Sensitive absorption measurements of hydrogen sulfide at 1.578 μm using wavelength modulation spectroscopy

Sensitive detection of hydrogen sulfide(H2S) has been performed by means of wavelength modulation spectroscopy(WMS) near 1.578 μm. With the scan amplitude and the stability of the background baseline taken into account, the response time is 4 s for a 0.8 L multi-pass cell with a 56.7 m effective optical path length. Moreover, the linearity has been tested in the 0–50 ppmv range. The detection limit achievable by the Allan variance is 224 ppb within 24 s under room temperature and ambient pressure conditions. This tunable diode laser absorption spectroscopy(TDLAS) system for H2 S detection has the feasibility of real-time online monitoring in many applications.     

Novel method for correcting light intensity fluctuation in the TDLAS system

A novel method for online correction of light intensity fluctuation in a practical tunable diode laser ab-sorption spectroscopy(TDLAS)system with wavelength modulation is presented.The proposed method is developed according to the linear relation between peaks at multiple frequencies of sine modulation in the power spectral density of the demodulated second-harmonic(2f)signal and the incident light intensity.Those peaks are demonstrated experimentally and explained as residual power at the first-harmonic and third-harmonic frequencies after 2f demodulation of the residual amplitude modulation signal due to the limited integrating time constant of the lock-in-amplifier.This method can achieve real-time correction of light intensity fluctuations with only little calculation.It can work well in a very large range of light intensity and has great potential applications in the wavelength modulation spectroscopy system.     

Large scale gas leakage monitoring with tunable diode laser absorption spectroscopy

Tunable diode laser absorption spectroscopy (TDLAS) has been widely employed in atmospheric trace gases detecting and industrial control due to its high sensitivity, selectivity, and rapidity of response. An open path TDLAS system is developed for monitoring large scale methane leakage around the oil refinery. The tunable distributed feedback (DFB) diode laser emits at 1.65 fun. In order to enhance the sensitivity, a system combining long open path and second harmonic detection technique is developed. The test results show that the time resolution is less than 0.1 second and the detection limit is lower than 3.6 ppmv. This system is adapted for monitoring a large scale methane concentration changing trend instead of measuring its absolute concentration.     

Large scale gas leakage monitoring with tunable diode laser absorption spectroscopy

Tunable diode laser absorption spectroscopy (TDLAS) has been widely employed in atmospheric trace gases detecting and industrial control due to its high sensitivity, selectivity, and rapidity of response. An open path TDLAS system is developed for monitoring large scale methane leakage around the oil refinery.The tunable distributed feedback (DFB) diode laser emits at 1.65μm. In order to enhance the sensitivity,a system combining long open path and second harmonic detection technique is developed. The test results show that the time resolution is less than 0.1 second and the detection limit is lower than 3.6 ppmv. This system is adapted for monitoring a large scale methane concentration changing trend instead of measuring its absolute concentration.     

Hydrogen sulphide detection using near-infrared diode laser and compact dense-pattern multipass cell

Sub-ppmv level detection of hydrogen sulphide(H_2 S) using a 1.578-μm distributed feedback tunable diode laser combining with wavelength modulation spectroscopy and second harmonic detection scheme is reported. A home-developed novel compact dense-pattern multipass gas cell with an effective optical path length of 29.37 m is used to improve sensitivity and reduce sample volume. Detection parameters are optimized, including modulation frequency and amplitude. The analysis of Allan variance shows that a minimum detectable concentration 60 ppbv is obtained with a lock-in time constant of 10 ms, and a detection limit of 13 ppbv can be achieved by average in 300 s. The demonstrated H_2 S sensor has a strong penitential application in natural gas process for regulating and controlling H_2 S concentration.     

