The detection and measurement of gas properties has become essential to meet rigorous criteria of environmental unfriendly emissions and to increase the energy production efficiency. Although low cost devices such as pellistors, semiconductor gas sensors or electrochemical gas sensors can be used for these applications, they offer a very limited lifetime and suffer from cross-response and drift. On the contrary, gas sensors based on optical absorption offer fast response, zero drift, and high sensitivity with zero cross response to other gases. Hence, over the last forty years, diode laser spectroscopy (DLS) has become an established method for non-intrusive measurement of gas properties in scientific as well as industrial applications. Wavelength modulation spectroscopy (WMS) is derivative form of DLS that has been increasingly applied for making self-calibrated measurements in harsh environments due to its improved sensitivity and noise rejection capability compared to direct absorption detection. But, the complexity in signal processing and higher scope of error (when certain restrictions on operating conditions are not met), have inhibited the widespread use of the technique. This dissertation presents a simple and novel strategy for practical implementation of WMS with commercial diode lasers. It eliminates the need for pre-characterization of laser intensity parameters or making any design changes to the conventional WMS system. Consequently, sensitivity and signal strength remain the same as that obtained from traditional WMS setup at low modulation amplitude. Like previously proposed calibration-free approaches, this new method also yields absolute gas absorption line shape or absorbance function. Residual Amplitude Modulation (RAM) contributions present in the first and second harmonic signals of WMS are recovered by exploiting their even or odd symmetric nature. These isolated RAM signals are then used to estimate the absolute line shape function and thus removing the impact of optical intensity fluctuations on measurement. Uncertainties and noises associated with the estimated absolute line shape function, and the applicability of this new method for detecting several important gases in the near infrared region are also discussed. Absorbance measurements from 1% and 8% methane-air mixtures in 60 to 100 kPa pressure range are used to demonstrate simultaneous recovery of gas concentration and pressure. The system is also proved to be self-calibrated by measuring the gas absorbance for 1% methane-air mixture while optical transmission loss changes by 12 dB. In addition to this, a novel method for diode laser absorption spectroscopy has been proposed to accomplish spatially distributed monitoring of gases. Emission frequency chirp exhibited by semiconductor diode lasers operating in pulsed current mode, is exploited to capture full absorption response spectrum from a target gas. This new technique is referred to as frequency chirped diode laser spectroscopy (FC-DLS). By applying an injection current pulse of nanosecond duration to the diode laser, both spectroscopic properties of the gas and spatial location of sensing probe can be recovered following traditional Optical Time Domain Reflectometry (OTDR) approach. Based on FC-DLS principle, calibration-free measurement of gas absorbance is experimentally demonstrated for two separate sets of gas mixtures of approximately 5% to 20% methane-air and 0.5% to 20% acetylene-air. Finally, distributed gas monitoring is shown by measuring acetylene absorbance from two sensor probes connected in series along a single mode fiber. Optical pulse width being 10 nanosecond or smaller in the sensing optical fiber, a spatial resolution better than 1 meter has been realized by this technique. These demonstrations prove that accurate, non-intrusive, single point, and spatially distributed measurements can be made in harsh environments using the diode laser spectroscopy technology. Consequently, it opens the door to practical implementation of optical gas sensors in a variety of new environments that were previously too difficult. / Ph. D.

Near-infrared (NIR) absorption spectroscopy with tunable diode lasers allows the simultaneous detection of the three most important isotopologues of carbon dioxide (<SUP>12</SUP>CO<SUB>2</SUB>, <SUP>13</SUP>CO<SUB>2</SUB>, <SUP>12</SUP>C<SUP>18</SUP>O<SUP>16</SUP>O) and carbon monoxide (<SUP>12</SUP>CO, <SUP>13</SUP>CO, <SUP>12</SUP>C<SUP>18</SUP>O). The flexible and compact fiber-optic tunable diode laser absorption spectrometer (TDLAS) allows selective measurements of CO<SUB>2</SUB> and CO with high isotopic resolution without sample preparation since there is no interference with water vapour. For each species, linear calibration plots with a dynamic range of four orders of magnitude and detection limits (LOD) in the range of a few ppm were obtained utilizing wavelength modulation spectroscopy (WMS) with balanced detection in a Herriott-type multipass cell. The high performance of the apparatus is illustrated by fill-evacuation-refill cycles.

The performance of a home-built tunable diode laser (TDL) spectrometer, aimed at multi-line detection of carbon dioxide, has been evaluated and optimized. In the regime of the (30<SUP>0</SUP>1)<SUB>III</SUB> / (000) band of <SUP>12</SUP>CO<SUB>2</SUB> around 1.6 μm, the dominating isotope species <SUP>12</SUP>CO<SUB>2</SUB>, <SUP>13</SUP>CO<SUB>2</SUB>, and <SUP>12</SUP>C<SUP>18</SUP>O<SUP>16</SUP>O were detected simultaneously without interference by water vapor. Detection limits in the range of few ppmv were obtained for each species utilizing wavelength modulation (WM) spectroscopy with balanced detection in a long-path absorption cell set-up. High sensitivity in conjunction with high precision —typically ±1‰ and ±6‰ for 3% and 0.7% of CO<SUB>2</SUB>, respectively— renders this experimental approach a promising analytical concept for isotope-ratio determination of carbon dioxide in soil and breath gas. For a moderate <SUP>12</SUP>CO<SUB>2</SUB> line, the pressure dependence of the line profile was characterized in detail, to account for pressure effects on sensitive measurements.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第19029号 / 農博第2107号 / 新制||農||1030(附属図書館) / 学位論文||H27||N4911(農学部図書室) / 31980 / 京都大学大学院農学研究科地域環境科学専攻 / (主査)教授 谷 誠, 教授 北山 兼弘, 教授 川島 茂人 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM