傅立叶变换激光腔内吸收光谱方法研究吸收谱线的强度与线形

在原有傅立叶变换激光腔内吸收光谱实验装置的基础上,利用信号差分方法减少了光强波动对实验干涉谱图的影响,改善了信噪比.通过对大气中氧气在760nm处的吸收谱线的绝对强度测量,验证了该方法的定量测量能力.在不同压力条件下对磷烷v=6伸缩局域模泛频吸收谱带进行了测量,获得了其谱线的自压力加宽和自压力线移参数.     

高温高压下基于TDLAS的二氧化碳浓度测量方法研究

通过具有高灵敏度、非侵入式等特性的可调谐二极管激光吸收光谱技术对发动机气缸工作过程等高温高压燃烧环境进行实时在线检测,是了解其内部燃烧过程进而研发高效发动机的重要手段之一。作为一种重要的温室气体和化石燃料燃烧的主要产物,二氧化碳对于了解燃烧过程具有重要的意义。为了寻找一种能够对高温高压燃烧过程中的二氧化碳浓度进行快速检测的方法,利用工作在室温条件下的近红外可调谐二极管激光器作为光源,以二氧化碳位于5 006.140 cm-1处的跃迁作为传感谱线,结合固定波长的吸收光谱调制技术,通过该CO₂谱线的一次谐波归一化的二次谐波信号峰值实现对高温高压环境中CO₂浓度测量,建立了一种可用于高温高压环境下的组份浓度的测量方法,通过实验验证得出该方法在5 atm压力、500 K温度下和10 atm压力、1 000 K温度下对于CO₂浓度测量的平均标准偏差为3.99%;另外还对实验中所得CO₂直接吸收及二次谐波信号进行了分析,得到了其吸收光谱在高温高压环境下的特性。     

Infrared Optoacoustic Spectroscopy of CHD2OH Around 10R and 10P CO2 Laser Lines

In this work we present results of an investigation on Doppler limited infrared absorbing transitions of CHD₂OH by optoacoustic detection. It is an alternative and attractive technique to be applied to this methanol isotopomer, in comparison to Fourier transform spectroscopy. Using a waveguide CO₂ laser of 290 MHz tunability on each line, we were able to observe 60 IR absorptions, most of them of large offset. The data will be useful in the theoretical analysis of this molecule, as well as in the generation of far-infrared (FIR) laser radiation in optically pumped molecular lasers.     

Absorption spectra of CO2 and CO2 near 1.05 μm

The absolute line intensities of the Fermi triad 2003i-00001 (i = 1, 2, 3) of ¹²C¹⁶O₂ and ¹³C¹⁶O₂ isotopic species of carbon dioxide were retrieved from Fourier-transform spectra recorded at Doppler limited resolution in the region 9200-9700 cm⁻¹. The accuracy of the line intensity determination is estimated to be better than 15% for most lines. The vibrational transition dipole moments squared and Herman-Wallis coefficients have been determined. The global fittings of the observed line intensities within the framework of the effective operators method have been performed. The fitting results reproduce the data within experimental uncertainty.     

小型可调谐单纵模TEA CO2激光器

对在三镜腔中插入法布里-珀罗(F-P)标准具实现单纵模激光输出的方法进行了分析,计算了激光器的输出特性。设计研制了一台单纵模可调谐TEA CO2激光器。采用在三镜腔中插入F-P标准具的方法实现了单纵模激光的调谐输出。当激光器以5 Hz重复频率运转时,得到9P(16)谱线能量大于200 mJ,脉冲宽度约为150 ns。     

CO2及其碳同位素比值高精度检测研究

改进了一种基于傅里叶变换红外光谱法测量CO₂气体的装置, 改进后的装置能够提高CO₂检测精度, 并能同时测量CO₂碳同位素比值. 研究了温度和压力对CO₂浓度值和CO₂碳同位素比值测量的影响规律. 利用该装置连续测量了标准CO₂气体和环境大气, 对标准CO₂气体测量得到的CO₂浓度值及其碳同位素比值进行温度和压力影响修正, 获得了较好的精度和准确度. 关键词： 光谱学 同位素比值 傅里叶变换红外光谱 二氧化碳     

Spectroscopy in propyne and ethyl-Chloride by means a tunable CO2 RF laser

Some lines in 5 band of propyne (CH₃CCH) and many strongest lines in the 9 band of ethyl- Chloride (C₂H₅Cl³⁵ A-type) are measured and identified, giving a new set of spectroscopic constants. In particular the ethyl-Chloride set allows to assign all the FIR transitions reported in literature.     

