特征谱线FeⅠ：404.581 nm和CaⅠ：422.67 nm谱线强度随时间的演化特性以及4条特征谱线信背比随光谱采集延时的变化关系,双脉冲能有效延长光谱强度的衰减时间以及提高特征谱线的信背比;比较分析了等离子体温度和电子密度随时间的演化特性,在双脉冲条件下,等离子体温度最大升高了730 K,电子密度最大增加了1.8×1016 cm-3。单脉冲和双脉冲条件下获得重金属元素Cr的检测限分别为38和20 μg·g-1,再加热正交双脉冲技术使元素检测限下降近2倍。以上结果表明：再加热正交双脉冲能有效地提升LIBS技术的检测灵敏度和光谱特性,为进一步降低元素的检测限提供了有效的方法。     

多次放电的激光诱导击穿光谱信号增强

激光诱导击穿光谱技术(LIBS)是一种广泛应用于科学和工程方面的元素分析技术。LIBS测量一些微量元素时存在探测极限高的不足,因此增强LIBS信号强度,降低元素探测极限,对扩展其应用范围有着重要的意义。为了实现LIBS光谱信号的增强,提出多次放电增强激光诱导击穿光谱方法,并以固体铝合金材料为例进行了光谱信号强度增强的研究。实验发现,激光作用在铝合金材料上烧蚀样品产生等离子体并溅射到样品上方高压放电电极所在区域,该区域在等离子体产生之后50 μs之内均可以诱导高压电极放电。因此采用高频脉冲电源可以实现一次LIBS产生的等离子体诱导电极多次放电。多次放电会对等离子体进行多次激发,同时多次放电对等离子的加热作用会延缓等离子体冷却速率从而延长等离子体的持续时间,两者共同作用可以增强LIBS光谱信号强度,进而降低LIBS对微量元素的探测极限。使用频率为100 kHz的高频直流脉冲电源,利用数字延迟脉冲发生器同步激光与高压电源,在激光过后3.6 μs触发高压放电,一次LIBS产生的等离子体可以诱导电极5次放电,即对等离子体进行5次激发和加热。利用光谱仪对5次放电等离子体光谱进行积分测量。实验结果表明：使用多次放电增强之后,等离子体持续时间得到大幅延长,光谱信号强度得到大幅增强,其中,Mg Ⅱ (~279 nm)的信号强度可以增强约48倍,Al Ⅱ (~358 nm)的信号强度可以增强约72倍,微量元素Mn Ⅰ (~403 nm)的信号强度增强约6.3倍,微量元素Cu Ⅰ (~403 nm) 的信号强度增强约8.3倍。Mn Ⅰ (~403 nm)和Cu Ⅰ (~403 nm) 的探测极限分别降低为LIBS单次放电的1/6和1/8。多次放电增强激光诱导击穿光谱方法很好地增强了LIBS的光谱信号强度,降低了对微量元素的探测极限,扩展了LIBS技术的应用范围。该方法有潜力应用到贵重物品、稀有材料及文物的鉴定之中。     

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.     

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.     

皮秒双脉冲LA-LIBS对合金样品的微损元素分析

研究了基于一台皮秒Nd∶YAG激光器实现合金样品的双脉冲激光剥离-激光诱导击穿光谱(LA-LIBS)微损元素分析。实验采用低能量的532 nm二倍频激光烧蚀并剥离出微量样品,然后采用较高能量的延时1064 nm激光对剥离出的样品进行二次激发,以增强等离子体中的原子辐射强度和提高光谱检测灵敏度。实验分别研究了烧蚀激光脉冲和二次激发光脉冲的能量对信号强度的影响。在烧蚀激光脉冲能量为10 μJ,二次激发光脉冲能量为2.5 mJ的条件下,LA-LIBS中Cu Ⅰ 324.75 nm原子谱线的强度与单脉冲LIBS相比改善了86倍,激光烧蚀坑洞的直径小于10 μm。研究表明：基于一台皮秒Nd∶YAG激光器,采用双脉冲LA-LIBS技术可以较好地实现对固体样品的微损元素分析。该技术在贵重样品分析和高空间分辨的二维元素显微分析中具有一定的应用价值。     

