Comparative study of laser-induced plasma emission of hydrogen from zircaloy-2 samples in atmospheric and low pressure ambient helium gas

An experimental study has been performed to demonstrate the advantage of employing ambient helium gas in the spectral quality improvement of hydrogen emission in laser-induced plasma from zircaloy-2 samples at both atmospheric and low gas pressure. It was further shown that the optimal results achieved in the two pressure regimes require the adoption of different sets of experimental parameters consisting of the laser energy, the focusing lens position and the detection gate delay. A strictly linear calibration line with extrapolated zero intercept was nevertheless exhibited in the case of atmospheric gas pressure only. Additional time-evolution measurement of the emission intensities of hydrogen, helium and zirconium clearly suggests a distinctly different excitation mechanism for hydrogen atoms associated with the presence of ambient helium atoms and their meta-stable excited state. PACS 52.38 Mf     

Shielding effect of laser-induced plasma in glass: pulse-to-pulse evolution of nitrogen and analyte emission lines

A characteristic of the plasma shielding effect was investigated through simultaneous measurement of time evolution of nitrogen emission in ambient air and analyte-specific emission in a glass matrix with varying lens-to-sample distance (LTSD), laser pulse energy, and repetition rate. Even under the threshold energy of air breakdown, strong nitrogen-emission lines could be measured by laser-induced breakdown spectroscopy (LIBS) for the glass samples in air at atmospheric pressure. The time evolution of the nitrogen emission was correlated reversely with a variation of various analyte emissions in the glass samples. Based on the reverse relation between the intensities of nitrogen and calcium emission intensities, the corrected values of the calcium emission line were calculated. This methodology shows consistent results independent of experimental conditions such as different LTSDs, laser energies, and repetition rates.     

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     

Hydrogen and Deuterium Analysis Using Laser‐Induced Plasma Spectroscopy

Abstract

Hydrogen emission in laser plasma has been studied by focusing a TEA CO₂ laser and Nd‐YAG lasers on various types of samples, such as glass, quartz, and zircaloy pipes doped with hydrogen. It was found that H_α emission with a narrow spectral width occurs with high efficiency when the laser plasma is produced in low‐pressure host gas. In contrast, the conventional well‐known laser‐induced breakdown spectroscopy (LIBS), which operates at atmospheric air pressure, cannot be applied for the analysis of hydrogen as impurity. The specific characteristic of hydrogen emission in low‐pressure plasma is interpreted on the basis of our shock wave model, taking account of the fact that the hydrogen mass is extremely light compared to that of the host target. Another experimental study on gas analysis was conducted using an Nd‐YAG laser and helium host gas at atmospheric pressure on a sample of mixed water (H₂O) and heavy water (D₂O) in vapor form. It was shown that completely resolved hydrogen (H_α) and deuterium (D_α) emission lines that are separated by only 0.179 nm could be obtained at a properly delayed detection time when the charged particles responsible for the strong Stark broadening effect in the plasma have mostly disappeared. It is argued that a helium metastable excited state plays the important role in the hydrogen excitation process.     

空气及水汽的激光诱导击穿光谱特性实验研究

以大气颗粒物测量为目标,实验研究了作为背景的空气分子的激光诱导击穿光谱(laser induced breakdown spectrometry, LIBS),以NIST原子发射谱线数据库为参考,对其中的O,N,H等主要元素的特征谱线进行了标识。研究了CCD光谱仪实验参数对空气等离子体发射谱线的影响,得出积分延时大于7 μs时可以较好地减小空气分子所产生的干扰谱线,积分时间宽度大于仪器最小值(1. 1 ms)时对谱线信号强度影响较小等结论。还研究了水汽的激光诱导击穿光谱,分析了O,N,H等元素的发射谱线信号强度的变化,发现H的发射谱线信号强度与水汽含量之间具有很好的线性关系。这些结果对于在大气环境条件下,对大气颗粒物的识别具有重要的指导意义。     

Review of Laser-Induced Plasma,Its Mechanism,and Application to Quantitative Analysis of Hydrogen and Deuterium

