光纤倏逝波型石英增强光声光谱技术

采用块状光学准直聚焦透镜组的传统石英增强光声光谱(QEPAS)技术存在体积难以缩减,结构稳定性不佳,无法适应空间狭小、振动复杂的特殊环境等缺点.基于此,将光纤倏逝波技术与QEPAS技术相结合,提出了一种新型微纳结构光纤QEPAS痕量气体检测技术.实验中,为了提高QEPAS系统信号幅值,优化了石英音叉与激光束的空间位置、激光波长调制深度,同时对比了两种不同共振频率的石英音叉,最终采用共振频率较低的30.720 kHz石英音叉作为声波探测元件,获得的检测极限为6.25×10~(-4)(体积分数),归一化噪声等效吸收系数为4.18×10~(-7)cm~(-1).W·Hz~(-1/2).     

Open-path measurement of ozone and methane gases using quartz-enhanced photoacoustic spectroscopy

We demonstrate a standoff system based on quartz-enhanced photoacoustic spectroscopy technique for the concentration measurements of atmospheric ozone and methane. The technique is a modified version of Photoacoustic spectroscopy. Two primary features of this technique are the employment of a tunable quantum cascade laser and a resonant quartz-crystal tuning fork detector. Both of these features facilitate simultaneous sensing of multiple molecular species. External-cavity quantum cascade laser having a spectral range from 7 to 10 micron is used. Diurnal concentration variations of methane and ozone are estimated for open-path up to 25 m. The ambient methane and ozone concentration maxima were observed to have values of 3.5 parts per million by volume and 140 parts per billion by volume, respectively. Finite-element mesh-based software is used to simulate the Eigen frequency of the tuning fork sensor. High-resolution transmission molecular spectroscopic database of atmospheric gases and the real-time gas concentration data from the Delhi Pollution Control Committee have been used as references.     

Theoretical analysis of off beam quartz-enhanced photoacoustic spectroscopy sensor

Off beam quartz-enhanced photoacoustic spectroscopy (OB-QEPAS) sensors are based on a recently developed approach to off-beam photoacoustic (PA) detection which employs a quartz tuning fork (QTF) as an acoustic transducer. A microresonator (mR) with a side slit in the middle is used to enhance PA signal. This paper describes a theoretical model of an OB-QEPAS-based sensor. By deriving the acoustic impedances of the mR at two ends and the side slit in the middle in the model, we obtain a formula for numerically calculating the optimal mRs' parameters of OB-QEPAS-based sensor. We use the model to calculate the optimal mRs' lengths with respect to the resonant frequency of the QTF, acoustic velocities inside mRs, inner diameters of mRs, and acoustic conductivities of the mRs' side slits, and found out that the calculated results closely match experimental data. We also investigated the relationship between the mR selected in “on beam” QEPAS, OB-QEPAS, and an acoustic resonator (AR) excited in its first longitudinal mode used in conventional photoacoustic spectroscopy (PAS).     

灵敏的基于分布反馈式半导体激光波长调制光声光谱

利用室温下单模运行的近红外半导体二极管激光,报导了波长调制共振光声光谱结合二次谐波探测技术.实验系统应用到乙炔探测,在1个标准大气压和3毫瓦平均光功率以及3毫秒锁相积分时间条件下其探测灵敏度可达10ppm(体积比),归一化到激光功率和系统带宽最小可探测吸收为4.0×10-8Wcm-1/Hz,并且实验中发现系统最佳压力响应值在2.66×104Pa附近.本实验装置可有效的消除光声光谱系统中常见的窗片和光声腔壁吸收入射光而引起的背景噪声.此外,相对于其他方法我们描述的基于半导体激光共振光声光谱具有很大的优点,为进一步发展便利、实用、便携式环境监测仪器奠定了坚实的基础.     