双飞秒激光脉冲诱导击穿光谱增强特性研究

在大气环境中,以钴为样品,通过单脉冲飞秒激光诱导击穿光谱及共轴双飞秒脉冲激光诱导击穿光谱的对比实验,研究了双脉冲激光诱导击穿光谱的谱线增强机制,测量了双脉冲激光诱导击穿光谱随脉冲时间间隔的变化趋势。结果表明,在最优化的脉冲时间间隔条件下,双脉冲激光诱导等离子体光谱获得明显增强。进一步,通过线性Boltzmann法得出了电子温度随脉冲时间间隔的演化,发现了谱线增强因子和电子温度随脉冲时间间隔呈现出相同的演化趋势,并经历两个明显的变化过程,得出了谱线信号强度的增强依赖于电子温度升高的结论。     

用光电双脉冲LIBS技术快速测量水中痕量汞元素

用木片吸收水溶液,将水溶液样品转变为固体样品,从而解决用激光诱导击穿光谱(LIBS)技术直接分析水样品所带来的诸多问题,并首次采用光电双脉冲LIBs技术来增强激光等离子体中汞的原子辐射.实验绘制了用单脉冲LIBS技术和光电舣脉冲LIBS技术所得到的汞的校正曲线并得出这两种技术中汞的最低检出限分别为2.4和0.3 mg·...     

基于Abel逆变换的激光诱导等离子体辐射特性研究

激光诱导击穿光谱(LIBS)作为一种新型的物质成分测量方法已经在越来越多的领域得到广泛应用，但是与传统的分析方法相比，LIBS技术的分析性能还需进一步提高。LIBS技术的理论基础是激光诱导等离子体，从物理机理上研究等离子体特性，对LIBS系统实验参数的优化具有指导作用，也为提高LIBS技术的检测能力奠定理论基础。激光诱导等离子体是一个与空间相关的非稳态辐射源，空间分辨光谱测量是探究等离子体物理特性的重要手段之一。为研究激光诱导等离子体的辐射特性，采用1 064 nm的Nd∶YAG调Q固体激光器烧蚀合金钢样品产生等离子体，利用空间分辨装置测量二维空间的等离子体辐射光谱信号，通过分析可知实验采集的光谱信号是信号探测器测量路径上的积分光谱强度，由此计算得到的等离子体参数也是观测路径上的平均值。为了深入研究等离子体由内层到外层的辐射规律，首先测量得到等离子体路径积分光谱强度的横向空间分布，然后以等离子体为光学薄和圆柱对称的前提条件，采用三次样条函数算法对路径积分光谱强度进行Abel逆变换，反演得到等离子体由内层到外层谱线辐射率的径向空间分布。选取等离子体辐射光谱中的原子谱线Fe Ⅰ: 374.55 nm和Mn Ⅰ: 403.08 nm为研究对象，分析等离子体辐射光谱的空间分布特征，研究结果表明，等离子体辐射路径积分光谱强度的横向分布呈现出中心位置强度大边缘位置强度小的特征，这是由于等离子体膨胀扩张的结果引起的；通过Abel逆变换得到等离子体光谱辐射率的径向分布，结果表明等离子体从内层到外层谱线的辐射率经过了先增加后减小的变化规律，等离子体中心处出现辐射率的极小值，造成这种现象的主要原因是由于等离子体辐射源中心区域具有较低的电子密度；选取等离子体辐射光谱中Fe元素的11条原子谱线，采用Boltzman法分别由谱线相应的积分光谱强度和辐射率计算等离子体温度，得到等离子体温度的横向空间和径向空间的二维分布，两者具有类似的变化规律；由等离子体温度的横向空间分布可以看出，随着离样品表面距离的增加，等离子体温度呈现单调减小的趋势，等离子体中心到边缘区域等离子体温度逐渐降低，这是由等离子体膨胀扩张以及与环境气体相互作用共同的结果；由等离子体温度的径向空间分布可以看出等离子体由内层到外层等离子体温度逐渐降低，这是由于等离子体膨胀扩张冷却引起的。由此可见，采用Abel逆变换能够实现等离子体由内层到外层的辐射特性分析，为深入理解等离子体产生和演变的物理机理提供实验依据，从而为提高激光诱导击穿光谱技术的分析性能奠定理论基础。     

