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.     

光声光谱技术在多组分气体浓度探测中的应用

CO和CH_4气体作为判断变压器运行状态的故障气体,对其浓度的探测在变压器维护中具有重要意义.为了准确探测变压器运行过程中产生的CH_4和CO气体浓度,本文利用光声光谱技术,设计了一套基于宽带光源的多组分气体探测系统,和共振型光声系统相比,该系统中所用的非共振型光声池体积小,易加工,池内各处信号强度相同,降低了对声学信号探测器的安装要求.系统的性能通过对CO和CH_4气体的探测进行评估.首先,从理论上分析了信号强度与调制频率呈反比,然后根据宽带光声系统在不同调制频率下的响应,确定系统的最佳调制频率为22 Hz.在最佳调制频率下,根据温度与待测气体光声信号的关系,对光声信号进行温度补偿,消除温度变化对光声信号的影响,进一步提高了系统的稳定性.最后,通过不同浓度的CH_4和CO气体对系统进行标定.实验表明,温度补偿前后,光声信号随温度的漂移分别为0.023 23V/℃和8.383 48×10~(-5) V/℃,通过对不同浓度CH_4和CO气体的探测,系统的线性度分别达到0.995和0.998 4.在一个大气压下,积分时间为1s时,宽带光声探测系统对CO和CH_4气体的探测极限浓度能够达到1μL/L.该系统成本低,线性度好,探测灵敏度符合国标对变压器维护过程中CO和CH_4气体的探测要求.     

Simultaneous sensing of temperature,CO, and CO2 in a scramjet combustor using quantum cascade laser absorption spectroscopy

A mid-infrared laser absorption sensor was developed for gas temperature and carbon oxide (CO, CO₂) concentrations in high-enthalpy, hydrocarbon combustion flows. This diagnostic enables non-intrusive, in situ measurements in harsh environments produced by hypersonic propulsion ground test facilities. The sensing system utilizes tunable quantum cascade lasers capable of probing the fundamental mid-infrared absorption bands of CO and CO₂ in the 4–5 µm wavelength domain. A scanned-wavelength direct absorption technique was employed with two lasers, one dedicated to each species, free-space fiber-coupled using a bifurcated hollow-core fiber for remote light delivery on a single line of sight. Scanned-wavelength modulation spectroscopy with second-harmonic detection was utilized to extend the dynamic range of the CO measurement. The diagnostic was field-tested on a direct-connect scramjet combustor for ethylene–air combustion. Simultaneous, laser-based measurements of carbon monoxide and carbon dioxide provide a basis for evaluating combustion completion or efficiency with temporal and spatial resolution in practical hydrocarbon-fueled engines.     

Optimization of Generation and Detection of WDM Signals with Advanced Modulation Formats

This paper presents optimal generation and detection of wavelength division multiplexed (WDM) signals with advanced modulation formats. We investigate the relative phase alignment between phase modulation and data bits for chirped return-to-zero (CRZ) signals, and the frequency offset between the RZ carrier and various optical filters for vestigial side band (VSB)-RZ signals.     

Interactions between NO and CO on Pt(111)

Temperature programmed desorption (TPD) of coadsorbed NO and CO on Pt(111) shows that no reaction occurs (less than 2%) up to the desorption temperature of NO. At 100 K, adsorption is competitive, but neither gas displaces the other from the surface. Coadsorbed CO causes the NO desorption temperature to be lowered by as much as 100 K, but NO does not affect the CO desorption temperature. TPD spectra for NO depend on which gas is adsorbed first, indicating that equilibrium between species is not established on the surface during desorption. Electron energy loss spectra show that the vibrational spectrum of each gas is only weakly affected by the other. When NO is adsorbed first, CO does not affect the ratio of bridged and terminal NO but lowers the frequencies of the bridged NO by approximately 50 cm^?1 and lowers the intensities of vibrational peaks of both species by a factor of about four. When CO is adsorbed first, the ratio of terminal to bridged NO increases for given coverage of NO, and the frequency of the bridged NO remains at the pure NO value. These results are explained in terms of CO island formation, repulsive interactions between NO and CO, and low adsorbate mobilities.     

