TDLAS测量甲烷／空气预混平面火焰温度和H2O浓度

基于可调谐二极管激光器吸收光谱技术(TDLAS)建立了温度和H20浓度测量系统，利用光谱数据库Hi— tran2004在1393nm附近选择了在500～1300K有很高测温灵敏度的两条水吸收线：7168.437 cm- ，7185.597 cm- 。 在1kHz的扫描频率下，利用直接吸收一扫描波长法对甲烷／空气预混平面火焰进行测量，并进行边界层修正，与热电 偶的对比结果显示，在温度区间1100～1350K，两者最大相差80K(6.7％)；水蒸气组分浓度与计算值平均相差小于 O.02(10％)．

TDLAS测量甲烷/空气预混平面火焰温度和H2O浓度

基于可调谐二极管激光器吸收光谱技术(TDLAS)建立了温度和H2O浓度测量系统，利用光谱数据库Hitran2004在1393nm附近选择了在500-1300K有很高测温灵敏度两条水吸收线:7168.437 cm-1,7185.597 cm-1。在1KHz的扫描频率下，利用直接吸收-扫描波长法对甲烷/空气预混平面火焰进行测量，并进行边界层修正，与热电偶的对比结果显示，在温度区间1100-1350K，两者最大相差80K(6.7%);水蒸气组分浓度与计算值平均相差小于0.02(10%)。

Laser Spectroscopy: TDLAS instrumentation and NIR analysis of some organic materials

Near-infrared spectroscopy can be a workhorse technique for materials analysis in industries such as agriculture, pharmaceuticals, chemicals and polymers. A near-infrared spectrum represents combination bands and overtone bands that are harmonics of absorption frequencies in the mid-infrared. Near-infrared absorption includes a combination-band region immediately adjacent to the mid-infrared and three overtone regions. All four near-infrared regions contain "echoes" of the fundamental mid-infrared absorptions. For example, vibrations in the mid-infrared due to the C-H stretches will produce four distinct bands in each of the overtone and combination regions. As the bands become more removed from the fundamental frequencies they become more widely separated from their neighbors, more broadened and are dramatically reduced in intensity. Because near-infrared bands are much less intense, more of the sample can be used to produce a spectra and with near-infrared, sample preparation activities are greatly reduced or eliminated so more of the sample can be utilized. In addition, long path lengths and the ability to sample through glass in the near-infrared allows samples to be measured in common media such as culture tubes, cuvettes and reaction bottles. This is unlike mid-infrared where very small amounts of a sample produce a strong spectrum; thus sample preparation techniques must be employed to limit the amount of the sample that interacts with the beam. In the present work we describe the successful the fabrication and calibration of a linear high resolution linear spectrometer using tunable diode laser and a 36 m path length cell and meuurement of a highly resolved structure of OH group in methanol in the transition region A v =3. We then analyse the NIR spectrum of certain aromatic molecules and study the substituent effects using local mode theory

Experimental Analysis of Water Vapor Diffusion Through Porous Membranes in a Proton Exchange Membrane Fuel Cell

We report the diffusion characteristics of water vapor through two different porous media, viz., membrane electrode assembly (MEA) and gas diffusion layer (GDL) in a nonoperational fuel cell. Tunable diode laser absorption spectroscopy (TDLAS) was employed for measuring water vapor concentration in the test channel. Effects of the membrane pore size and the inlet humidity on the water vapor transport are quantified through mass flux and diffusion coefficient. Water vapor transport rate is found to be higher for GDL than for MEA. The flexibility and wide range of application of TDLAS in a fuel cell setup is demonstrated through experiments with a stagnant flow field on the dry side.

Spatial resolved temperature measurement based on absorption spectroscopy using a single tunable diode laser

A novel method based on wavelength-multiplexed line-of-sight absorption and profile fitting for non-uniform flow field measurement is reported. A wavelength scanning combing laser temperature and current modulation WMS scheme is used to implement the wavelength-multiplexed-profile fitting method. Second harmonic (2f) signal of eight H2O transitions features near 7,170 cm(-1) are measured in one period using a single tunable diode laser. Spatial resolved temperature distribution upon a CH4/air premixed flat flame burner is obtained. The result validates the feasibility of strategy for non-uniform flow field diagnostics by means of WMS-2f TDLAS.