非标定波长调制吸收光谱气体测量研究

为消除可调谐激光调制吸收光谱气体测量技术对于标定过程的依赖,研究了二次谐波信号的非标定波长调制气体测量方法.通过对测量的二次谐波线型进行分析,给出相同工况下二次谐波模拟信号,并利用测量与模拟二次谐波信号进行线性拟合直接计算气体浓度.实验室内采用非标定波长调制气体测量方法,利用 6336.24 cm^-1处特征吸收谱线对10 cm长气体吸收池内的CO₂进行了测量.结果表明,非标定波长调制气体测量方法可适应各种不同条件,适合于现场气体在线测量.当调制系数在1.8—3. 关键词： 波长调制 二次谐波 吸收光谱 半导体激光器     

基于中红外量子级联激光器和石英增强光声光谱的CO超高灵敏度检测研究

采用石英增强光声光谱(QEPAS)技术对CO痕量气体展开检测研究. 为了实现超高灵敏度探测, 采用输出波长为4.6 μm的新颖中红外高功率分布反馈量子级联激光器为光源, 实现了对CO气体基频吸收带的激发与测量. 在优化了调制深度、气体压强和提高了CO分子的振动-转动弛豫速率后, 获得了1.95 ppbv的优异探测极限. 在分析检测结果的过程中, 讨论了能级寿命对信号强度的影响, 并对QEPAS信号强度的表达式进行了修正.     

Calibration-free wavelength modulation spectroscopy for gas concentration measurements under low-absorbance conditions

<正>We derive the expressions of the first and second harmonic signals on the basis of absorption spectral and lock-in theories,and determine the gas concentration according to the ratio of second and first harmonic signals.It is found that the X and Y components of the harmonic signals are influenced by the phase shift between the detection and reference signal,and the phase shift can be any value in a range from 0 to 2π,which is different from the results obtained previously.Meanwhile,an additional item caused by the residual amplitude modulation will make a great contribution to the second harmonic signal,and may not be neglected under low absorbance conditions.Theoretical analysis indicates that subtracting back-ground signal from the second harmonic signal can remove the influence of this item,and can improve the measurement accuracy of gas concentration.On this basis,we select the transition of CO₂ at 6527.64 cm^-1 to analyse the approximation errors during the derivation by numerical simulation and then measure the CO₂ concentration under low absorbance conditions,with absorbance varying from l%o to 6‰.     

基于微型非共振腔的石英增强光声光谱用于氦气纯度分析的实验研究

实验中设计了一种基于微型非共振腔的石英增强光声光谱痕量气体传感器, 用来检测非纯氦气中的痕量氨气浓度. 该传感器采用的微型非共振腔只在空间上限制声波扩散以达到增强信号目的, 而不是像传统微型共振腔一样依靠共振效应. 如此的设计使探测小分子无机气体的光谱测声器尺寸远远小于共振腔的配置而有利于准直. 不同气压下的信号和噪声也被研究, 用来优化传感器性能. 在这种配置下和27.7 kPa的最优气压下, 获得的最佳氨气探测灵敏度为463 ppb (1σ , 1 s积分时间), 相应的归一化噪声等效吸收系数为4.3×10^-9cm^-1W/√Hz. 关键词： 气体传感器 石英增强光声光谱 音叉式石英晶振 类氢气体纯度分析     

Application of α——β——γ filtering to real-time atmosphere methane concentration measurement

A real time $\alpha$--$\beta$--$\gamma$ filtering technique is applied to the monitoring of atmosphere CH可调二极管激光吸收光谱 谐波检测 物理光学 激光技术tunable diode laser absorption spectroscopy, multi-pass cell, harmonic detectionProject supported by the National Natural Science Foundation of China (Grant No 10274080) and the National High Technology Research and Development Program of China (Grant No 2003AA641010).8/5/2005 12:00:00 AM2005-08-052006-01-19A real time α-β-γ filtering technique is applied to the monitoring of atmosphere CH4 based on a tunable diode laser spectrum system operating at 1.654μm. This technique is developed for improving the sensitivity and precision of CH4 concentration measurement with slow concentration change. The effectiveness of this technique is evaluated by performing CH4 concentration measurement and using it to monitor the varying methane level in the atmosphere. It was proved that signal noise ratio enhancement factor is 4.25. The comparison between this filter and moving average is also included in this article. It indicates the advantage of the α-β-γ real time filter.     

