Influence of laser intensity in second-harmonic detection with tunable diode laser multi-pass absorption spectroscopy

Tunable diode laser absorption spectroscopy （TDLAS） has been widely employed in atmospheric trace gases detection. The ratio of the second-harmonic signal to the intensity of laser beam incident to the multi-pass cell is proved to be proportional to the product of the path length and the gas concentration under any condition. A new calibration method based on this relation in TDLAS system for the measurement of trace gas concentration is proposed for the first time. The detection limit and the sensitivity of the system are below 110 and 31ppbv （parts-per-billion in volume）, respectively.

Measurements of argon metastable density using the tunable diode laser absorption spectroscopy in Ar and Ar/O2

Densities of Ar metastable states 1s5 and 1s3 are measured by using the tunable diode laser absorption spectroscopy（TDLAS） in Ar and Ar/O2 mixture dual-frequency capacitively coupled plasma（DF-CCP）. We investigate the effects of high-frequency（HF, 60 MHz） power, low-frequency（LF, 2 MHz） power, and working pressure on the density of Ar metastable states for three different gas components（0%, 5%, and 10% oxygen mixed in argon）. The dependence of Ar metastable state density on the oxygen content is also studied at different working pressures. It is found that densities of Ar metastable states in discharges with different gas components exhibit different behaviors as HF power increases. With the increase of HF power, the metastable density increases rapidly at the initial stage, and then tends to be saturated at a higher HF power. With a small fraction（5% or 10%） of oxygen added in argon plasma, a similar change of the Ar metastable density with HF power can be observed, but the metastable density is saturated at a higher HF power than in the pure argon discharge. In the DF-CCP, the metastable density is found to be higher than in a single frequency discharge, and has weak dependence on LF power. As working pressure increases, the metastable state density first increases and then decreases,and the pressure value, at which the density maximum occurs, decreases with oxygen content increasing. Besides, adding a small fraction of oxygen into argon plasma will significantly dwindle the metastable state density as a result of quenching loss by oxygen molecules.

Quantitative measurement of hydroxyl radical(OH) concentration in premixed flat flame by combining laser-induced fluorescence and direct absorption spectroscopy

An accurate and reasonable technique combining direct absorption spectroscopy and laser-induced fluorescence（LIF）methods is developed to quantitatively measure the concentrations of hydroxyl in CH;/air flat laminar flame. In our approach, particular attention is paid to the linear laser-induced fluorescence and absorption processes, and experimental details as well. Through measuring the temperature, LIF signal distribution and integrated absorption, spatially absolute OH concentrations profiles are successfully resolved. These experimental results are then compared with the numerical simulation. It is proved that the good quality of the results implies that this method is suitable for calibrating the OH-PLIF measurement in a practical combustor.

Laser absorption spectroscopy for high temperature H_2O time-history measurement at 2.55 μm during oxidation of hydrogen

Concentration time-histories of H20 were measured behind reflected shock waves during hydrogen combustion. Experiments were conducted at temperatures of 1117-1282 K, the equivalence ratios of 0.5 and 0.25, and a pressure at 2 atm using a mixture of H2/O2 highly diluted with argon. H2O was monitored using tunable mid-infrared diode laser absorption at 2.55 μm （3920.09 cm-1）. These time-histories provide kinetic targets to test and refine reaction mechanisms for hydrogen. Comparisons were made with the predictions of four detailed kinetic mechanisms published in the last four years. Such comparisons of H2O concentration profiles indicate that the AramcoMech 2.0 mechanism yields the best agreement with the experimental data, while CRECK, San Diego, and HP-Mech mechanisms show significantly poor predictions. Reaction pathway analysis for hydrogen oxidation indicates that the reaction H ＋ OH ＋ M = H20 ＋ M is the key reaction for controlling the H2O formation by hydrogen oxidation. It is inferred that the discrepancy of the conversion percentage from H to H20 among these four mechanisms induces the difference of performance on H2O time-history predictions. This work demonstrates the potential of time-history measurement for validation of large reaction mechanisms.

Self-Absorption Effects on Electron Temperature-Measurements Utilizing Laser Induced Breakdown Spectroscopy (LIBS)-Techniques

In the present work, we have studied the temporal evolution of aluminum alloy plasma produced by the fundamental (1064 nm) of a Q-switched Nd:YAG laser by placing the target material in air at atmospheric pressure. The four Al I-neutral lines at 308.21, 309.27, 394.40 and 369.15 nm as well as Al II-ionic lines at 281.61, 385.64 and 466.30 nm are used for the determination of the electron temperature Te using Saha-Boltzmann plot method. The neutral aluminum lines were found to suffer from optical thickness which manifested itself on the form of scattered points around the Saha-Boltzmann line. The isolated optically thin hydrogen Hα-line at 656.27 nm appeared in the spectra under the same experimental conditions was used to correct the Al I-lines which contained some optical thickness. The measurements were repeated at different delay times ranging from 1 to 5 μs. The comparison between the deduced electron temperatures from aluminum neutral lines before correction against the effect self-absorption to that after correction revealed a precise value in temperature. The results sure that, in case of the presence of self-absorption effect the temperature varies from (1.4067 - 1.2548 eV) as the delay time is varied from 0 to 5 μs. Whereas, in the case of repairing against the effect, it varies from (1.2826 - 0.8961 eV) for the same delay time variation.

