横向射流式单重态氧发生器的性能实验研究

 对氧碘化学激光器的单重态氧发生器（SOG）进行了改进，采用横向射流方式，并对该横向射流式单重态氧发生器的性能进行了检测。实验中过氧化氢碱溶液温度控制在－16℃左右,氯气流量为530mmol/s，He与氯气的流量比为3;采用PS法测量单重态氧分子的产率,吸收法测量氯气的利用率和相对水含量。得出如下结论:在不使用冷阱和分离器的情况下，最高单重态氧分子产率达到58%, 氯气利用率在80%以上,相对水含量小于等于0.5;气体达到最大流量时,发生器仍然能稳定地工作。     

单重态氧发生器出口气流中O_2(~1Δ)及水汽绝对浓度的测量

单重态氧发生器是氧碘化学激光器的核心部件 ,O2 (1Δ)和水汽的粒子数密度 (绝对浓度 )是单重态氧发生器的两个重要参量 ,其中O2 (1Δ)是氧碘化学激光器的能源 ,而水汽对氧碘化学激光器的发光介质—I 有强烈的淬灭作用。如何简单准确地测量这两个参量 ,一直是氧碘化学激光器研究中的一个难题。利用体光源模拟标定法 ,得到了O2 (1Δ)和水汽的绝对浓度 ,并且成功地用一套实验装置对射流式单重态氧发生器的上述两个参量进行了实时测量 ,得到了两个参量的变化曲线 ,同时还提供了O2 (1Δ)的产率以及水汽体积浓度等参量的变化曲线 ,通过大量实验结果 ,给出了各参量的变化规律 ,为射流式单重态氧发生器研究提供了有力的参考依据。     

JSOG中水蒸汽含量的模拟计算

氧碘化学激光（简称 COIL）系统中，水是影响激光功率输出的最重要的原因之一。气流中的水不仅对激发态碘原子有严重的猝灭作用，另外对碘分子解离、超音速流动特性也有很坏的负面作用。单重态氧发生器的BHP（Basic Hydrogen Peroxide ）溶液是最主要的水蒸汽源。利用传质模型对射流式单重态氧发生器（简称JSOG）中产生的水蒸汽进行了计算，所得的数值结果与实验测量结果基本相符。根据模拟结果，对发生器的设计及实验条件进行了优化。     

单重态氧发生器出口气流中O2(1△)及水汽绝对浓度的测量

单重态氧发生器是氧碘化学激光器的核心部件．O2(^1△)和水汽的粒子数密度(绝对浓度)是单重态氧发生器的两个重要参量，其中O2(^1△)是氧碘化学激光器的能源，而水汽对氧碘化学激光器的发光介质-I^ 有强烈的淬灭作用。如何简单准确地测量这两个参量，一直是氧碘化学激光器研究中的一个难题。利用体光源模拟标定法，得到了O2(^1△)和水汽的绝对浓度，并且成功地用一套实验装置对射流式单重态氧发生器的上述两个参量进行了实时测量，得到了两个参量的变化曲线，同时还提供了O2(^1△)的产率以及水汽体积浓度等参量的变化曲线，通过大量实验结果，给出了各参量的变化规律，为射流式单重态氧发生器研究提供了有力的参考依据。     

JSOG中水蒸汽含量的模拟计算

 氧碘化学激光（简称 COIL）系统中，水是影响激光功率输出的最重要的原因之一。气流中的水不仅对激发态碘原子有严重的猝灭作用，另外对碘分子解离、超音速流动特性也有很坏的负面作用。单重态氧发生器的BHP（Basic Hydrogen Peroxide ）溶液是最主要的水蒸汽源。利用传质模型对射流式单重态氧发生器（简称JSOG）中产生的水蒸汽进行了计算，所得的数值结果与实验测量结果基本相符。根据模拟结果，对发生器的设计及实验条件进行了优化。     

p-τ值对COIL的影响的实验研究

 实验研究了单重态氧发生器（SOG）的p-τ值，即初始氯气分压与停留时间的乘积，对化学氧碘激光器（COIL）的影响，并分析了诸多实验因素对SOG的p-τ值的影响。对于提高COIL的化学效率具有很重要的实际意义。     