利用可调谐二极管激光吸收光谱诊断超声速流动

本文利用建立的TDLAS测量系统，应用于氢氧燃烧驱动Φ800低密度激波管，进行了高超声速气流诊断实验。由于激波管③区的气流速度，温度和水蒸气组分分压等参数和超燃燃烧台尾喷管出口气体状态较为接近。因此对激波管③区水蒸气的测量模拟了对超燃台尾喷管气流的吸收诊断。

利用吸收光谱方法诊断超燃直联台燃烧效率

燃烧效率是超声速燃烧优劣的直接评价，一直是超燃实验研究的测量难点。本文发展了基于可调谐二极管激光器吸收光谱技术(TDLAS)的燃烧效率测量方法。利用3条水蒸气吸收谱线(7168.437cm-1,7185.597cm-1和6807.834cm-1)，在4kHz的测量频率下，采用分时扫描-直接探测的策略测量了以氢气为燃料的超燃直联台燃烧室入口的气体参数，并利用位移机构扫描测量捕捉了燃烧室后段某垂直截面的温度、水蒸气浓度分布和截面的平均气流速度。分别根据水蒸气浓度和总温分布计算得到燃烧效率。

航天器行星再入辐射现象研究的初步设想

当空间飞行器再入地球大气层、进入别的星球大气圈时,飞行器周边的气体受到头部弓形激波的作用将生成几种具有强烈辐射的组分,正确预测产生的辐射热流对于飞行器设计及材料选择有重要意义。可调谐半导体激光吸收光谱(TDLAS)测量技术具有定量准确、时间分辨率高、灵敏度高、环境适应性好等优点,是近年来广受关注的气体检测方法。本文设想建立一套结合吸收光谱(TDLAS)和发射光谱的测量系统,并将其用于行星再入的非平衡辐射测量。

超燃燃烧室气流参数诊断

本文基于可调谐二极管激光器吸收光谱技术(TDLAS)，利用7185.597 cm-1、7444.37cm-1+7444.37cm-1(重合吸收线)两条H2O吸收线，采用分时扫描-直接探测策略组建多光路吸收测量系统，在4kHz的测量频率下，定量测量了燃烧室气流的静温、水蒸气浓度和流向速度。利用位移机构，在以C2H4为燃料的超燃直连式试验台中，在单次试验中同时诊断燃烧室内某截面和燃烧室出口的气流参数截面分布。具体工作可分为以下三部分：测量燃烧室出口截面的水蒸气浓度分布和壁面静压判断燃烧效率；测量燃烧室出口截面的静温和速度分布，获得出口气流马赫数截面分布；测量凹腔后部某截面的温度和水蒸气浓度分布，以此判读凹腔附近流场特征。

Tunable diode Laser Absorption Spectroscopy ,Nir Overtone and Life Studies of Some Organic Compound

The present work is mainly concentrated on setting up a NIR tunable diode laser absorption (TDLA) spectrometer for high-resolution molecular spectroscopic studies. For successfully recording the high-resolution tunable diode laser spectrum, various experimental considerations are to be taken into account like the setup should be free from mechanical vibrations, sample should be kept at a low pressure, laser should be in a single mode operation etc. The present experimental set up considers all these factors. It is to be mentioned here that the setting up of a high resolution NIR TDLA spectrometer is a novel experiment requiring much effort and patience. The analysis of near infrared (NIR) vibrational overtone spectra of some substituted benzene compounds using local mode model forms another part of the present work. An attempt is made to record the pulsed laser induced fluorescence/Raman spectra of some organic compounds. A Q-switched Nd:YAG laser is used as the excitation source. A TRIAX monochromator and CCD detector is used for the spectral recording. The observed fluorescence emission for carbon disulphide is centered at 680 nm; this is assigned as due to the n, p* transition. Aniline also shows a broad fluorescence emission centered at 725 nm, which is due to the p,p* transition. The pulsed laser Raman spectra of some organic compounds are also recorded using the same experimental setup. The calibration of the set up is done using the laser Raman spectra of carbon tetrachloride and carbon disulphide. The observed laser Raman spectra for aniline, o-chloroaniline and m-chlorotoluene show peaks characteristics of the aromatic ring in common and the characteristics peaks due to the substitutuent groups. Some new peaks corresponding to low-lying vibrations of these molecules are also assigned

NIR Spectroscopic and Laser Induced Fluorescence studies of some organic molecules