Abstract

A comprehensive review of important progress achieved over the last 30 years regarding knowledge of laser-induced plasmas generated by CO₂ and Nd:YAG lasers in a variety of ambient gases is presented in this article, as well as research results on the extension of laser-induced breakdown spectroscopy (LIBS) for quantitative analysis of light elements, especially hydrogen and deuterium. First, the formation of shock wave–induced expanding secondary plasma in low-pressure ambient gases is discussed along with the dynamic characteristics of the secondary plasma expansion process. The unique advantages of low-pressure gas plasma are explained in relation to the successful detection of the sharp H and D emission lines. The experimental results using helium ambient gas are presented with emphasis on the role of He gas plasma in introducing an additional delayed excitation mechanism involving the helium metastable excited state, which resulted in the complete resolution of H and D emission lines, separated by only 0.18 nm. The development of a laser precleaning treatment and special double-pulse techniques further produced a linear calibration line with zero intercept applicable to quantitative H and D analyses of zircaloy sample, with either low- or high-pressure ambient He gas. More recent use of a transversely excited atmospheric (TEA) CO₂ laser in place of an Nd:YAG laser has demonstrated the much desired larger excited helium plasma and thereby resulted in significant emission enhancement and improved detection sensitivity.     

Early stage expansion and time-resolved spectral emission of laser-induced plasma from polymer

In the nanosecond laser ablation regime, absorption of laser energy by the plasma during its early stage expansion critically influences the properties of the plasma and thus its interaction with ambient air. These influences can significantly alter spectral emission of the plasma. For organic samples especially, recombination of the plasma with the ambient air leads to interfering emissions with respect to emissions due to native species evaporated from the sample. Distinguishing interfering emissions due to ambient air represents a critical issue for the application of laser-induced breakdown spectroscopy (LIBS) to the analysis of organic materials. In this paper, we report observations of early stage expansion and interaction with ambient air of the plasma induced on a typical organic sample (nylon) using time-resolved shadowgraph. We compare, in the nanosecond ablation regime, plasmas induced by infrared (IR) laser pulses (1064 nm) and ultraviolet (UV) laser pulses (266 nm). Nanosecond ablation is compared with femtosecond ablation where the post-ablation interaction is absent. Subsequent to the early stage expansion, we observe for each studied ablation regime, spectral emission from CN, a typical radical for organic and biological samples. Time-resolved LIBS allows identifying emissions from native molecular species and those due to recombination with ambient air through their different time evolution behaviors.     

气体压强对纳秒激光诱导空气等离子体特性的影响

环境气体的压强对激光诱导等离子体特性有重要影响.基于发射光谱法开展了气体压强对纳秒激光诱导空气等离子体特性影响的研究,探讨了气体压强对空气等离子体发射光谱强度、电子温度和电子密度的影响.实验结果表明,在10-100 kPa空气压强条件下,空气等离子体发射光谱中的线状光谱和连续光谱依赖于气体压强变化,且原子谱线和离子谱线强度随气体压强的变化有明显差别.随着空气压强增大,激光击穿作用区域的空气密度增加,造成激光诱导击穿空气几率升高,从而等离子体辐射光谱强度增大.空气等离子体膨胀区域空气的约束作用,增加了等离子体内粒子间的碰撞几率以及能量交换几率,并且使离子-电子-原子的三体复合几率增加,因此造成原子谱线OⅠ777.2 nm与NⅠ821.6 nm谱线强度随着气体压强增大而增大,在80 kPa时谱线强度最高,随后谱线强度缓慢降低.而离子谱线N Ⅱ 500.5 nm谱线强度在40 kPa时达到最大值,气体压强大于40 kPa后,谱线强度随压强增加而逐渐降低.空气等离子体电子密度均随压强升高而增大,在80 kPa后增长速度变缓.等离子体电子温度在30 kPa时达到最大值,气体压强大于30 kPa后,等离子体电子温度逐渐降低.研究结果可为不同海拔高度的激光诱导空气等离子体特性的研究提供重要实验基础,为今后激光大气传输、大气组成分析提供重要的技术支持.     

激光诱导击穿空气等离子体时间分辨特性的光谱研究

空气等离子体的时间行为对空气环境下激光诱导等离子体形成过程的研究有重要意义.本文将纳秒Nd:YAG脉冲激光(1064 nm)聚焦于一个大气压的空气中,诱导其产生等离子体.利用具有纳秒时间分辨功能的PI-MAX-II型ICCD,采用时间分辨光谱方法,研究了大气环境下激光诱导等离子体的时间行为.大气环境下的激光诱导等离子体光谱广泛分布于300—900 nm范围内,并且是由带状光谱和线状光谱叠加而成的.根据美国国家标准与技术研究院原子发射谱线数据库,对等离子体光谱中的氧、氮、氢等元素的特征谱线进行了识别和归属.给出了激光诱导击穿大气等离子体光谱随时间演化的直观图像,根据空气等离子体发射谱线计算了等离子体电子温度和等离子体电子密度.这些结果对于提高在大气环境下进行的在线测量结果的准确性和精确性具有重要的科学意义.     