旋流喷雾式单重态氧发生器的气液分离初步研究

为解决气液分离问题,提出了粒径可控离心分离的设想,即通过某种雾化技术产生粒径可控的液滴,然后根据液滴的粒径确定气液分离所需要的离心力,在高速旋转的叶片所产生的离心力作用下液滴一边与气流发生反应一边完成气液分离。为验证这一思想,搭建了一台旋流喷雾式单重态氧发生器（TFA-SOG）,并通过计算流体力学模拟和实验对这台TFA-SOG进行了研究。研究结果表明,模拟的气液分离效率与实验的相一致,粒径可控离心分离的设想是可行的。     

射流式单重态氧发生器理论模型

 射流式单重态氧发生器(JSOG)是化学氧碘激光器十分重要的能源部分，它主要是通过解气相、液相扩散方程来求解发生器出口的氯的利用率和单重态氧的产率。在实际工作中的射流发生器非常复杂，其扩散方程和边界条件为非线性，非齐次边界条件，非齐次泛定方程组，求解难度较大。通过边界条件，采用试探解的方法，解得氯、总氧、单重态氧的气相、液相扩散方程，得到了氯的利用率，及单重态氧产率的解析解，与实验结果基本相符。     

射流式单重态氧发生器研究

单重态氧O2 (a1Δg)是迄今唯一能用纯化学反应高效产生的具有长寿命的亚稳激发态分子 .为了考察提出的用两个O2 (1Δ)能量汇集反应生成氧第二单重激发态O2 (b1Σ+ g)以实现近可见短波长化学激光方案的现实性 ,设计和实验了一个氯流量为 3～ 10mmol/s的射流式单重态氧发生器 (JSOG) .考察了三种具有不同孔径和孔数目的喷头、氯气流量和脱水冷阱温度等对JSOG出口的O2 (1Δ)浓度、O2 (1Δ)分压、氯利用率及水蒸气含量的影响 .发现用聚氯乙烯管作冷阱时 ,最佳冷阱介质温度为 - 140～ - 15 0℃ ,对此提出了O2 (1Δ)表面脱活与脱水互相竞争的解释 .在最佳条件下 ,可将O2 (1Δ)气中水分压降低至 4Pa ,这一结果是首次报导     

氧碘化学激光器中转盘式单重态氧发生器研究

 通过对单重态氧发生器（SOG）内的传质、传热及化学动力学过程的研究，提出高效SOG的设计原则，并研制出一台可用于高功率超音速氧碘化学激光器（COIL）的SOG， 其Cl₂流量在0.6~1mol/s时，O₂(¹Δ)分压可达333.3~519.9Pa； O₂(¹Δ)浓度达到50%~68%；Cl₂利用率大于90%；混合气中水蒸汽含量小于10%。     

Centrifugal spray generator of singlet oxygen for a chemical oxygen-iodine laser

A centrifugal spray generator of singlet oxygen, O₂(¹Δ_g), for driving a chemical oxygen-iodine laser was developed and its operation was experimentally studied. Modeling of the liquid separation from the gas flow showed that the separator designed could remove droplets larger than 0.5 μm from gas, which is very important for the laser operation. This result was confirmed by experiments. Experimental studies proved that O₂(¹Δ_g) could be produced with a high efficiency (chlorine utilization 0.68–0.87 and O₂(¹Δ_g) yield 0.35–0.7) even at very high generator pressures (25–70 kPa), which cannot be attained by other O₂(¹Δ_g) generators.     

High throughput jet singlet oxygen generator for multi kilowatt SCOIL

A jet flow singlet oxygen generator (JSOG) capable of handling chlorine flows of nearly 1.5 mol s⁻¹ has been designed, developed, and tested. The generator is designed in a modular configuration taking into consideration the practical aspects of handling high throughput flows without catastrophic BHP carry over. While for such high flow rates a cross-flow configuration has been reported, the generator utilized in the present study is a counter flow configuration. A near vertical extraction of singlet oxygen is effected at the generator exit, followed by a 90° rotation of the flow forming a novel verti-horizontal COIL scheme. This allows the COIL to be operated with a vertical extraction SOG followed by the horizontal arrangement of subsequent COIL systems such as supersonic nozzle, cavity, supersonic diffuser, etc. This enables a more uniform weight distribution from point of view of mobile and other platform mounted systems, which is highly relevant for large scale systems. The present study discusses the design aspects of the jet singlet oxygen generator along with its test results for various operating ranges. Typically, for the intended design flow rates, the chlorine utilization and singlet oxygen yield have been observed to be ∼94% and ∼64%, respectively.     

