Mid-infrared polarization spectroscopy of C2H2: Non-intrusive spatial-resolved measurements of polyatomic hydrocarbon molecules for combustion diagnostics

Polarization spectroscopy in the mid-infrared (IRPS) has been applied to the detection of acetylene molecules making use of the asymmetric C-H stretching vibration at around 3 μm. The infrared laser pulses were produced through difference frequency generation in a LiNbO₃ crystal pumped by a Nd:YAG and dye laser system. By directly probing the ro-vibrational transitions with IRPS, sensitive detection of molecules with otherwise inaccessible electronic states was realized with high temporal and spatial resolution by using a pulsed laser and a cross-beam geometry. Detection sensitivities of 2 × 10¹³ molecules/cm³ (10 ppm in 70 mbar gas mixture) of C₂H₂ were achieved using the P(1 1) line of the (0 1 0(1 1)⁰)-(0 0 0 0⁰ 0⁰) band. The dependence of the IRPS signal on the pump laser fluence, acetylene mole fraction, and buffer gas pressure of Ar, N₂, H₂, and CO₂ has been studied experimentally. The investigation demonstrates the quantitative nature of IRPS for sensitive detection of polyatomic IR active molecules. In order to fully demonstrate the technique for combustion applications, nascent acetylene molecules were measured in a low pressure methane/oxygen flame.     

The potential of CO2 laser photoacoustic spectrometry for?detection of methanol in alcoholic beverage

The first use of CO₂ laser photoacoustic measurements for detecting the methanol contents in alcohol-like solutions is presented. With an intracavity cell configuration, the minimum detectable concentration was ∼200 ppm for methanol and the linear range of the calibration curve for methanol was from 200 to 70000 ppm. For demonstrating the reliability of analysis in alcoholic beverages, a series of different concentrations of two-component samples was prepared and measured by the same procedures. The results showed the feasibility on determining methanol and ethanol contents accurately within a specific tolerance, limited mainly by background signal and laser stability. This potential method with no pre-treatment of samples takes only ∼10 min to finish one single measurement. It suggests that the PA detection is suitable for routine diagnosis of adulterated wines in commercial products.     

Hydrogen and Deuterium Analysis Using Laser‐Induced Plasma Spectroscopy

Abstract

Hydrogen emission in laser plasma has been studied by focusing a TEA CO₂ laser and Nd‐YAG lasers on various types of samples, such as glass, quartz, and zircaloy pipes doped with hydrogen. It was found that H_α emission with a narrow spectral width occurs with high efficiency when the laser plasma is produced in low‐pressure host gas. In contrast, the conventional well‐known laser‐induced breakdown spectroscopy (LIBS), which operates at atmospheric air pressure, cannot be applied for the analysis of hydrogen as impurity. The specific characteristic of hydrogen emission in low‐pressure plasma is interpreted on the basis of our shock wave model, taking account of the fact that the hydrogen mass is extremely light compared to that of the host target. Another experimental study on gas analysis was conducted using an Nd‐YAG laser and helium host gas at atmospheric pressure on a sample of mixed water (H₂O) and heavy water (D₂O) in vapor form. It was shown that completely resolved hydrogen (H_α) and deuterium (D_α) emission lines that are separated by only 0.179 nm could be obtained at a properly delayed detection time when the charged particles responsible for the strong Stark broadening effect in the plasma have mostly disappeared. It is argued that a helium metastable excited state plays the important role in the hydrogen excitation process.     

Acoustooptic extension of the frequency tunability of CW CO2 lasers: New FIR lasers emissions from CH3OH and13CH3OH

We have increased the frequency tunability of our CW waveguide CO₂ lasers by means of an acoustooptic amplitude modulator, operating at the fixed frequency of 90 MHz. The up-shifted, or down-shifted, laser optical sideband can be generated independently by adjusting the orientation of the modulator. The efficiency is larger than 50%. The frequency tunability of the CO₂ laser around each laser line is thus increased by 180 MHz. To demonstrate the possibilities of this method, a source composed of the above modulator and of a CW, 300 MHz tunable waveguide CO₂ laser has been used for the search of new large offset FIR laser lines from optically pumped CH₃OH and¹³CH₃OH molecules. As a result 15 and 10 new large offset laser lines were discovered respectively. New assignments of some laser lines are also proposed. We have also measured the Stark effect, the offset, and the polarization of other already known lines. In particular a Stark effect frequency tuning of about 1 GHz is demonstrated for a laser line at 208.399 m.     