Influence of electron energy distribution on helium recombining plasma diagnostics using line emissions

The influence of electron energy distribution on helium recombining plasma diagnostics is investigated using a helium collisional‐radiative model. The population densities of excited helium atoms are calculated for Maxwellian and non‐Maxwellian distribution plasma cases. In the case of the Maxwellian distribution plasma, the electron temperature and electron density determined by the Boltzmann plot method agree well with the input plasma parameters. On the other hand, it is indicated that the electron temperature and electron density are significantly underestimated in the bi‐Maxwellian distribution plasma case, even though the density of the hot electron components is three orders smaller than that of the bulk electrons. This result indicates that in a non‐Maxwellian helium recombining plasma, evaluation of the particle balance based on line emissions from excited helium atoms would be difficult because the reaction rate of atomic and molecular processes is strongly dependent on the electron temperature and density.     

Kaonic helium atoms

Recent progress on the x-ray spectroscopy of kaonic helium atoms as well as on the precision laser spectroscopy of antiprotonic helium atoms are presented. Some historical background connecting these two exotic helium atoms is also discussed.     

A novel double-pulse laser plasma spectroscopic technique for H analysis in metal samples utilizing transversely excited atmospheric-pressure CO2 laser-induced metastable He atoms

The analysis of hydrogen in a metal sample (zircaloy-4), which is usually difficult to perform using conventional laser-induced breakdown spectroscopy (LIBS) techniques, has been achieved using a double-pulse technique under He gas at atmospheric pressure. In this technique, a transversely excited atmospheric-pressure (TEA) CO₂ laser (1.5 J, 200 ns) was focused onto the metal surface to induce a strong He gas plasma whilst simultaneously focussing a Nd-doped yttrium aluminum garnet (Nd:YAG) laser (120 mJ, 8 ns), synchronized with the TEA CO2 laser, onto the metal to ablate atoms into the resulting He gas plasma. The emission spectrum obtained shows a narrow H linewidth with low background intensity and long lifetime emission, thereby indicating that excitation takes place via metastable He atoms. The H emission from H₂O can be suppressed by a careful pretreatment involving heating the sample in a vacuum chamber.     

激光烧蚀金属靶时气体电离分析

我们使用Ｎｄ：ＹＡＧ激光器烧蚀金属Ａｌ靶获得等离子体,利用光谱时－空分辨技术,关于环境气体分解及其对等离子体辐射特征的影响进行了研究。使用的气体是Ａｒ,Ａｉｒ,Ｎ２。结果发现,在等离子体形成初期,等离子体时－空分辨谱中有大量的环境气体离子谱线。基于Ａｌ等离子体不同激光能量下的时间－空间分辨谱。对激光烧蚀金属靶时气体电离现象进行了分析,对气体分解造成的影响进行了简单的讨论。     

激光诱导击穿光谱测量偏差的物理影响因素研究

为了消除LIBS实际测量光谱谱线与标准的LIBS光谱谱线间存在的差值,提高元素测量精准度,提出了针对激光诱导击穿光谱测量偏差的物理影响因素研究。实验在相同条件下,对烧蚀孔效应和光谱波长的关系进行了测试,研究了激光诱导击穿光谱高温Mg等离子体在1.00～3.00 μs范围采样延时下的斯塔克(Stark)展宽数据,从而得出烧蚀孔效应和斯塔克延时展宽等物理因素对采集光谱造成的具体影响。研究结果及方法完全可以应用于其他激光诱导击穿光谱实验系统的误差分析,这对于提高LIBS技术的物质元素测量精准度,研究LIBS技术的最佳采样延时时间,具有重要意义。     

Role of ion-ion recombination in population of triplet resonance levels of cadmium and mercury

In this paper, we present the results of the experimental study of the spectral line emission of cadmium and mercury atoms in the pulsed discharge afterglow in gas mixtures containing vapors of bromides of these metals, hydrogen, and helium buffer gas. It was shown that the population of triplet resonance levels is controlled by recombination of positive metal ions and negative bromine ions.     

