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研究生: 陸志忠
Lu, Chih-Chung
論文名稱: 高壓甲烷火焰預分解雷射激發螢光之氫氧基定量分析
QUANTITATIVE ANALYSIS OF OH-LIPF IN HIGH-PRESSURE METHANE FLAMES
指導教授: 袁曉峰
Yuan, Tony
學位類別: 博士
Doctor
系所名稱: 工學院 - 航空太空工程學系
Department of Aeronautics & Astronautics
論文出版年: 2002
畢業學年度: 90
語文別: 英文
論文頁數: 198
中文關鍵詞: 甲烷高壓火焰定量雷射激發螢光氫氧基
外文關鍵詞: OH radical, LIPF, quantitative, methane, LIF, high-pressure flame
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  •   本論文利用高壓甲烷預混平板火焰﹐進行高壓火焰中預分解雷射激發螢光之氫氧基(OH-LIPF)定量分析研究。氫氧基分子經由氟化氪準分子雷射從X2P(n² = 0)激發至A2S+(n¢ = 3)﹐觀察(3,2)與(3,1)的螢光光譜。在後焰區域中氫氧基螢光強度對火焰模擬計算的氫氧基濃度做校正﹐而火焰模擬計算結果是利用美國Sandia國家實驗室的火焰程式﹐配合GRI反應機構而得。經由對冷卻速率與Voigt profile的嚴謹計算﹐並且對室內空氣中的N2 Raman訊號做校正﹐OH-LIPF量測而得的校正曲線可以正確的描述出氫氧基的濃度變化﹐在後焰區域中最大誤差不超過±29%。氫氧基的濃度與螢光訊號之間的關係式可用下述方程式表示:

    利用能量解而得的反應區火焰溫度分佈結合熱電偶量測的下游火焰溫度分佈可以得到比較精確的火焰溫度分佈﹐使用此種改良型的火焰溫度分佈作為火焰模擬計算的輸入溫度﹐可以避免得到不正確的反應區位置。火焰模擬計算的氫氧基濃度與OH-LIPF定量量測結果相比較﹐在後焰區相當一致﹐在反應區亦具有合理性的符合。然而﹐在靠近反應區之火焰模擬計算氫氧基濃度﹐顯示有系統化高估的現象。這種現象指出GRI反應機構可能低估了低溫預熱區的反應速率。因此﹐低溫下的反應動力學資料需要再進一步研究。OH-LIPF雙線法量測而得的溫度分佈與熱電偶相比較﹐顯示結果尚可接受。並且發現使用文獻上各種不同的先分解速率﹐會對OH-LIPF雙線法量測溫度的結果造成最大誤差有±250K。

      Quantitative analysis of OH-LIPF in high-pressure (1–5 atm) premixed CH4/air flat flames (F = 0.75–1.25) has been performed. OH was excited (A2S+, n¢ = 3–X2P, n² = 0, P28 and Q111) using a KrF excimer laser and observed (3,2) and (3,1) band fluorescence, respectively. OH fluorescence intensities were calibrated against the OH concentration from flame simulation results in the post flame zone by Sandia flame code in conjunction with GRI mechanism. With careful evaluations of quenching rates, voigt profiles, and normalization against N2 Raman scattering intensity, the calibration curves for OH-LIPF measurements can adequately describe the concentration profiles of OH with an uncertainty of ±29% in the post flame zone. The semi-theoretical correlation between OH number density (cm-3) and fluorescence intensities was then deduced to be
    .
    A modification of input temperature profiles was performed to avoid misidentifying the correct position of reaction zone by combining near burner surface temperatures generated from flame simulation using energy-solution mode with the thermocouple measured temperatures downstream. The computed OH concentrations by flame simulation showed a good agreement with the quantitative OH-LIPF measurements in the post flame zone and a reasonable match in the reaction zone in high-pressure flames. However, simulation systematically overestimates the OH concentrations near reaction zone with given-temperature mode. The phenomena indicate GRI mechanism might underpredict the reactions rates in the low-temperature preheat zone. Further studies of low-temperature kinetics are required. The temperature from two-line OH-LIPF showed an acceptable agreement in the trend of profiles with from thermocouple measured. Using the predissociation rates in the different literatures, two-line OH-LIPF temperature might be introduced uncertainties about ±250 K.

    ABSTRACT x CONTENTS xi LIST OF TABLES xiv LIST OF FIGURE xv NOMENCLATURE xviii CHAPTER I INTRODUCTION 1   1.1 Background 1   1.2 Laser Diagnostic Techniques 2   1.3 OH Concentration Measurements 6   1.4 Temperature Measurements 9   1.5 Measurements in High-Pressure Flames 15   1.6 Kinetics and Mechanism 20   1.7 Motivations and Objectives 22   1.8 Thesis Overview 23 II THEORY OF LASER-INDUCED FLUORESCENCE 25   2.1 Background 25   2.2 State-to-State Transfer Approach 26   2.3 Four Level Model 28   2.4 OH Concentration Measurements 32   2.5 Temperature from Two-Line LIF 35   2.6 Some Considerations using OH LIPF 37     2.6.1 VET Effects 38     2.6.2 RET Effects 39     2.6.3 Polarization of OH-LIPF 40     2.6.4 Photobleaching and Photochemistry Phenomena 40     2.6.5 Collisional Quenching Effects and Rotational Level Dependence 41 III EXPERIMENTAL APPARATUS AND PROCEDURES 43   3.1 System Component 43   3.2 Laser System and Lenses 43   3.3 Fluorescence Detection 45   3.4 High Pressure and Flat Flame Burner 46   3.5 Temperature Measurements by Thermocouple 48   3.6 Operation Considerations 49   3.7 Flame Modeling 50 IV OH-LIPF MEASUREMENTS AND CALIBRATION 52   4.1 Overview 52   4.2 OH Concentration Measurements 53   4.3 Calibration 57   4.4 N2 Raman Scattering in Room-Air 58   4.5 Einstein Absorption and Emission Coefficients 59   4.6 Boltzmann Fraction 61   4.7 Voigt Profile 62   4.8 Quenching Rate 65   4.9 Predissociation Rate 67   4.10 Calibration Constant 68 V RESULTS AND DISCUSSION 70   5.1 Overview 70   5.2 OH Concentration Measurements 71   5.3 OH Sensitivity Analysis and Modifications of GRI Mechanism 73   5.4 Temperature Measurements by Two-Line LIF 85   5.5 Errors and Uncertainties 88 VI CONCLUSIONS 92   6.1 Conclusions 92   6.2 Suggestions to Further Research 93 REFERENCES 95 APPENDIX A 115 APPENDIX B 127 APPENDIX C 130 APPENDIX D 132 APPENDIX E 134 TABLES 138 FIGURES 143 PUBLICATION LIST 195 VITA 197

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