激光波长对水中金属元素激光诱导击穿光谱探测的影响

针对激光诱导击穿光谱(LIBS)在海洋应用中的问题,对1 064和532nm两个激发波长下水中LIBS光谱特性进行探测分析,以比较其烧蚀效果。通过激光诱导等离子体的时间分辨光谱,分析水下等离子体电子密度随时间的演化规律,1 064nm激光诱导等离子体寿命约为1 200ns,而532nm激光激发情况下等离子体寿命仅约为600ns。基于光在水中的传输特性和LIBS的实验结果,建立了获得最佳LIBS探测效果所需的入水前激光脉冲能量Eiopt(r)与探测距离r的关系,并应用到水下原位探测的模拟分析。结果表明,当探测距离不大于5cm时,所需的入水前1 064nm激光单脉冲能量小于100mJ,该激发波长可用于LIBS的水下探测;当探测距离增至10cm时,所需的入水前532nm激光单脉冲能量只需30mJ左右。因此,当原位探测距离增加时,则需考虑选择532nm激光作为烧蚀光源。     

液相射流中中Al元素单双脉冲LIBS研究

为了综合比较单双脉冲激光诱导击穿光谱技术(LIBS)在液体中重金属元素的检测效果,利用自建的液相射流单-双脉冲LIBS技术装置,对AlCl₃水溶液中的Al元素LIBS特性进行测量和分析。实验中使用两台532 nm Nd∶YAG激光器作为激发光源,等离子体辐射信号通过光谱仪和ICCD进行采集。实验研究了单脉冲下Al(396.15 nm)发射谱线的谱线强度随激光能量、ICCD门延时、门宽之间的变化关系,获得了最优化实验参数激光能量为50 mJ,ICCD门延迟为1 200 ns,门宽为150 ns。在相同的实验条件下,实验考察了Al(369.15 nm)发射谱线的谱线强度随双脉冲之间的延时,激光总能量,ICCD门延时的变化关系,获得了最优化实验参数为两双脉冲之间的延时为1 000 ns,激光总能量为50 mJ,ICCD门延时为1 100 ns。单脉冲和双脉冲条件下获得重金属Al的LIBS检测限分别为26.79和10.80 ppm,双脉冲LIBS技术使元素检测限下降2倍多。实验结果表明双脉冲可以提升LIBS技术的探测灵敏度,为LIBS技术应用于水体中重金属快速检测提供了依据。     

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.     

共线DP-LIBS定量分析水中Cu含量的试验研究

为研究双脉冲激光诱导击穿光谱(DP-LIBS)对水体中铜(Cu)元素检测灵敏度的影响,采用共线双脉冲LIBS检测装置对所配置的含Cu水溶液进行激光诱导击穿光谱试验。结果显示：与运用单脉冲激光诱导击穿光谱(SP-LIBS)检测水体中Cu元素相比,运用DP-LIBS探测到的光谱明显增强,并且其检测结果受光谱仪采集的延迟时间、两脉冲之间的脉冲延迟时间、双脉冲激光能量等因素的影响显著。确定最佳的试验条件为：光谱采集延迟时间为1 380 ns,脉冲延迟时间为25 ns,双脉冲激光能量为100 mJ。分别对铜元素324.7和327.4 nm的特征谱线进行定量分析,两谱线的检测限分别是3.5和4.84 μg·mL-1,且相对标准偏差都在10%以内。用500 μg·mL-1样品对特征谱线为324.7 nm所建立的定标曲线进行验证,反演得出该样品的浓度为446 μg·mL-1,相对误差为10.8%。研究表明DP-LIBS能够提高Cu元素的检测灵敏度,同时具有较高的稳定性。     