Vibrational overtone spectroscopy of molecules containing X-H oscillators (X = C, N, O...) has become an effective tool for the study of molecular structure, dynamics, inter and intramolecular interactions, conformational aspects and substituent effects in aliphatic and aromatic compounds. In the present work, the author studied the NIR overtone spectra of some liquid phase organic compounds. The analysis of the CH, NH and OH overtones yielded important structural information about these systems. In an attempt to get information on electronic energy levels, we studied the pulsed Nd:YAG laser induced fluorescence spectra of certain organic compounds. The pulsed laser Raman spectra of some organic compounds are also studied. The novel high resolution technique of near infrared tunable diode laser absorption spectroscopy (TDLAS) is used to record the rotational structure of the second OH overtone spectrum of 2-propanol. The spectral features corresponding to the different molecular conformations could be identified from the high resolution spectrum. The whole work described in this thesis is divided into five chapters.

Gasleckortungsmethoden für autonome mobile Inspektionsroboter mit optischer Gasfernmesstechnik in industrieller Umgebung

In vielen Industrieanlagen werden verschiedenste Fluide in der Produktion eingesetzt, die bei einer Freisetzung, z. B. durch ihre toxische oder karzinogene Eigenschaft oder wegen der Brand- und Explosionsgefahr, sowohl die Umwelt als auch Investitionsgüter gefährden können. In Deutschland sind zur Risikominimierung die maximal zulässigen Emissionsmengen von Stoffen und Stoffgruppen in verschiedenen Umweltvorschriften festgelegt, wodurch zu deren Einhaltung eine ausreichende Überwachung aller relevanten Anlagenkomponenten seitens der Betreiber notwendig ist. Eine kontinuierliche und flächendeckende Überwachung der Anlagen ist aber weder personell, noch finanziell mit klassischer In-situ-Sensorik realisierbar. In der vorliegenden Arbeit wird die Problemstellung der autonomen mobilen Gasferndetektion und Gasleckortung in industrieller Umgebung mittels optischer Gasfernmesstechnik adressiert, die zum Teil im Rahmen des Verbundprojekts RoboGasInspector entstand. Neben der Beschreibung des verwendeten mobilen Robotersystems und der Sensorik, werden die eingesetzten Techniken zur Messdatenverarbeitung vorgestellt. Für die Leckortung, als Sonderfall im Inspektionsablauf, wurde die TriMax-Methode entwickelt, die zusätzlich durch einen Bayes-Klassifikator basierten Gasleckschätzer (Bayes classification based gas leak estimator (BeaGLE)) erweitert wurde, um die Erstellung von Leckhypothesen zu verbessern. Der BeaGLE basiert auf Techniken, die in der mobilen Robotik bei der Erstellung von digitalen Karten mittels Entfernungsmessungen genutzt werden. Die vorgestellten Strategien wurden in industrieller Umgebung mittels simulierter Lecks entwickelt und getestet. Zur Bestimmung der Strategieparameter wurden diverse Laborund Freifelduntersuchungen mit dem verwendeten Gasfernmessgerät durchgeführt. Die abschließenden Testergebnisse mit dem Gesamtsystem haben gezeigt, dass die automatische Gasdetektion und Gaslecksuche mittels autonomer mobiler Roboter und optischer Gasfernmesstechnik innerhalb praktikabler Zeiten und mit hinreichender Präzision realisierbar sind. Die Gasdetektion und Gasleckortung mittels autonomer mobiler Roboter und optischer Gasfernmesstechnik ist noch ein junger Forschungszweig der industriellen Servicerobotik. In der abschließenden Diskussion der vorliegenden Arbeit wird deutlich, dass noch weitergehende, interessante Forschungs- und Entwicklungspotentiale erkennbar sind.