Characterization of CO tolerance of PEMFC by ac impedance spectroscopy

The CO tolerance of a proton exchange membrane fuel cell (PEMFC) was investigated by ac impedance spectroscopy. The impedance of the fuel cell could be obtained by feeding oxygen into the cathode side and simulated gas into anode side. Furthermore, the anode impedance could be obtained by feeding hydrogen into the cathode side and simulated gas into anode side. The CO gas had a greater effect on the charge transfer reaction (high frequency arc) and hydrogen dissociative chemisorption (medium frequency arc) but little effect on the low frequency arc. Although the cathode impedance is a main part at high temperature, irrespective of CO concentration (≤100 ppm), the impedance of the full cell depends on anode impedance at low temperature and high CO concentration. It was found that CO gas has little effect on cathode impedance.     

Frequency stabilization of diode laser to 1.637μm based on the methane absorption line

The frequency of an external-cavity diode laser has been stabilized to 1.637 μm by using the reference of absorption lines of methane.The method can be applied to wavelength division multiplexed optical communication,fiber-optic sensing systems,as well as the high-sensitivity detection of methane.The derivative-like error signal yielded by frequency modulation and phase sensitivity detection technology is inputted into the PI feedback loop circuit in order to stabilize the frequency to the line center.After stabilization,the frequency fluctuation of diode laser is held within 5.6 MHz,and the root of Allan variance of error signal reaches a minimum of 1.66×10-10 for an average time of 10 s.     

可调谐半导体激光吸收光谱法监测燃烧过程中CO浓度的变化

可调谐半导体激光吸收光谱技术(tunable diode laser absorption spectroscopy, TDLAS)是利用二极管激光器的波长调谐特性,获得被选定的待测气体特征吸收线的吸收光谱,从而对待测气体进行定性或定量分析。它具有高灵敏、高分辨以及快速检测等特点,已经广泛用于大气中多种痕量气体的检测以及泄漏气体的检测,也是在燃烧环境下对气体进行非侵入式实时测量的理想方法。TDLAS技术与开放式的多次反射池相结合,并利用自平衡探测加波长调制的新型检测方法,测量了酒精喷灯燃烧过程中产生的CO浓度,从测量结果中发现酒精喷灯火焰中CO的浓度成一定的周期性,并且得到火焰中CO的平均浓度为49.4(10-6体积比)。实验结果表明利用开放式多次反射池,结合自平衡探测加波长调制探测的新方法,满足了酒精喷灯燃烧过程中CO检测的需要,此系统为发展基于TDLAS的燃烧在线诊断技术奠定了基础。     

The Impact of Different CO Admixtures on the Electron Kinetics in Collision Dominated RF He/CO Bulk Plasmas

Electron energy distribution functions and mean collision frequencles for the uniform bulk plasma of established rf discharges in He/CO have been obtained by solving the time dependent Boltzmann equation. The results, which are of importance for plasma processing and laser technology, show that already small CO admixtures to He remarkably changes the periodic behaviour of the energy distribution of the electrons by drastical enhancement of the collisional energy dissipation effectiveness in the mixture. These changes can be interpreted on the basis of a lumped energy dissipation frequency in all electron collisions which is determined by the atomic data of the electron collision processes as well as by the admixture fractions and which drastically increases with increasing CO admixture. The degree of modulation of the energy distribution in different parts of the electron energy space and its population on the time average at higher energies are determined by the relation between the rf field frequency and the mentioned lumped energy dissipation frequency.     