Double-pulse LIBS of gadolinium oxide ablated by femto- and nano-second laser pulses

Emission characteristics of gadolinium (Gd) oxide are studied, using ns and fs laser pulses for ablation in double-pulse laser induced breakdown spectroscopy (LIBS). In the current conditions of pulse energy and signal detection timing, emission intensity enhancement in the reheating mode is 25-fold, but little effect can be observed in a pre-pulse mode. It is shown that the optimum focus position of the ablation pulse is about 5 mm apart from the sample surface in the reheating mode. Although little emission can be observed in the single-pulse configuration with fs ablation pulses, the intense emission can be observed in the reheating mode in the double-pulse configuration.     

Effects of pulse energy ratios on plasma characteristics of dual-pulse fiber-optic laser-induced breakdown spectroscopy

Laser-induced plasmas of dual-pulse fiber-optic laser-induced breakdown spectroscopy with different pulse energy ratios are studied by using the optical emission spectroscopy(OES)and fast imaging.The energy of the two laser pulses is independently adjusted within 0–30 m J with the total energy fixed at 30 m J.The inter-pulse delay remains 450 ns constantly.As the energy share of the first pulse increases,a similar bimodal variation trend of line intensities is observed.The two peaks are obtained at the point where the first pulse is half or twice of the second one,and the maximum spectral enhancement is at the first peak.The bimodal variation trend is induced by the change in the dominated mechanism of dual-pulse excitation with the trough between the two peaks caused by the weak coupling between the two mechanisms.By increasing the first pulse energy,there is a transition from the ablation enhancement dominance near the first peak to the plasma reheating dominance near the second peak.The calculations of plasma temperature and electron number density are consistent with the bimodal trend,which have the values of 17024.47 K,2.75×10¹⁷cm;and 12215.93 K,1.17×10¹⁷cm;at a time delay of 550 ns.In addition,the difference between the two peaks decreases with time delay.With the increase in the first pulse energy share,the plasma morphology undergoes a transformation from hemispherical to shiny-dot and to oblate-cylinder structure during the second laser irradiation from the recorded images by using an intensified charge-coupled device(ICCD)camera.Correspondingly,the peak expansion distance of the plasma front first decreases significantly from 1.99 mm in the single-pulse case to 1.34 mm at 12/18(dominated by ablation enhancement)and then increases slightly with increasing the plasma reheating effect.The variations in plasma dynamics verify that the change of pulse energy ratios leads to a transformation in the dual-pulse excitation mechanism.     

Simulation of THz emission from laser interaction with plasmas

One-dimensional particle-in-cell (PIC) program is used to simulate the generation of high power terahertz (THz) emission from the interaction of an ultrashort intense laser pulse with underdense plasma. The spectra of THz radiation are discussed under different laser intensity, pulse width, incident angle and density scale length. High-amplitude electron plasma wave driven by a laser wakefield can produce powerful THz emission through linear mode conversion under certain conditions. With incident laser intensity of 10¹⁸ W/cm², the generated emission is computed to be of the order of several MV/cm field and tens of MW level power. The corresponding energy conversion efficiency is several ten thousandths, which is higher then the efficiency of other THz source and suitable for the studies of THz nonlinear physics.     

X-ray spectrometry of laser-produced aluminum plasmas

X-ray lines and continuum emission from a laser-produced aluminum plasma have been studied. The electron temperature variations during the laser pulse (30 ns) were deduced from time-dependent measurements of intensities of resonance lines (2.5 ns time-resolution). Comparison is made with electron temperature values deduced from ion emission measurements.