Flugzeuggetragene Spurengasmessungen in der Tropopausenregion

ZusammenfassungIm Rahmen der EU-Projekte POLSTAR (Polar StratosphericAerosol Experiment) und STREAM (Stratosphere TroposphereExperiment by Airborne Measurements) wurden flugzeuggetragene Spurengasmessungen in verschiedenen geografischen Breiten durchgeführt. Zwei Messkampagnen fanden im Januar (POLSTAR 97) und März (STREAM 97) 1997 über Kiruna (Schweden, 67°N, 20°O) statt, eine Kampagne wurde im Juli 1998 von Timmins (Kanada, 47°N, 81°W) aus durchgeführt (STREAM 98).CO und N2O wurden mittels TDLAS (Tunable Diode Laser Absorption Spectroscopy) nachgewiesen, CO2 wurde mit einem modifizierten kommerziellen Messgerät breitbandig gemessen. Zur Untersuchung von Mischungsvorgängen in der Tropopausenregion wurden Korrelationenzwischen CO, O3, N2O, CO2 und NOy herangezogen.Dabei konnte festgestellt werden, dass im Winter in der untersten Stratosphäre Mischung mit troposphärischen Luftmassen durch isentropen Transport im Bereich der Polarfront bis zu potentiellen Temperaturen von Theta=335K auftritt. Im Sommer lässt sich Mischung mit troposphärischen Luftmassen bis mindestens Theta=360K nachweisen, die effektiver als im Winter abläuft.Exemplarisch kann an einem Flug gezeigt werden, dassbis Theta=349K die Ausbildung der Mischungsschicht durchLuftmassenaustausch an der Polarfront verursacht wird, während oberhalb von Theta=349K Signaturen subtropischertroposphärischer Luftmassen gefunden werden.Der stratosphärische Hintergrund wird mitbestimmt durch photochemisch gealterte Luftmassen, die ihren Ursprung höchstwahrscheinlich in der Vortexregion des vorangegangenen Winters haben.

Vibrational Relaxation of N2O (v2) by Atomic Oxygen Measured by Tunable Diode Laser Absorption Spectroscopy

Through the use of Transient Diode Laser Absorption Spectroscopy (TDLAS), the rate coefficient for the vibrational relaxation of N2O (ν2) by O(3P) at room temperature (32 ºC)) was determined to be (1.51 ± 0.11)x10-12 cm3molecule-1sec-1. A Q-switched, frequency quadrupled (266 nm) Nd:YAG laser pulse was used as the pump for this experiment. This pulse caused the photodissociation of O3 into O2 and O atoms.Excited oxygen (O(1D)) was collisionally quenched to ground state (O(3P)) by Ar and/or Xe. Photodissociation also caused a temperature jump within the system, exciting the ν2 state of N2O molecules. Population in the ν2 state was monitored through a TDLASobservation of a ν3 transition. Data were fit using a Visual Fortran 6.0 Global Fitting program. Analysis of room temperature data taken using only Ar to quench O atoms to the ground state gave the same rate coefficient as analysis of data taken using an Ar/Xe mixture, suggesting Ar alone is a sufficient bath gas. Experimentation was alsoperformed at -27 ºC and -82 ºC for a temperature dependence analysis. A linear regression analysis gave a rate coefficient dependence on temperature of ... for the rate coefficient of the vibrational relaxation of N2O (ν2) by atomic oxygen.

Vibrational Relaxation of 13CO2(v2) by Atomic Oxygen

Carbon dioxide (CO2) has been of recent interest due to the issue of greenhouse cooling in the upper atmosphere by species such as CO2 and NO. In the Earth’s upper atmosphere, between altitudes of 75 and 110 km, a collisional energy exchange occurs between CO2 and atomic oxygen, which promotes a population of ground state CO2 to the bend excited state. The relaxation of CO2 following this excitation is characterized by spontaneous emission of 15-μm. Most of this energy is emitted away from Earth. Due to the low density in the upper atmosphere, most of this energy is not reabsorbed and thus escapes into space, leading to a local cooling effect in the upper atmosphere. To determine the efficiency of the CO2- O atom collisional energy exchange, transient diode laser absorption spectroscopy was used to monitor the population of the first vibrationally excited state, 13CO2(0110) or ν2, as a function of time. The rate coefficient, kO(ν2), for the vibrational relaxation 13CO2 (ν2)-O was determined by fitting laboratory measurements using a home-written linear least squares algorithm. The rate coefficient, kO(ν2), of the vibrational relaxation of 13CO2(ν2), by atomic oxygen at room temperature was determined to be (1.6 ± 0.3 x 10-12 cm3 s-1), which is within the uncertainty of the rate coefficient previously found in this group for 12CO2(ν2) relaxation. The cold temperature kO(ν2) values were determined to be: (2.1 ± 0.8) x 10-12 cm3 s-1 at Tfinal = 274 K, (1.8 ± 0.3) x 10-12 cm3 s-1 at Tfinal = 239 K, (2 ± 1) x 10-12 cm3 s-1 at Tfinal = 208 K, and (1.7 ± 0.3) x 10-12 cm3 s-1 at Tfinal = 186 K. These data did not show a definitive negative temperature dependence comparable to that found for 12CO2 previously.