High sensitivity refractive index gas sensing enhanced by surface plasmon resonance with nano-cavity antenna array

The surface plasmon resonance gas sensor is presented for refractive index detection using nano-cavity antenna array.The gas sensor monitors the changes of the refractive index by measuring the spectral shift of the resonance dip,for modulating the wavelength of incident light.It is demonstrated that minute changes in the refractive index of a medium close to the surface of a metal film,owing to a shift in the resonance dip of the wavelength,can be detected.The average detection sensitivity is about 3200 nm/RIU(refractive index units),which is more than twice that of a metal grating-based gas sensor.The reflectivity of the surface plasmon resonance dip is only ～ 0.03%,and the full widths at half maximum(FWHMs) of bandwidth of the angle and wavelength are ～ 0.20° and 4.71nm,respectively.     

Atmospheric N_2O gas detection based on an inter-band cascade laser around 3.939 μm

N_2O is a significant atmospheric greenhouse gas that contributes to global warming and climate change. In this work,the high sensitivity detection of atmospheric N_2O is achieved using wavelength modulation spectroscopy(WMS) with an inter-band cascade laser operating around 3.939 μm. A Lab VIEW-based software signal generator and software lock-in amplifiers are designed to simplify the system. In order to eliminate the interference from water vapor, the detection was performed at a pressure of 0.1 atm(1 atm = 1.01325×10~5 Pa) and a drying tube was added to the system. To improve the system performance for long term detection, a novel frequency locking method and 2 f/1 f calibration-free method were employed to lock the laser frequency and calibrate the power fluctuations, respectively. The Allan deviation analysis of the results indicates a detection limit of ～ 20 ppb(1 ppb = 1.81205 μg/m~3) for a 1 s integration time, and the optimal detection limit is ～ 5 ppb for a 40-s integration time.     

An approach of open-path gas sensor based on tunable diode laser absorption spectroscopy

Tunable diode laser absorption spectroscopy(TDLAS)is a new method to detect trace-gas qualitatively or quantificationally based on the scan characteristic of the diode laser to obtain the absorption spectroscopy in the characteristic absorption region.A time-sharing scanning open-path TDLAS system using two near infrared distributed feedback(DFB)tunable diode lasers is designed to detect CH_4 and H_2S in leakage of natural gas.A low-cost Fresnel lens is used in this system as receiving optics which receives the laser beam reflected by a solid corner cube reflector with a distance of up to about 60 m.High sensitivity is achieved by means of wavelength-modulation spectroscopy with second-harmonic detection.The minimum detection limits of 1.1 ppm·m for CH_4 and 15 ppm·m for H_2S are demonstrated with a total optical path of 120 m.The simulation monitoring experiment of nature gas leakage was carried out with this system. According to the receiving light efficiency of optical system and detectable minimum light intensity of detection,the detectable optical path of the system can achieve 1-2 km.The sensor is suitable for natural gas leakage monitoring application.     

Ultraviolet Raman lidar for high-accuracy profiling of aerosol extinction coefficient

An ultraviolet （UV） Raman lidar system at 354.7 nm has been developed for accurately measuring the aerosol extinction profiles. A spectroscopic filter combining a high-spectral-resolution grating with two narrowband mirrors is used to separate the vibrational Raman scattering signal of N2 at a central wavelength of 386.7 nm and the elastic scattering signal at 354.7 nm. The aerosol extinction is derived from the Raman scattering of N2 and the elastic scattering by the use of Raman method and Klett method, respectively. The derived results of aerosol extinction are used to compare the difference of two retrieval methods, and the preliminary experiment shows that the Raman lidar system operated in analog detection mode has the capability of measuring aerosol profiles up to a height of 3 km with a laser energy of 250 mJ and an integration time of 8 min.     

High-resolution Reflection Spectroscopy ofCs D_2 Line Studied by High-order-harmonic Detection

In this paper, by numerical analysis the relationship of the modulation broaden index with modulation index using high-order-harmonic detection is investigated. Using the voltage modulation the 2f,4f and 6f harmonic signals about the reflection spectroscopy of 6S1/2(F = 4) →6P3/2 transition of the cesium D2 line are also be measured. The experimental results are in good agreement with the theoretical predictions. It is found that narrower line-width can be achieved by higher-harmonic detection than the line-width detected by direct absorption when the modulation index is smaller than 1.81, 2.98 and 4.14 for 2f, 4f, and 6f signals, respectively.     