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.     

光纤气体传感器解调方法的研究

利用可调谐激光光谱技术并结合二次谐波检测的波长调制方法对气体浓度进行检测,大大提高了检测灵敏度.然而光的传输和电路自身延时都会产生未知的相位延时,含有气体浓度信息的被测信号和二倍频参考信号的相位差变化严重影响二次谐波信号测量结果.本文设计出一种4路乘法锁相解调电路,设计中分别用正弦信号和余弦信号对被测信号进行解调,经积分电路后得到两路分别与相位差的正弦值和余弦值相关的解调信号.将两路解调信号平方,再通过加法器相加后消除相位差,得到完全与相位差无关的幅值信号.实验证明当被测信号相位在0°—90°变化时,解调 关键词： 可调谐半导体激光吸收光谱 波长调制 解调电路 相位差     

基于可调谐半导体激光吸收光谱的瓦斯监测方法研究

瓦斯爆炸是煤矿安全的主要威胁,对瓦斯气体浓度进行准确、快速、实时监测和预警是治理瓦斯灾害的有效手段。实验研究了近红外半导体激光吸收光谱技术在煤矿瓦斯气体安全检测中的应用。系统光源采用的是1.65μm波长的近红外可调谐DFB激光器,使用了波长调制和二次谐波检测技术,通过光纤进行信号传输。系统检测限低于0.09%,气体浓度的检测速度最高可达到0.02s。研究表明:该技术具有实时、连续、快速、非接触检测的特点;现场无带电部件,具有多点分布式遥测的能力,能够满足煤矿瓦斯安全检测的要求。     

凝聚态物质中的光声喇曼效应理论

用热弹性理论系统地分析了凝聚态物质的光声喇曼效应,分别导出了连续和脉冲激光泵浦下的光声喇曼信号表达式,并做了数值估算.     

基于可调谐二极管激光吸收光谱波长调制技术在线测量燃烧场温度

介绍了可调谐二极管激光吸收光谱（TDLAS）波长调制技术的测温原理。通过选择水在1 397.75 nm和1 397.87 nm处两条邻近的吸收线,运用多功能数据采集卡对二极管激光器进行控制和信号采集,实现了TDLAS波长调制技术对标定燃烧炉甲烷/空气预混火焰温度的实时在线测量,测量重复频率为250 Hz。分析了温度测量数据抖动的原因,结果表明燃烧过程中火焰本身温度的抖动是测量结果波动的主要原因,测量系统的A类标准不确定度小于53 K。     

基于可调谐半导体激光吸收光谱的酒精蒸汽检测方法

采用窄带半导体激光器开展了酒精蒸汽浓度检测方法研究.使用酒精分子在7180 cm-1附近的一个相对较窄的吸收峰作为酒精分子的鉴别信息.为消除水汽对酒精分子检测的干扰,提出了建立多元线性回归方程拟合求解多分子吸收共存的问题.实验表明,系统的检测限达到25 ppm·m.     