基于可调谐多模二极管激光吸收光谱的二氧化碳浓度测量

可调谐二极管激光吸收光谱技术(TDLAS)具有高分辨率、高灵敏度和快速测量等特点,是气体探测中的主流技术。使用多模二极管激光器作为光源,将多模二极管激光吸收光谱技术与关联光谱技术相结合有助于提高测试可靠性和稳定性,同时还可有效解决单模二极管激光器长时间工作时中心波长随外界温度或机械特性的变化而发生偏移的问题。以1 570 nm多模二极管激光器为光源,利用多模二极管激光关联光谱和波长调制的气体测量技术(TMDL-COSPEC-WMS),通过计算待测气体和参考池气体之间二次谐波信号峰值高度之间的关系,实现了对二氧化碳浓度的测量。实验中二氧化碳浓度测量范围在0.6%～30%之间,计算结果表明,二氧化碳浓度与真实浓度值之间具有良好的线性关系,其线性度为0.998 7,线性拟合的斜率为1.061±0.016 8。对二氧化碳与氮气混合气体的连续测量结果表明,系统的探测极限达到335 ppm·m,对同一样品在20 min内的20次连续测量的标准偏差为0.036 7%,表明了系统良好的稳定性,所有测量结果都显示了系统用于二氧化碳气体监测的有效性。     

H_2(v=1)与CO_2碰撞中CO_2的振动和转动激发

利用高分辨率瞬时激光光谱技术,研究了H2(1,1)与CO2碰撞中的能量转移。受激拉曼泵浦把H2(0,1)激发到H2(1,1)能级,H2(1,1)与CO2碰撞,使CO2的振转态得到布居,通过泛频吸收得到CO2(0000)和(0001)的转动态分布,测量H2(0,1)和H2(1,1)的CARS(相干反斯托克斯拉曼散射)谱,得到这二个能级布居数密度之比,而H2(0,1)密度通过在池温300K下H2(v=0)的转动Boltzmann分布得到。碰撞转移速率系数由一个速率方程得到,对于CO2(0000)J=48~76,速率系数ktr从(3.9±0.8)×10-11单调递增到(1.4±0.3)×10-10 cm3·molecule-1·s-1,而对于(0001)J=5~33,速率系数均在(4.3±0.9)×10-12cm3·molecule-1·s-1附近。随H2(1,1)的激发,在0.5μs内测量CO2(0000)和(0001)原生态的转动布居,得到玻尔兹曼转动温度Trot,对于(0000)态,有Trot=1 100K,对于(0001)态有Trot=310K,与池温接近。利用泛频吸收线的多普勒增宽测量,得到CO2各转动态的实验室平移温度Ttran和质心平移温度Trel,对于(0000)J=48和76,Trel分别为454和1 532K,平动能平均变化在231~1 848cm-1之间,而对于(0001)J=5~33,平均平动能基本无变化。     

中红外波段大气碳同位素激光吸收光谱研究

大气碳同位素在环境污染源汇示踪和地球化学发展等方面的应用越来越广泛,在其探测技术方面,激光吸收光谱技术具有体积小、可在线、灵敏度高等优点,在气体同位素探测中越来越受到重视。工作中研究了2.7 μm波段的分布式反馈激光器(distributed feedback laser, DFB)可调谐半导体激光器的性能,在遵循12CO₂和13CO₂同位素分子吸收谱线特征和同位素分子谱线选择原则的基础上,确定了合适的激光器输出波长。结合光程390.3 m的新型多次反射池,实现了大气中CO₂分子的δ13C同位素丰度探测。     

Spectroscopy of nickel chloride: Identification of the [15.0] Π3/2 and [15.0] Δ5/2 states

Vibrational bands belonging to the [15.0] ²Δ_5/2-A²Δ_5/2, [15.0] ²Δ_5/2-X²Π_3/2, and [15.0] ²Π_3/2-X²Π_3/2 electronic transitions of NiCl have been observed in the 14 000-16 000 cm⁻¹ region. The [15.0] ²Δ_5/2 and [15.0] ²Π_3/2 states are identified for the first time. The observed bands have been recorded at high spectral resolution using several techniques, which include intracavity laser spectroscopy (ILS), Fourier transform emission spectroscopy (FTS), and laser induced fluorescence (LIF) spectroscopy. For the ILS absorption spectra, NiCl molecules were produced in a nickel hollow cathode operated with a small amount of CCl₄. For the FTS emission spectra, excited NiCl molecules were produced in a King-type carbon tube furnace loaded with NiCl₂ and heated to 1600 °C. In the LIF work, NiCl molecules were produced by reacting laser-ablated nickel with PCl₃ seeded in argon. Detailed analysis of rotational transition lines indicates that the observed [15.0] ²Δ_5/2 and [15.0] ²Π_3/2 states are only separated by 10 cm⁻¹ and are interacting with each other. Molecular constants for these newly observed electronic states are reported.     