Near-Infrared Methane Detection Device Using Wavelength-Modulated Distributed Feedback Diode Laser around 1.654 µm

By using a wavelength-modulated distributed feedback laser centered at 1.654 µm, a stand-alone near-infrared methane detection device was experimentally proposed based on the tunable diode laser absorption spectroscopy technique. An intelligent temperature controller, a scan and modulation module, and a cost-effective lock-in amplifier were developed to drive the distributed feedback laser and extract the second harmonic signal. Experimental results show that the relative detection error is less than 7% within the detection range of 0–10⁶ ppm, and the limit of detection is about 11 ppm with an absorption length of 0.2 m. Long-term monitoring on two gas samples (10³ ppm and 2 × 10⁵ ppm) suggests good stability with the maximum detection errors smaller than 7% and 2.5%, respectively. Due to careful design and integration, the developed near-infrared sensor reveals competitive performances compared with our previously reported sensing devices at the mid-infrared region.     

A twin optically-pumped far-infrared CH3OH laser for plasma diagnostics

A twin optically-pumped far-infrared CH₃OH laser has been constructed for use in plasma diagnostics. The antisymmetric doublet due to the Raman-type resonant two-photon transition is reproducibly observed at 118.8 m. With the 118.8-m line, it is obtained from the frequency separation of the anti-symmetric doublet that CH₃OH absorption line center is 16±1 MHz higher than the pump 9.7-m P(36) CO₂ laser line center. It is shown that the Raman-type resonant two-photon transition is useful in order to get several-MHz phase modulation for the far-infrared laser interferometer. Some preliminary performances of this twin laser for the modulated interferometer are described.This work was carried out under the collaborating research program at the Institute of Plasma Physics, Nagoya University, Nagoya 464, Japan.     

YbVO4晶体的受激拉曼散射

采用腔外单次通过方式,研究了一种新型晶体YbVO₄的受激拉曼散射.当抽运激光为532 nm皮秒脉冲时获得了3级斯托克斯线(558.47 nm, 587.92 nm, 620.67 nm)和1级反斯托克斯线(507.58 nm),测得YbVO₄晶体1级斯托克斯受激拉曼散射的稳态增益系数为17.8±0.2 cm/GW,受激拉曼散射的整体转换效率达到37%.实现了YbVO₄晶体对355 nm皮秒激光的受激拉曼散射,观察到1级斯托克斯线(366.1 关键词： 受激拉曼散射 稳态增益系数 转换效率 4晶体')" href="#">YbVO₄晶体     

New FIR Laser Lines from CHD2OH Methanol

We have investigated CHD₂OH methanol as source of far-infrared (FIR) laser radiation using the optical pumping technique. Our new waveguide pulsed CO₂ laser, with peak powers as high as some kW, has allowed us to observe 12 new lines. Each of them is characterized in wavelength, relative polarization, intensity, optimum operating pressure and pump offset from the center of the exciting CO₂ line.     

Surface study of fine MgFe2O4 ferrite powder prepared by chemical methods

To study surface behaviors, MgFe₂O₄ ferrite materials having different grain sizes were synthesized by two different chemical methods, i.e., a polymerization method and a reverse coprecipitation method. The single phase of the cubic MgFe₂O₄ was confirmed by the X-ray diffraction method for both the precursors decomposed at 600-1000 °C except for a very small peak of Fe₂O₃ was detected for the samples calcined at 600 and 700 °C by the polymerization method. The crystal size and particle size increased with an increase in the sintering temperature using both methods. The conductance of the MgFe₂O₄ decreased when the atmosphere was changed from ambient air to air containing 10.0 ppm NO₂. The conductance change, C = G(air)/G(10 ppm NO₂), was reduced with an increase in the operating temperature. For the polymerization method, the maximum C-value was ca. 40 at 300 °C for the samples sintered at 900 °C. However, the samples sintered at 1000 °C showed a low conductance change in the 10 ppm NO₂ gas, because the ratio of the O₂ gas adsorption sites on the particle surface is smaller than those of the samples having a high C-value. The low Mg content on the surface affects the low ratio of the gas adsorption sites. For the reverse coprecipitation method, the particle size was smaller than that of the polymerization method. Although a stable conductance was obtained for the sample sintered at 900 and 1000 °C, its conductance change was less than that of the polymerization method.     