Consistency of intensity ratio between spectral lines with similar self-absorption characteristics during ungated laser induced breakdown spectroscopy measurements

This work reports that the intensity ratio of spectral lines having similar self-absorption characteristics during laser induced breakdown spectroscopy(LIBS) analysis can become nearly constant over a wide range of irradiation conditions if the intensities are integrated over a sufficiently long time. It is shown that the plasma temperature and intensity ratio of these spectral lines have temporal similarity. The spectral lines with similar self-absorption properties may be selected to improve the accuracy and consistency of LIBS analysis results under an environment with fluctuating measurement conditions.

fast neutron absorption spectroscopy;laser plasma accelerator;photo-nuclear neutrons;single neutron count

Fast neutron absorption spectroscopy is widely used in the study of nuclear structure and element analysis. However,due to the traditional neutron source pulse duration being of the order of nanoseconds, it is difficult to obtain a high-resolution absorption spectrum. Thus, we present a method of ultrahigh energy-resolution absorption spectroscopy via a high repetition rate, picosecond duration pulsed neutron source driven by a terawatt laser. The technology of single neutron count is used, which results in easily distinguishing the width of approximately 20 keV at 2 MeV and an asymmetric shape of the neutron absorption peak. The absorption spectroscopy based on a laser neutron source has one order of magnitude higher energy-resolution power than the state-of-the-art traditional neutron sources, which could be of benefit for precisely measuring nuclear structure data.

Low temperature laser absorption spectra of methane in the near-infrared at 1.65 μm for lower state energy determination

Direct absorption spectra of the 2v3 band of methane （CH4） from 6038 to 6050 cm 1 were studied at different low temperatures using a newly developed cryogenic cell in combination with a distributed feedback （DFB） diode laser. The cryogenic cell can operate at any stabilized temperature ranging from room temperature down to 100 K with temperature fluctuation less than =t=1 K within 1 hour. In the present work, the CH4 spectra in the range of 6038-6050 cm-1 were recorded at 296, 266, 248, 223, 198, and 176 K. The lower state energy Ett and the rotational assignment of the angular momentum J were determined by a ＂2-low-temperature spectra method＂ using the spectra recorded at 198 and 176 K. The results were compared with the data from the GOSAT and the recently reported results from Campargue and co-workers using two spectra measured at room temperature and 81 K. We demonstrated that the use of a 2-low-temperature spectra method permits one to complete the Ett and J values missed in the previous studies.

Analysis of Pulverized Coal by Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy （LIBS） has been used to detect atomic species in various enviromnents. The quantitative analysis （C, H, O, N and S） of representative coal samples are being carried out with LIBS, and the effects of particle size are analyzed. A powerful pulse Nd：YAG laser is focused on the coal sample at atmosphere pressure, and the emission spectra from laser-induced plasmas are measured by time-resolved spectroscopy, and the intensity of analyzed spectral lines is obtained through observing the laser plasma with a delay time of 0.4 #s. The experimental results show that the slope of calibration curve is nearly 1 when the concentration of the analyzed element is relatively low, and the slope of curve is nearly 0.5 when the concentration of C is higher than other elements. In addition, using the calibration-free model without self-absorption effect, the results show that the decreasing of particle size leads to an increase of the plasma temperature.

Mechanisms and efficient elimination approaches of self-absorption in LIBS

Laser-induced breakdown spectroscopy(LIBS) is a promising analytical spectroscopy technology based on spectroscopic analysis of the radiation emitted by laser-produced plasma.However, for quantitative analysis by LIBS, the so-called self-absorption effects on the spectral lines, which affect plasma characteristics, emission line shapes, calibration curves, etc, can no longer be neglected. Hence, understanding and determining the self-absorption effects are of utmost importance to LIBS research. The purpose of this review is to provide a global overview of self-absorption in LIBS on the issues of experimental observations and adverse effects,physical mechanisms, correction or elimination approaches, and utilizations in the past century.We believe that better understanding and effective solving the self-absorption effect will further enhance the development and maturity of LIBS.