CO2 laser beam modulating for surface texturing machining

Laser texturing is a novel technique that may be used to texture a cold roller in the process of manufacturing high quality steel sheets. With the aim of improving the quality of the textured roller by using a CO₂ laser, a new laser beam modulating device is proposed. An optical beam expander with a fast rotating chopper system is designed. The laser pulse is split into two parts by the chopper blades; one is the preheating pulse that is reflected onto optical loop mirrors; the other is the directly transmitted pulse that creates the craters at the preheated spots. The preheating beam focus spot size and position can be adjusted. The focusing characteristics and optical parameter compensation for the flying optics are investigated. The heat transfer and melt process of laser texturing are numerically simulated. The effects of the double pulses on the texturing are analyzed. The effect of preheating the sample ahead of the laser texturing pulse is examined. The surface profile and bump hardness show improvements by using this approach.     

振动激发KH与CO_2碰撞中能量的时间分辨分布

K(5P)与H2反应产生KH(Х1Σ+)的ν″=0~3振动能级,泛频激发KH至ν″=17高位振动态。通过测定KH(ν″=17,3)与CO2碰撞过程中振动能的时间分辨分布(即Tν的变化过程),研究了高低振动态碰撞传能的不同特点。对于KH(ν″=17),振动温度Tν的变化分为三个阶段:第一阶段(0~5μs)Tν迅速下降,能量应主要转移至CO2(0001)振动态或(0000)高位转动态;第二阶段(5~20μs)Tν仅稍有下降,向CO2振动态及高位转动态的能量转移已结束;第三阶段(20μs后)Tν虽然缓慢但明显下降,表明向CO2低转动态及平动能的转移加速。对于KH(ν″=3),Tν的变化只分为两个阶段:第一阶段(0~10μs)的共振V-R过程迅速降低了振动温度;第二阶段(10~80μs)Tν有一个缓慢下倾,只能转移到很低的转动态和小的平动能。这些结果表明了振动激发态分子与基态分子碰撞中仅用单一速率系数不能正确揭示复杂平衡过程的本质,不同的阶段应该用不同的速率系数来描述。利用瞬时吸收技术得到CO2(0000)和(0001)的原生态转动布居分布,通过速率方程分析,得到平衡过程中不同阶段的速率系数。     

CO2/CO2 isotopic ratio measurements with a continuous-wave quantum cascade laser in exhaled breath

A laser spectrometer based on a continuous-wave thermoelectrically-cooled distributed feedback quantum cascade laser at ∼2308 cm⁻¹ has been evaluated for measurement of ¹³CO₂/¹²CO₂ isotopic ratio (δ¹³C) changes in exhaled breath samples and in CO₂ gas flows in the concentration range 1-5%. Mid-infrared CO₂ absorption spectra were measured in a 54.2-cm long optical cell using balanced detection whereby the beam passing through the cell was ratioed against a reference beam split-off from the main beam before the cell. Signal-to-noise ratios (SNR) were estimated for CO₂ concentration measurements determined from either absorption peak amplitude or absorption peak area. The highest SNR were achieved in the measurements based upon a fitted absorption peak area. Typical short-term δ¹³C precisions of 1.1⁰/₀₀ (1-s integration time) and 0.5⁰/₀₀ (8-12-s integration time) were estimated from the two-sample (Allan) variance plots of data recorded in the optical cell at a pressure of 20 Torr and with no active temperature stabilization of the cell and gas flow. The best precision of 0.12⁰/₀₀ was achieved for averaging 80 successive 1-s integration time measurements.     

Processing of concretes with a high power CO2 laser

Laser material processing, being a non-contact process, minimizes many of the complexities involved in the decontamination and decommissioning of nuclear facilities. A high power laser beam incident on a concrete surface can produce spalling, glazing or vaporization, depending upon the laser power density and scan speed. This paper presents effect of various laser processing parameters on the efficiency of material removal by surface spalling and glazing. The size of laser beam at constant fluence or energy density had significantly different effect on the spalling process. In thick concrete block cutting the flow or removal of molten material limits the cutting depth. By employing repeated laser glazing followed by mechanical scrubbing process cutting of 150 mm thick concrete block was carried out. Gravitation force was utilized for molten materials to flow out while drilling holes on vertical concrete walls. The dependence of the incident laser beam angle on drilling time was experimentally studied.     