中红外痕量乙烷传感器设计与稳定性分析

根据乙烷气体分子在3.3 μm处的基频吸收特性,使用中心波长为3.337 μm室温连续带间级联激光器(ICL)和有效光程为54.6 m密集光斑多通气体吸收气室(600 mL)研制了基于波长调制光谱技术(WMS)的乙烷传感器。详细介绍了基于WMS和二次谐波(2f)探测技术的光谱吸收法气体检测原理,给出了目标乙烷气体吸收线的遴选细节。此项技术的使用减小了光功率漂移对系统的影响,使得系统最低检测下限(MDL)和稳定性能得到提升。结合原理框图,通过光学和电学两个模块分别详细介绍了乙烷传感系统设计方案,描述了自主研制的软、硬件单元和商用仪器的使用及其型号供他人参考,并给出传感器光学配置实物图。而且,为匹配激光波长调制与基于压力的吸收线宽,对气压和调制深度进行优化,研究了调制幅度对应2f信号峰值及调制幅度与调制深度的关系,最终确定最优气压和调制深度分别为100 Torr和0.074 cm-1,对应的调制信号幅度为~0.026 V。此外,基于优化后的气压和调制深度,使用136.8 nmol·mol-1 乙烷标准气体进行了系统灵敏度估算。详细介绍了ICL扫描调制信号、锁相放大及数据采集单元的参数设置,并给出示波器记录的扫描调制信号及2f信号波形图片。通过对比DAQ采集的2f信号和背景噪声信号,估算系统最低检测下限为33 nmol·mol-1。最后,使用9个不同浓度乙烷标准气体(20～400 nmol·mol-1)分别进行~5 min系统标定测试,并列出了拟合曲线和拟合相关度等信息。而且,使用浓度为48 nmol·mol-1乙烷气体样品开展连续2 h系统稳定性测试并进行Allan-Werle 方差分析。结果显示,该系统工作稳定,积分时间为4 s时,乙烷气体检测灵敏度为~0.81 nmol·mol-1。通过增加系统积分时间至63 s,系统灵敏度可被提高至~0.36 nmol·mol-1。     

便携式FTIR的机动车尾气检测方法

随着汽车排放标准的提高,相关VOC标准从总烃检测变为非甲烷碳氢化合物(NMHC)检测;随着含氧燃料的增加,增加了非甲烷有机气体(NMOG)测量。针对国内汽车尾气分析仪分析组分单一、精度有限、VOCs检测过程复杂等问题,提出了基于便携式FTIR的机动车尾气检测方法,基于立体角镜优化FTIR光学系统结构,提高动镜扫描速度,设计便携式且满足抗振动需求的快速FTIR光谱仪。FTIR红外光源输出波段范围为2～20 μm,分辨率为0.5 cm-1,扫描速度1 Hz,气体池光程为10 m,采用斯特林探测器,其光谱响应范围为600～6 000 cm-1。选择CH₄,C₂H₂,C₂H₄,C₂H₆,C₃H₆,n-C₅H₁₂,i-C₅H₁₂,C₇H₈,HCHO,C₂H₅OH,CH₃CHO这些典型HC化合物作为VOC气体检测的替代物。通过标准谱确定尾气成分的波段为900～1 100和2 700～3 100 cm-1,涵盖所有待测气体吸收波段。基于AVL台架测试,开展NEDC和WLTC工况实验测试,测试车辆为丰田威驰,测试油品为92号国五。便携式FTIR采用抽取方式进行尾气测量,原始的废气样本来自安装在排气管延长部分的多孔探头,前端安装样气取样装置,主要包括颗粒物过滤和除水汽装置,以防止污染FTIR光学系统。实验表明FTIR可以有效快速测量汽车尾气中CO,CH₄,NO和主要HC化合物,在FTIR检测限0.5 μmol·mol-1下会引入噪声信号,浓度可信度降低。通过分析可以看出输出气体平均浓度降级排列依次是：CO,C₂H₄,CH₄,NO,i-C₅H₁₂,C₂H₆,C₇H₈,n-C₅H₁₂,C₂H₅OH,CH₃CHO。从3个循环的NEDC工况可以看出,每种气体排放呈现一致的规律性变化。针对CO进行了SEMTECH-DS与FTIR测量数据的时间序列比较,结果呈现了较好的规律一致性,但是由于FTIR和SEMTECH-DS测量技术和取样稀释系统不同导致二者浓度差异较大。与传统尾气检测技术相比,便携式FTIR测量系统对瞬态事件有良好的响应,可以在线进行多组分浓度实时测量获取机动车的瞬时排放数据,在满足新规测试要求下,也可以为后期的机动车在实际道路上的排放特征分析和模拟提供可靠的数据支持。     