Effect of parameter setting and spectral normalization approach on study of matrix effect by laser induced breakdown spectroscopy of Ag–Zn binary composites

The complex nature of laser-material interaction causes non-stoichiometric ablation of alloy samples.This is attributed to matrix effect, which reduces analyzing capability. To address this issue, the analytical performance of three different normalization methods, namely normalization with background, internal normalization and three point smoothing techniques at different parameter settings is studied for quantification of Ag and Zn by Laser induced breakdown spectroscopy(LIBS).The LIBS spectra of five known concentration of silver zinc binary composites have been investigated at various laser irradiances(LIs). Calibration curves for both Ag(I) line(4d^(10)5s^2S_(1/2)→4d^(10)5p^2P_(1/2) at 338.28 nm) and Zn(I) line(4s5s^3S_1→4s4p^3P_2 at 481.053 nm) have been determined at LI of 5.86?×?10^(10)W cm^(-2). Slopes of these calibration curves provide the valuation of matrix effect in the Ag–Zn composites. With careful sample preparation and normalization after smoothing at optimum parameter setting(OPS), the minimization of sample matrix effect has been successfully achieved. A good linearity has been obtained in Ag and Zn calibration curve at OPS when normalized the whole area of spectrum after smoothing and the obtained coefficients of determination values were R^2?=?0.995 and 0.998 closer to 1. The results of matrix effect have been further verified by analysis of plasma parameters. Both plasma parameters showed no change with varying concentration at OPS. However, at high concentration of Ag, the observed significant changes in both plasma parameters at common parameter setting PS-1 and PS-2 were the gesture of matrix effect. In our case, the better analytical results were obtained at smoothing function with optimized parameter setting that indicates it is more efficient than normalization with background and internal normalization method.

Absorption Line Profile Recovery Based on TDLS and MEMS Micro-Mirror for Photoacoustic Gas Sensing

A novel and efficient absorption line recovery technique is presented.A micro-electromechanical systems(MEMS) mirror driven by an electrothermal actuator is used to generate laser intensity modulation through the mirror reflection.Tunable diode laser spectroscopy(TDLS) and photoacoustic spectroscopy(PAS) are used to recover the target absorption line profile which is compared with the theoretical Voigt profile.The target gas is 0.01% acetylene(C2H2) in a nitrogen host gas.The laser diode wavelength is swept across the P17 absorption line of acetylene at 1 535.4 nm by a current ramp,and an erbium-doped fibre amplifier(EDFA) is used to enhance the optical intensity and increase the signal-to-noise ratio(SNR).A SNR of about 35 is obtained with 100 mW laser power from the EDFA.Good agreement is achieved between the experimental results and the theoretical simulation for the P17 absorption line profile.

Effect of Temperature on Optical Properties of Vegetable Oils Using UV-Vis and Laser Fluorescence Spectroscopy

UV-Vis absorption and fluorescence spectroscopy are used to test the quality and changes in the composition of extra virgin olive oil (EVOO) and canola oil (CO) with temperature. The increase of temperature caused a change in the molecular structures of both types of oils seen as a gradual decrease of intensity amplitudes of absorption and fluorescence signals. A significant alteration occurred at ≈200&#176C where almost the main spectra of pheophytin-a, b, carotenoids, lutein and vitamin E in EVOO and linoleic acid and oleic acid in CO disappeared. An independent experiment showed the output of laser changes linearly with the input in oil at constant temperature (i.e., room temperature) where the transmission values of ≈33% and ≈75% are determined for EVOO and CO respectively. However, the transmission through a heated oil exhibited a non-linear behaviour which indicates the molecular optical response to thermal changes. The effect of storage time and adulteration of oils were also evaluated.

Calculation of Complete Absorption and Intensity of Optical Radiation Spectrum of HeI (λ= 5875Å) with Fine Structure

Theoretical calculations which account for the complete absorption and intensity for the optical radiation He I (λ= 5875 ?) spectral line with fine structure of the transition 23P2,1,0 - 33D3,2,1 during He nanosecond discharge are presented. For different values of the absorption parameter (χ 0?), the absorption quantity A of the three components distorted as a result of reabsorption multiple process has been numerically obtained and graphically presented. The theoretical results for small values of χ 0? (≤4) give a good agreement with the experimental data in literature.

Spectroscopy system based on a single quantum cascade laser for simultaneous detection of CO and CO_2

A quantum cascade laser（QCL） based system for simultaneous detection of CO and CO_2 is developed.The QCL can scan over two neighboring CO（2055.40 cm^（-1）） and CO_2（2055.16 cm^（-1）） lines with a single current scan.The wavelength modulation spectroscopy（ f = 20 k Hz） is utilized to enhance the signal-to-noise ratio.A white cell with an effective optical path length of 74 m is used.The calibration of the sensor is performed and minimum detection limits of 1.3 ppb（1 × 10^（-9））for CO and 0.44 ppm（1 × 10^（-6）） for CO_2 are achieved.