Diode laser measurement of line strengths and air-broadening coefficients of CO2 and CO in the 1.57 μm region for combustion diagnostics

Spectral measurements of two line pairs of CO₂ and CO in the temperature range 300–1000 K at 1.573 µm were performed using a fiber-coupled distributed feedback (DFB) diode laser. The two line pairs can be used in a tunable diode laser (TDL) absorption sensor for simultaneously detecting CO₂ and CO gas in a single scan of the diode laser. The spectral parameters (line strengths, air-broadening coefficients and the temperature exponent n) of the two pairs are presented. The measured data agree well with existing databases (HITRAN 2004 and HITRAN 2008), the discrepancies being less than 5% for most of the probed transitions. Although the HITRAN database is a useful tool for sensor design, we found that laboratory measurements of the spectroscopic data for the line pair selected for high-temperature sensors are necessary for establishing the uncertainty for accurate measurements.     

Simultaneous detection of ammonia, methane and ethylene at 1.63 μm with diode laser photoacoustic spectroscopy

Spectral investigation around 6115 cm^-1 for simultaneous detection of ammonia, methane and ethylene in gas samples is presented. Experimental data on the ν₂+ν₃+ν₄ combination band of ammonia are reported with a resolution of 1.5 GHz. A trace gas analyzer based on a resonant photoacoustic cell and an external cavity diode laser has been used for detection. A data fitting procedure has been developed in order to improve the system sensitivity and to limit the need of a reference cell. The selected spectral region allows a sensitivity of about 60 ppm for ammonia, 6 ppm for methane and 30 ppm for ethylene with 0.3 mW laser power. An application of simultaneous detection of such molecules in a mixture reproducing their typical abundances in real gas samples from biomass gasification is discussed. PACS 42.62.Fi; 42.55.Px; 82.80.Ch     

Experimental and theoretical study of N2-broadened acetylene line parameters in the ν1 + ν3 band over a range of temperatures

N₂-broadened line widths and N₂-pressure induced line shifts have been measured for transitions in the ν₁?+?ν₃ band of acetylene at seven temperatures in the range 213–333?K to obtain the temperature dependences of broadening and shift coefficients. For the room-temperature spectra the line mixing effects have been also investigated. The Voigt and hard-collision line profile models were used to retrieve the line parameters. All spectra were recorded using a 3-channel tuneable diode laser spectrometer. The line-broadening and line-shifting coefficients as well as their temperature-dependence parameters have been also evaluated theoretically, in the frame of a semi-classical approach based on an exponential representation of the scattering operator, an intermolecular potential composed of electrostatic quadrupole–quadrupole and pairwise atom–atom interactions as well as on exact trajectories driven by an effective isotropic potential.     

Detection of ozone by differential absorption using CO2 laser

The differential absorption method with the conventional CO₂ laser is discussed for the detection and monitoring of ozone in ambient atmosphere. By using the P(14) line in the (00°1 to 02°0) and the R(16) line in the (00°1 to 10°0) band, the measurement of ozone was made in a field. As an experimental result, the minimum detectable concentration of 0.15 ppm was obtained with the system, and the concentration of 0.2 ppm was measured in a photo-chemical smog.     

Frequencies and wavelengths from a new, efficient FIR lasing gas: CD2F2

We report for the first time wavelength, relative polarization, and frequency measurements for 47 new cw FIR laser lines in the wavelength region from 120 to 1714 m, all obtained by optically pumping CD₂F₂ with a CO₂ laser. Relative output powers were also measured. For comparison, the 189.8 m line pumped by R_I(34) is nearly five times as efficient as the 118.8 m methyl alcohol line.Contribution of the U.S. Government, not subject to copyright.     

N2O molecular tagging velocimetry

A new seeded velocity measurement technique, N₂O molecular tagging velocimetry (MTV), is developed to measure velocity in wind tunnels by photochemically creating an NO tag line. Nitrous oxide “laughing gas” is seeded into the air flow. A 193 nm ArF excimer laser dissociates the N₂O to O(¹D) that subsequently reacts with N₂O to form NO. O₂ fluorescence induced by the ArF laser “writes” the original position of the NO line. After a time delay, the shifted NO line is “read” by a 226-nm laser sheet and the velocity is determined by time-of-flight. At standard atmospheric conditions with 4% N₂O in air, ∼1000 ppm of NO is photochemically created in an air jet based on experiment and simulation. Chemical kinetic simulations predict 800–1200 ppm of NO for 190–750 K at 1 atm and 850–1000 ppm of NO for 0.25–1 atm at 190 K. Decreasing the gas pressure (or increasing the temperature) increases the NO ppm level. The presence of humid air has no significant effect on NO formation. The very short NO formation time (<10 ns) makes the N₂O MTV method amenable to low- and high-speed air flow measurements. The N₂O MTV technique is demonstrated in air jet to measure its velocity profile. The N₂O MTV method should work in other gas flows as well (e.g., helium) since the NO tag line is created by chemical reaction of N₂O with O(¹D) from N₂O photodissociation and thus does not depend on the bulk gas composition.     