Space resolved density measurements of argon and helium metastable atoms in radio-frequency generated He-Ar micro-plasmas

Space resolved concentrations of helium He* (³S₁) and argon Ar* (³P₂) metastable atoms in an atmospheric pressure radio frequency micro-plasma jet were measured using tunable diode laser absorption spectroscopy. Even small absorptions down to 10^-4 could be measured using lock-in technique. The absolute density of metastable atoms densities at different rf-power, flow rate and gas mixture was deduced from measured absorption rates. Metastable concentrations range from 10⁹ to 10¹¹ cm^-3. Analysis of spectral profiles provided the pressure broadening coefficients of both metastable atoms by helium. The spatial distribution of metastable atoms in the plasma volume was obtained for various discharge conditions. Density profiles between the electrodes reveal the sheath structure and reflect the plasma excitation distributions in the discharge volume. It reveals the dominance of the α-mode discharge.     

Excitation of Doubly‐Charged Ion Emission Lines from a Grimm‐Style Glow Discharge Plasma—Comparison Between Yttrium and Zirconium

Spectra of yttrium and zirconium emitted from a Grimm‐style glow discharge plasma were investigated to elucidate the excitation mechanism of doubly‐charged ionic lines when using argon–helium mixed gas as well as argon gas alone. The energy sum for exciting doubly‐charged ion species of yttrium is slightly smaller compared to the case of zirconium, which yields an interesting correlation in the excitation energy between their ionic species and excited species of helium or argon. The Y III emission lines which were assigned to the 4p⁶5p–4p⁶5s(4p⁶4d) transitions could be observed in the argon–helium mixed gas plasma, but those were hardly excited with argon gas only. The Zr III emission lines did not appear in the spectra emitted by the argon gas plasma nor by the mixed gas plasma. A possible explanation for these phenomena is that the excitation of these ionic species is caused principally by collisional energy transfer from helium species to the analyte atoms.     

Major elements analysis in bituminous coals under different ambient gases by laser-induced breakdown spectroscopy with PLS modeling

Three major elements, carbon, hydrogen, and nitrogen, in twenty-four bituminous coal samples, were measured by laser-induced breakdown spectroscopy. Argon and helium were applied as ambient gas to enhance the signals and eliminate the interference of nitrogen from surrounding air. The relative standard deviation of the related emission lines and the performance in the partial least squares (PLS) modeling were compared for different ambient environments. The results showed that argon not only improved the intensity, but also reduced signal fluctuation. The PLS model also had the optimal performance in multi-element analysis using argon as ambient gas. The root mean square error of prediction of carbon concentration decreased from 4.25% in air to 3.49% in argon, while the average relative error reduced from 4.96% to 2.98%. Hydrogen line demonstrated similar improvement. Yet, the nitrogen lines were too weak to be detected even in an argon environment which suggested the nitrogen signal measured in air come from the breakdown of nitrogen molecules in the atmosphere.     

Production of Capacitively Coupled Atmospheric Plasma Jet With Multiring Electrodes for the Medical Plasma Tool

An atmospheric capacitively coupled plasma jet has been developed by using multiring-electrode configurations for medical applications. It was found that the discharge conditions for plasma-jet production expanded with the increase of the number of pairs of multiring electrodes. The length of the plasma jet increased with the increase of the injected power and helium-gas flow rate. The temperature of the plasma jet, measured by a thermocouple, decreased with the increase of gas flow rate and was then attained to be around 50 $^{circ}hbox{C}$ at a helium flow rate of 30 L/min. Optical measurements of plasma-jet emission showed various optical emissions from helium atoms, nitrogen atoms, hydroxyl radicals, and metal atoms originating from the electrode material.      

激光烧蚀高纯Zn形成的微米金属球体对后续脉冲激光的耦合增强效应

脉冲激光束在低真空(约2 Pa)环境下聚焦到高纯Zn靶表面, 烧蚀区域不仅有中心深孔的宏观损伤, 而且还发现大量微米量级的类似足球形状的金属Zn球体结构附着生长在孔洞内侧表面. 实验过程中采用等离子体光谱诊断技术研究宏观和微观损伤对后续脉冲激光的影响程度. 与聚焦于金属Zn平滑表面相比, 宏观损伤可以使后续激光诱导的Zn原子334.5 nm谱线强度提高10.3%, 在此基础上大量Zn微米球体附着在内表面可以使谱线强度再提高34.3%. 因此, 推断这些金属Zn微球表面镶嵌着光洁的纳米量级六边形和五边形小平面, 可以对后续脉冲激光产生镜面反射, 使得激光能量汇聚并耦合增强, 提高烧蚀效率. 实验结果还表明, 这些微米球体的数目随着激光脉冲次数的增加而增多, 使得后续激光能够诱导产生更为致密高温的等离子体. 研究结果有望为激光-金属微孔技术提供新思路. 关键词： 脉冲激光烧蚀 微纳米结构 激光诱导等离子体