渐变折射率传感气室中干涉噪声的数值模拟与分析

在直接红外吸收式光纤气体传感器中，由渐变折射率（Graduated Refractive Index，GRIN）棒透镜构成的微型传感气室有着广泛的应用。分析了GRIN气室中的干涉噪声信号和甲烷信号，并利用MATLAB对干涉噪声信号的幅值与分布反馈式半导体激光器（DFBLD）的频率调制幅度之间的关系以及干涉噪声对气体检测灵敏度的影响进行了数值模拟与分析。当前谐波检测技术是气体检测的一种非常重要的技术，这种技术需要检测气体吸收信号的一次、二次或更高次谐波。而GRIN气室的二次干涉噪声对浓度信号有很大的影响，研究发现当频率调制幅度达到某些特定频率值时，二次干涉噪声信号的幅值变为零，通过调整气室参数和DFBLD的调制频率可以削减干涉噪声的影响从而提高谐波检测技术的检测灵敏度。     

基于多路复用体全息光栅的角度放大器设计

为设计基于多路复用体全息光栅的角度放大器, 建立了多路复用角度放大器(MAM)模型, 从效率均衡性和角度分布均匀性两个方面归纳了其设计规则; 研究了光刻过程中的误差对MAM性能的影响; 分析了实际发散光束对MAM性能的影响. 研究表明:控制光栅空间频率和光栅倾斜角可以实现需要的MAM角度分布, 控制光栅厚度和折射率调制深度可以实现MAM最佳衍射效率; MAM最大复用路数不超过10路; 增大光栅倾角或者记录光与工作光波长之比有利于抑制参考光角度误差带来的MAM出射角分布误差, 减小光栅厚度有利于抑制厚度误差与折射率调制深度误差对衍射效率的影响; 当远场发散角大于光栅角半宽时, 最佳衍射效率下降到50%以下且角度选择曲线失去局部最小值; 增大空间频率或者光栅厚度可以减小所需的折射率调制深度, 增多MAM可复用路数, 但是不利于效率均衡性设计和抑制发散光束的影响.     

基于多路复用体全息光栅的角度放大器设计

为设计基于多路复用体全息光栅的角度放大器, 建立了多路复用角度放大器(MAM)模型, 从效率均衡性和角度分布均匀性两个方面归纳了其设计规则; 研究了光刻过程中的误差对MAM性能的影响; 分析了实际发散光束对MAM性能的影响. 研究表明:控制光栅空间频率和光栅倾斜角可以实现需要的MAM角度分布, 控制光栅厚度和折射率调制深度可以实现MAM最佳衍射效率; MAM最大复用路数不超过10路; 增大光栅倾角或者记录光与工作光波长之比有利于抑制参考光角度误差带来的MAM出射角分布误差, 减小光栅厚度有利于抑制厚度误差     

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.     

Fast simultaneous measurement of multi-gases using quantum cascade laser photoacoustic spectroscopy

The authors developed a fast simultaneous method in detecting multi-gases using quantum cascade laser (QCL) based photoacoustic (PA) spectroscopy. We demonstrated the simultaneous measurement of CO and SO₂ concentrations using two QCLs working at 4.56 and 7.38 μm, corresponding to the absorption bands of CO and SO₂, respectively. The modulation frequencies of the two QCLs were 234 and 244 Hz. The response time was 0.6 seconds. A computer sound card was used to process the PA signals. Fast Fourier transform was an essential step to get the amplitudes of the PA signals at different frequencies. The concentration of each gas can be obtained from the PA signal amplitude at the corresponding modulation frequency.     

Compact waveguide CO2 laser excited by a RF power supply

The design and performance of radio frequency (RF) excited partial Z-fold waveguide CO2 laser with two channels are exposed. The length of the partial Z-fold channel is 3×460 mm and that of the single channel is 460 mm. The electrodes for the two channels are common and excited by a same RF source. According to our analysis, this kind of structure can greatly improve the laser offset frequency stability. In the experiments, we studied the variation of laser output power with gas pressure for two different channels.The maximum laser output power is about 23 W for the partial Z-fold channel and about 6 W for the single channel.     