Review of theoretical gain-optimization studies in 10.6µm CO2-N2 gasdynamic lasers

A comprehensive theoretical analysis of optimization of gain in CO₂-N₂ gasdynamic laser employing wedge or conical or hyperbolic nozzles with either H₂O or He as the catalyst is presented. After a review of previous work, the usual governing equations for the steady inviscid quasi-one-dimensional flow in a supersonic nozzle of a gasdynamic laser are used to obtain similar solutions for the various flow quantities, which variables are subsequently used to optimize the small-signal gain on theP(20) line of the (001) → (100) transition of CO₂ at wavelength 10.6μm. The corresponding optimum values like reservoir pressure and temperature and nozzle area ratio also have been predicted and presented in the form of graphs. The analysis predicts that employing of 2D-wedge nozzle results in higher gain values and the CO₂-N₂-H₂O gasdynamic laser employing 2D-wedge nozzle is operationally the best laser system for which the optimum value as high as 3.1 m⁻¹ gain can be obtained.     

The Spectrum of Ground-State Reversed Transition of CH3OH Far-Infrared Laser

Using the CH₃OH molecular energy levels data base management program, we deduced that when a CH₃OH laser pumped by CO₂-9P(16) line, there should be a FIR laser line of 918m wavelength, which corresponding to a transition in ground-state reversed three-level energy system. For the first time, the spectra of ground-state reversed three-level system transitions were calculated by solving the density matrix equations, and the spectrum characteristics of 918m line were studied. Experimentally, the CH₃OH FIR laser line of 918m wavelength was obtained by pumping with a TEA-CO₂ laser. The experimental results were in good agreement with the theoretical calculations.     

In situ measurement of ammonia with a 13CO2-waveguide laser system

A laser gas monitoring system has been developed to measure in situ concentrations of ammonia at various temperatures. The concentration is determined by measuring absorption with a tunable ¹³CO₂ waveguide laser that is frequency modulated between two adjacent emission lines. One line coincides with a strong ammonia absorption line, while the other is used as a reference. By this referencing the system is autocalibrated continuously. The high spectral resolution of the laser suppresses interferences by other species. The system was built up to be used in industrial environment and was successfully applied in the chemical industry and in several power plants. A detection limit of 1 ppm could be reached at a time constant of 5 s.     

Yb3+:Gd2SiO5晶体的结构和光谱性能

采用提拉法成功生长尺寸为φ30 mm× 75 mm的15at.%Yb³⁺:Gd₂SiO₅单晶, 并用Reitveld全谱拟合方法确定了其晶格常数、原子坐标和温度因子等参数. 用吸收光谱计算了Yb³⁺离子²F_7/2↔ ²F_5/2能级跃迁的振子强度、谱线强度、跃迁概率、 能级寿命和积分发射截面等光谱参数, 并根据激光性能评估得出结论: 表明该晶体具有较大的阈值特性, 有望采用大功率激光二极管泵浦实现可调谐或超快激光输出.     

Laser assisted modification and chemical metallization of electron-beam deposited ceria thin films

Excimer laser processing is applied for tailoring the surface morphology and phase composition of CeO₂ ceramic thin films. E-beam evaporation technique is used to deposit samples on stainless steel and silicate glass substrates. The films are then irradiated with ArF* excimer laser pulses under different exposure conditions. Scanning electron microscopy, optical spectrophotometry, X-ray diffractometry and EDS microanalysis are used to characterize the non-irradiated and laser-processed films. Upon UV laser exposure there is large increase of the surface roughness that is accompanied by photo-darkening and ceria reduction. It is shown that the laser induced changes in the CeO₂ films facilitate the deposition of metal nano-aggregates in a commercial copper electroless plating bath. The significance of laser modification as a novel approach for the production of CeO₂ based thin film catalysts is discussed.