Auger electron spectroscopy and electron energy loss spectroscopy studies on carbonization of Si(100) and (111) surfaces with ethylene

The reactions of Si(100) and Si(111) surfaces at 700 °C (973 K) with ethylene (C₂H₄) at a pressure of 1.3×10⁻⁴ Pa for various periods of time were studied by using Auger electron spectroscopy (AES) and electron energy loss spectroscopy (ELS). For a C₂H₄ exposure level, the amount of C on the (111) surface was larger than that on the (100) surface. The formation of β-SiC grain was deduced by comparing the C_KLL spectra from the sample subjected to various C₂H₄ exposure levels, and from β-SiC crystal.     

取代环戊二烯锆、铪络合物光解活泼自由基的ESR研究

本文用自旋捕捉术技与ESR相结合的方法,研究取代环成二烯锆、铪络物(RC₅H₄)₂ZrCl₂(R=H,CH₃,C₃H₇,C₄H₉,C₅H₁₁,C₆H₁₁)及(RC₅H₄)₂HfCl₂(R=CH₃,C₂H₅,C₃H₇)光解的活泼自由基。结果表明,取代环成二烯锆、铪络合物与取代环戊二烯钛结合物光解机理相同,即光解初级过程是M-(RC₅H₄)(M=Ti,Zr,Hf)π键的均裂。其差别在于RCpMCl₂(M=Zr,Hf)可为PBN及ND捕获,并后者的加合物表现出氯核的分裂。     

取代环戊二烯钛络合物光解活泼自由基的研究

本文用自旋捕捉技术与ESR相结合的方法,研究取代环戊二烯钛络合物(RC₅H₄)₂TiCl₂(R=H,CH₃,C₂H₅,C₃H₇,C₅H₁₁,C₆H₁₁)光解的活泼自由基。结果表明,光解初级过程是Ti-(RC₅H₄)π键均裂,以生成(RC₅H₄)^·和(RC₅H₄) TiCl₂。(RC₅H₄)^·可为ND捕捉,并生成两种自由基加合物,其浓度比约为1:1。     

高气压直流辉光CH4/H2等离子体的气相过程诊断

对高气压(约100 Torr) 直流辉光碳氢等离子体的气相过程进行了光谱和质谱原位诊断. 在高气压下, 等离子体不同区域光发射特性存在明显差异. 正柱区存在着以C₂和CH为主的多个带状谱和分立谱线, 阳极区粒子发射谱线明显减少, 而在阴极区则出现大量复杂的光谱成分, 表明高气压情形下等离子体与阴极间强烈的相互作用将导致复杂的原子分子过程. 从低气压到高气压演变过程中, 电子激发温度降低而气体分子转动温度升高. 在高气压下, 高甲烷浓度导致C₂, C₂H₂及C₂H₄增多而C₂H₆减少. 表明在高气压条件下, 气体温度对气相过程的影响作用显著增强. 关键词： 高气压直流等离子体 光发射谱 质谱     

光声光谱多组分气体分析仪的交叉干扰特性研究

设计了一套基于红外热辐射光源的光声光谱多组分气体分析仪.通过分析多组分气体间交叉干扰的主要因素以及特征气体的红外吸收谱线,确定了中红外带通滤光片的参数.利用标准气体对设计的光声光谱仪进行标定,研究了待测气体之间交叉干扰的定量关系,并利用湿度发生器对装置受到水气干扰情况进行分析.实验结果表明,C2H2对CH4、CH4对C...     