CO在1. 578 μ m的可调谐二极管激光光谱信号小波去噪研究

研究了一氧化碳(CO)近红外波段直接吸收和波长调制信号去噪处理算法。从HATRAN数据库中得到CO气体的吸收信号作为仿真数据,提取直接吸收信号、1-f和2-f解调信号作为原始信号,研究了不同小波基以及不同的分解层数对叠加高斯白噪声的光谱信号去噪的效果。最后利用基长为0.95 m有效光程为55.1 m的Herriott型多光程池对CO在1.578 μm处的第二泛频带P(4)吸收谱线信号进行测量和信号处理,与原始信号相比,经过信号处理过的直接吸收、1-f和2-f解调信号的信噪比都提高1～2个数量级;通过选择不同小波基和优化小波变换层数,增加了系统的抗干扰能力。     

Resonant optoacoustic detector in nondispersive gas analyzer scheme

A nondispersive gas analyzer scheme is suggested, in which the resonant optoacoustic device is used for detection of air sample absorption, where modulation with the appropriate spectral filtration is carried out with the help of pure detecting gas cells. Analyzer performance for CO₂, CO, CH₄, SO₂ and NO is studied. The modulation depth for gas cells was found to be between 0.45 for NO and 0.84 for CO₂. Trace-gas detectivity is limited by acoustical noise, originating from light beam chopper at a level of 10⁻²%. Information about the influence of spectral interference on detection selectivity was obtained.     

Investigation of the spectral content of a cw CO laser output using a high-resolution scanning Fabry-Perot interferometer

The use of a scanning Fabry-Perot interferometer of variable length (variable resolution) for investigating the output of a cw CO laser is reported. Under experimental conditions required to achieve maximum power it was found that the laser output consisted of two or more simultaneously occuring transitions due to the overlapping nature of the vibration- rotation bands. The frequency differences between these transitions were measured to an accuracy of 0.01 cm^-1. Operation of the CO laser on a single vibration-rotation transition was obtained by controlling the laser gain with the experimental variables of discharge pressure, gas temperature, and optical alignment. An alternative approach of obtaining monochromatic radiation, by using a Fabry-Perot interferometer as a frequency selective filter external to the CO laser, is reported.     

基于共振型高灵敏度光声光谱技术探测痕量乙炔气体浓度

乙炔气体作为判断变压器运行状态的一种故障气体,其浓度的高低反映了变压器的运行状况,因此对其浓度的探测在变压器的维护中具有重要意义。为了准确探测变压器运行过程中产生的乙炔气体浓度,为变压器的维护提供技术参数,针对基于DFB激光器的共振型光声光谱技术痕量乙炔气体检测技术开展研究,对传统的光声光谱探测系统进行改进。根据光声光谱技术的理论可知,光声信号的强度与入射激光的功率成正比,所以在光声池的出射窗口采用一个平面反射镜将红外光再次反射到光声池中以增加入射光功率,增强光声信号强度,进一步提高了光声系统的探测灵敏度。通过一定浓度的乙炔气体在不同调制频率和不同调制深度下光声信号强度的变化,确定光声探测系统的最佳调制频率和最佳调制深度为767 Hz和0.3 mV。利用不同浓度乙炔气体对系统进行标定,然后采用最小二乘法对光声信号与气体浓度进行拟合,二者具有很好的线性度。通过Allan方差计算可知,系统在平均时间达到200 s时,能够达到最低探测极限浓度。实验表明,在一个大气压下,积分时间为10 ms时,改进后的共振型光声光谱探测系统对乙炔气体的最低探测极限浓度达到了0.3 μL·L-1。还将小波去噪技术引入到低浓度下乙炔气体的光声信号处理中,有效消除了低浓度气体光声信号中的噪声,提高了信噪比。设计的共振型光声光谱探测系统操作简单,最低探测浓度符合国标中对变压器维护过程中对乙炔气体的探测需求,在变压器维护领域具有广阔的应用前景。     

Effect of CO on Characteristics of AlGaN/GaN Schottky Diode

Pt Schottky diode gas sensors for CO are fabricated using A1GaN/GaN high electron mobility transistor（HEMTs）structure. The diodes show a remarkable sensor signal （3 mA, in N2, 2mA in air ambient） biased 2 V after 1% CO is introduced at 50℃. The Schottky barrier heights decrease for 36meV and 27meV in the two cases respectively. The devices exhibit a slow recovery characteristic in air ambient but almost none in the background of pure N2, which reveals that oxygen molecules could accelerate the desorption of CO and offer restrictions to CO detection.