低频波长调制光谱的理论与实验研究

通过调制半导体激光外腔压电陶瓷的电压实现低频波长调制 ,并慢扫描激光器的波长 ,测量了CS 原子D2线 [6S1 2 (F =4)→ 6P3 2 ]的吸收光谱 ,利用锁相放大器处理了二次、四次、六次谐波信号 ,实验结果与理论分析相吻合 ,在实验过程中还发现高次谐波探测可以有效地提高探测信号的信噪比     

基于可调谐半导体激光器吸收光谱的高灵敏度甲烷浓度遥测技术

讨论了一种新的高灵敏度甲烷遥测方法,利用可调谐激光二极管的调制光谱技术扫描甲烷的吸收峰,通过在测量光路中插入参考气池,增强低浓度情况下的吸收峰辨识能力,以提高甲烷浓度遥测信号的信噪比.此外,可以将激光器的中心波长锁定至气体吸收峰的峰值位置从而使仪器工作于吸收峰锁定模式,进行甲烷浓度的连续监测.实验结果表明,在测量距离分别为10 m和20 m时,周围环境中的甲烷积分浓度探测极限可以分别达到5 ppm·m和16 ppm·m.在吸收峰锁定工作模式下,系统在37 m距离处具有22 ppm·m的检出限,并可以监测甲烷浓度的快速变化.     

相敏式激光啁啾色散光谱技术在高吸收度情况下的应用

研究了相敏式激光啁啾色散光谱法在高吸收度情况下的应用.用窄频半导体激光器作为光源,利用一工作于载波抑制模式的铌酸锂电光强度调制器调制单频激光,在单频激光两侧产生两个边频分量,并通过两边频分量产生外差干涉信号.利用外差干涉的相位波动来测量甲烷气体位于1653.7 nm附近的折射率波动,通过气体折射率与吸收系数之间的Kramers-Kronig关系计算甲烷气体浓度.传统的波长调制光谱法受限于郎伯-比尔定律,在应用于高吸收度的情况时,存在灵敏度下降的问题,甚至出现随气体浓度上升输出信号反而下降的现象.实验结果显示,相同实验条件下,波长调制光谱法的线性测量范围为38.1—1500 ppm·m,线性测量的动态范围仅为16 d B;而相敏式激光啁啾色散光谱法在很大的吸收度范围内均具有线性输出,检出限低至47.3 ppm·m,线性测量范围上限为174825 ppm·m,具有超过35 d B的动态范围.     

基于可调谐二极管激光吸收光谱波长调制技术在线测量燃烧场温度

 介绍了可调谐二极管激光吸收光谱（TDLAS）波长调制技术的测温原理。通过选择水在1 397.75 nm和1 397.87 nm处两条邻近的吸收线,运用多功能数据采集卡对二极管激光器进行控制和信号采集,实现了TDLAS波长调制技术对标定燃烧炉甲烷/空气预混火焰温度的实时在线测量,测量重复频率为250 Hz。分析了温度测量数据抖动的原因,结果表明燃烧过程中火焰本身温度的抖动是测量结果波动的主要原因,测量系统的A类标准不确定度小于53 K。     

基于可调谐二极管激光吸收光谱技术的密闭玻璃容器中水汽浓度及压力的探测

冻干法处理过的药品瓶中残存的水汽(H₂O)是药品变质的主要影响因素之一, 如何快速准确地测量瓶中的水汽浓度及压力, 是检测药瓶是否泄漏的关键. 本文报道了利用1.39 μm半导体激光器作为光源, 结合波长调制吸收光谱技术, 实现了对密闭玻璃容器(药瓶)中水汽浓度及压力的探测, 并通过转台模拟生产线对系统在动态条件下的性能进行了测试. 研究结果表明, 在0.2%-12%的H₂O浓度范围内真实值与测量值之间的相关度和标准偏差为0.9978 和4.81%, 在0.1-100 atm (1 atm=1.01325×10⁵ Pa)的压力范围内两者之间的相关度和标准偏差为0.982和5.6%, 系统对应的压力及浓度的最低检测限约为2.5 Torr (1 Torr=1.33×10² Pa)和400 ppm. 通过利用转台以及Labview编写的快速在线处理软件进行了动态条件下的测试, 一分钟可以处理300个左右的药瓶, 可以很好地满足快速实时探测的要求. 该方案可以直接应用于药瓶在线检测, 并且使用2台激光器可以实现多组分同时探测分析(如H₂O、氧气等).