基于VisuShrink小波阈值变换的甲烷检测降噪技术

在利用可调谐半导体激光吸收光谱技术探测甲烷气体泄漏时,复杂的环境光干扰会降低浓度检测信号的信噪比使波形失真。为了抑制噪声,增强电信号与浓度值的线性相关度,提出一种以VisuShrink方法改善小波阈值函数的小波阈值去噪算法。该算法针对小波阈值去噪算法的软硬度不能平衡信号,存在失真的问题,利用统计方法对阈值进行计算,弱化间断点阈值跳变影响。通过仿真计算对比未加噪声前的信号与滤波后的信号,提出算法的信噪比为28.405 30,优于四阶巴特沃斯滤波器。VisuShrink方法在SNR和NCC参数上性能远优于巴特沃斯滤波器,与软阈值函数相近,在MSE均方误差分析上远小于软阈值精度,与巴特沃斯相近,具有较好的平滑特性。实际搭建检测平台对多个浓度样本采样进行多次采样,采用VisuShrink方法设计的滤波器将系统误差精度从4.14%提升至2.472%,算法可有效用于甲烷检测系统提高光谱数据的平滑性和准确性。

高重频声光门控自吸收免疫激光诱导击穿光谱技术分析研究

为了消除激光诱导击穿光谱技术(laser-induced breakdown spectroscopy,LIBS)中的自吸收效应,提高元素定量分析的精确度,同时满足工业中便捷分析元素的要求,需将自吸收免疫激光诱导击穿光谱技术(self-absorption free laser-induced breakdown spectroscopy,SAF-LIBS)的装置小型化。本文提出了一项新型的高重频声光门控SAF-LIBS定量分析技术,使用高重频激光器产生准连续的等离子体以增强光谱强度,并将声光调制器(acousto-optic modulator,AOM)作为门控开关,从而使微型CCD光谱仪和AOM能够代替传统大型SAF-LIBS装置中的像增强探测器(intensified charge coupled device,ICCD)和中阶梯型光栅光谱仪,实现自吸收免疫的同时缩小了装置的体积,降低了装置的成本。将该系统参数进行优化选择后,对样品中的Al元素进行了定量分析和预测。实验结果表明,等离子体的特性受激光重复频率的影响进而会影响光谱信号的强度。在1~50 kHz激光重复频率范围内,Al I 394.4 nm和Al I 396.15 nm的双线强度先增强后减弱,确定最佳的激光重复频率为10 kHz。在不同的光纤采集角度下,Al的双线强度比随延迟时间的增加而减小,在45°处信噪比最高,且在一定的积分时间下,最佳光学薄时间t_(ot)为426 ns。在激光重复频率为10 kHz、光纤采集角为45°、延迟时间为400 ns的条件下,对Al元素进行定量分析和预测结果表明,Al元素定标曲线的线性度R2为0.982,平均绝对测量误差相对于单一LIBS的0.8%可以降低至0.18%。定量分析结果与传统大型SAF-LIBS装置的测量精度相持平。因此本高重频声光门控SAF-LIBS装置不仅有效地屏蔽了光学厚等离子体中的连续背景辐射和谱线加宽,同时具备小型化、低成本、高可靠性的优点,有助于推动SAF-LIBS技术由实验室走向工业应用。

小型化中红外直接吸收CO_(2)光谱仪

二氧化碳(Carbon Dioxide,CO_(2))是一种关键的温室气体,对地球气候和生态系统调节有重要作用,准确检测痕量CO_(2)浓度对评价温室效应意义重大。一般情况下,气体分子在中红外光谱范围存在强吸收,可以实现高灵敏探测,因此,以4.219μm中红外波段的带间级联激光器为光源结合可调谐半导体激光吸收光谱技术(Tunable Diode Laser Absorption Spectroscopy,TDLAS)设计了小型化CO_(2)监测仪器。在不同标气浓度下对仪器进行了标定,并通过分析Allan方差,得出积分时间在8.7 s时对应的最低检测限为16.6×10^(-9),满足温室效应研究对CO_(2)气体的高灵敏测量需求。采用仪器对大气CO_(2)连续监测8天,并与商用仪器LGR进行对比,充分验证了小型化CO_(2)监测仪器的可靠性,以及中红外光源与TDLAS技术相结合的气体浓度检测方法在大气CO_(2)准确测量方面的可行性。该系统具有结构简单、体积小、功耗低和质量轻的特点,为建设空基无人机平台的CO_(2)监测能力提供了技术支持。