CO2 laser cutting of slate

Slate is a natural stone which has the characteristic that shows a well-developed defoliation plane, allowing to easily split it in plates parallel to that plane which are particularly used as tiles for roof building. At present, the manufacturing of slate is mostly manual, being noisy, powdery and unsafe for the worker. Thus, there is a need to introduce new processing methods in order to improve both the working conditions and the quality of the products made of slate.Following the previous work focused on the drilling and cutting of slate tiles using a Nd : YAG laser, we present in this paper the results of the work carried out to explore the possibilities to cut slate plates by using a CO₂ laser. A 1.5 kW CO₂ laser was used to perform different experiments in which, the influence of some processing parameters (average power, assist gas pressure) on the geometry and quality of the cut was studied. The results obtained show that the CO₂ laser is a feasible tool for a successful cutting of slate.     

第三族金属氧化物离子对二氧化碳转化的红外光谱研究

本文利用红外光解离光谱研究了第三族金属氧化物离子对二氧化碳分子的转化机制. 研究表明,对于[ScO(CO₂)_n]⁺体系,在n≤4时,形成了溶剂化结构;在n=5时,形成了碳酸盐结构,实现了二氧化碳的转化. 对于[YO(CO₂)_n]⁺体系,需要4个二氧化碳分子就可以实现二氧化碳的转化. 而在[YO(CO₂)_n]⁺体系中,只发现了溶剂化结构,没有观察到碳酸盐结构. 理论计算表明,[YO(CO₂)_n]⁺体系拥有最小的溶剂化结构向碳酸盐结构转化能垒,[LaO(CO₂)_n]⁺体系拥有最大的溶剂化结构向碳酸盐结构转化能垒. 本文从分子水平揭示了不同金属氧化物离子对二氧化碳分子转化的影响规律.     

基于脉冲CO2激光锡等离子体光刻光源的极紫外辐射光谱特性研究

研究了不同条件下脉冲放电CO₂激光烧蚀平板锡靶产生的等离子体极紫外辐射特性, 设计并建立了一套掠入射极紫外平焦场光栅光谱仪, 结合X射线CCD探测了光源在6.5～16.8 nm波段的时间积分辐射光谱,得到了极紫外光谱随激光脉宽, 入射脉冲能量及背景气压的变化规律。实验结果发现：入射激光脉冲能量在30～600 mJ变化时,极紫外辐射光谱的强度随辐照激光脉冲能量的增加而增加, 但并不是线性关系, 具有饱和效应, 且产生极紫外辐射的脉冲能量阈值约为30 mJ,当激光脉冲能量为425 mJ时具有最高的转换效率,此时中心波长13.5 nm处2%带宽内的转换效率约为1.2%。激光脉冲半高全宽在50～120 ns范围内变化时, 极紫外辐射光谱的峰值位置均位于13.5 nm,光谱形状几乎没有什么变化, 但是脉宽从120 ns变到52 ns后,由于激光功率密度的提高,极紫外辐射强度也随之增强了约1.6倍。极紫外光谱的强度随背景气压的增大而迅速下降, 当腔内空气气压为200 Pa时, 极紫外辐射光子几乎被全部吸收,而当缓冲氦气气压为7×104 Pa时,仍能够探测到微弱的极紫外辐射信号,计算表明100 Pa的空气对13.5 nm极紫外光的吸收系数为3.0 m-1,而100 Pa的He气的吸收系数为0.96 m-1。     

Modelling of RF CO2 Laser Pulses

The usual laser rate equations have been applied to fit energy and shape of pulsed emissions of RF CO₂ single mode lasers starting from the discharge and cavity parameters. The model well reproduce the laser behaviour, if to fit the turn-off normally observed in these lasers we introduce a phase laser gain correction related to the frequency chirp.     

温度调谐技术测量CO2在6320～6336cm-1波段的吸收光谱

针对当前可调谐半导体激光器吸收光谱(TDLAS)技术中调谐范围、调谐时间以及系统复杂性方面存在的不足,提出了利用激光器模块中的热电制冷器(TEC)和负温度系数(NTC)热敏电阻等元件对激光二极管(LD)进行温度宽谱调谐的方法,并在快速温度调谐过程中精确计算激光器的辐射波长。利用温度调谐二极管吸收光谱技术在3s的时间内测得了CO2气体在6320～6336cm-1波段的高分辨率吸收光谱。在此波段共测得8个较强吸收线。将得到的光谱参数与HITRAN 2008中的数据比较,吸收线位置、线强以及半峰全宽(FWHM)的偏差分别小于1%,3%以及6%。另外,测得的14条较弱的吸收谱线也与谱库中的谱线参数吻合。