基于近红外TDLAS变压器油中溶解气体在线检测装置

变压器绝缘油以链烷烃（C_nH_2n+2）为主要化学成分,在变压器长期运行过程中因电弧、放电、过热、受潮等原因导致化学键逐步发生断裂,产生与故障有关的故障判别气体（CH₄,C₂H₂,C₂H₄,C₂H₆,CO和CO₂）,因此变压器绝缘油中会溶解多组分气体,故需要一种多组分气体的在线检测装置,以保证变压器的正常运行。针对电力行业装配需求,研制基于可调谐激光吸收光谱法（TDLAS）多组分气体的在线检测装置。针对6种故障特征气体的近红外吸收波段,分别选取1 580,1 654,1 626和1 530 nm四个近红外激光器,使用分时扫描的时分多路技术,实现对多组分气体的分时快速顺序检测并采用波长调制技术,消除背景气体的交叉干扰。主要检测气体为绝缘油化学键断裂所产生的烃类化合物（CH₄,C₂H₂,C₂H₄和C₂H₆）和碳氧化合物（CO和CO₂）。在线检测,与变压器油气象色谱测量方法进行对比实验,并对其进行工况稳定性测试。实验结果表明：乙炔浓度测量范围为0.5~1 000 μL·L-1,范围小于5 μL·L-1时最大测量误差小于0.8,5~1 000 μL·L-1时最大误差在6 μL·L-1以下;甲烷、乙烷、乙烯的浓度测量范围为0.5~1 000 μL·L-1,最大测量误差小于6 μL·L-1;碳氧化合物（CO和CO₂）测量范围分别为25～5 000,25～15 000 μL·L-1,最大测量误差分别在2与20 μL·L-1以下。所设计的近红外TDLAS多组分气体检测装置能够用于变压器油中溶解气体的在线检测,测量的气体浓度满足在线检测要求,能够稳定运行且适应恶劣工况条件,为检测变压器油中溶解气体在线测量提供了有效的实践经验。     

双重频率锁定的腔衰荡吸收光谱技术及信号处理

针对传统腔衰荡光谱技术浓度获取率低,提出基于双重锁定的连续波腔衰荡吸收光谱技术.通过波长调制一次谐波信号将激光器的频率锁定到C_2H_2吸收线上,同时使用PDH锁频技术将衰荡腔锁定到激光器上,从而避免了测量过程中激光器的频率漂移和腔长的抖动,使测量结果更加精确;并且,由于双重锁定,单次衰荡事件的发生率,也就是浓度信息的获取率只受衰荡时间以及重新锁定时间限制,在本试验系统中采集速率可以达到30 k Hz,可以实现对气体浓度的快速测量.为了提高信噪比,采用Kalman滤波技术,对浓度信息进行实时处理,有效抑制了噪声,根据阿伦方差分析,探测灵敏度可以达到4×10~(-9)cm~(-1)(2 s平均).     

Superhard nanocomposite nc-TiC/a-C:H film fabricated by filtered cathodic vacuum arc technique

Superhard nanocomposite nc-TiC/a-C:H films, with an excellent combination of high elastic recovery, low friction coefficient and good H/E ratio, were prepared by filtered cathodic vacuum arc technique using the C₂H₂ gas as the precursor. The effect of C₂H₂ flow rate on the microstructure, phase composition, mechanical and tribological properties of nanocomposite nc-TiC/a-C:H films have been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy disperse spectroscopy (EDS), microindentation and tribotester measurements. It was observed that the C₂H₂ flow rate significantly affected the Ti content and hardness of films. Furthermore, by selecting the proper value for C₂H₂ flow rate, 20 sccm, one can deposit the nanocomposite film nc-TiC/a-C:H with excellent properties such as superhardness (66.4 GPa), high elastic recovery (83.3%) and high H/E ratio (0.13).