Spray generator of singlet oxygen for a chemical oxygen-iodine laser

A spray type of singlet oxygen generator for driving the Chemical Oxygen-Iodine Laser was developed. Singlet oxygen, O₂(¹Δ_g), is generated by a fast reaction of chlorine with basic hydrogen peroxide solution in the form of a dense spray. A mathematical model of this reaction system showed that O₂(¹Δ_g) can be generated in this system with a high yield (0.70–0.80), high utilization of chlorine (0.75–0.95), and effective utilization of liquid (0.36–0.54) at very high generator pressures (35–75 kPa). Experimental studies of this reaction system without an efficient separation of liquid proved an efficient O₂(¹Δ_g) production characterized by a rather high product of chlorine utilization and O₂(¹Δ_g) yield (0.4–0.9) at very high generator pressures (30–80 kPa). This pressure is much higher than the operation pressure used in other generators, which should be beneficial for a pressure recovery system of the COIL. These results provided the basis for designing a centrifugal spray generator with an efficient separation of liquid from the gas flow, which is the subject of the following paper.     

Diagnostics of an O<Subscript>2</Subscript>(<Superscript>1</Superscript>Δ) generator using multichannel recording of oxygen emission spectra

The concentrations of water vapor and O₂(¹Δ), as well as the temperature in the gas flow at the exit of a singlet oxygen generator, are determined using multichannel recording of the singlet oxygen emission spectrum in the bands at 634, 703, 762, and 1268 nm. The water vapor concentration is found from the intensity ratio of the 762-nm band, which corresponds to the ¹Σ → ³Σ transition of the oxygen molecule, and the dimole emission band at 634 nm. From the ratio of the integrated intensities of the bands at 634 and 1268 nm, the O₂(¹Δ) concentration is determined and it is shown that the yield of O₂(¹Δ) at the exit from the gas generator is about 52%. The temperature of the gas flow, determined by the rotational structure of the oxygen emission spectrum in the band at 762 nm, is about 300 K under the nominal conditions of the gas generator operation. The ratio of the photon fluxes in the 703 and 634nm bands of the O₂(¹Δ) dimole emission is 1.06. The temperature dependence of the dimole emission bandwidths is determined, which can be used for estimating the gas temperature at the exit of the O₂(¹Δ) generator.     

The rate constants of singlet oxygen collision-induced emission at 634 and 703 nm wavelengths

Absolute spectral luminosity from an O₂–O₂(a)-H₂O gas flow formed by a chemical singlet oxygen generator was measured at 600–800 and 1230–1310 nm wavelengths. The results were used to determine the rate constants for O₂(a, 0) + O₂(a, 0) → O₂(X, 0) + O₂(X, 0) + hν (λ = 634 nm) and O₂(a, 0) + O₂(a, 0) → O₂(X, 1) + O₂(X, 0) + hν (λ = 703 nm) collision-induced emission ((6.72 ± 0.8) × 10⁻²³ and (7.17 ± 0.8) × 10⁻²³ cm³/s, respectively).     

Spectral dependence of the efficiency of direct optical excitation of molecular oxygen in tetrachloromethane

The spectral dependence of the efficiency of direct optical excitation of an oxygen molecule in tetrachloromethane using cw LED sources with different wavelengths and an optical parametric oscillator with single-shot output radiation (tuning range of 415–670 nm) has been studied by recording the phosphorescence of singlet oxygen at the O₂(¹Δ_g)–O₂(³Σ_g) transition (λ = 1270 nm). The results show that single-shot irradiation of tetrachloromethane in the short-wavelength spectral range leads to efficient quenching of singlet- oxygen phosphorescence by the products of photolytic decomposition of solvent.     

Discharged generator of singlet oxygen for oxygen-iodine laser. Transport kinetics of O2(a 1δg) and O2(b 1σ g + ) molecules and O(3 P) atoms in Ar:O2 and He:O2 flows excited by a 13.56-MHz discharge

To understand and reveal the basic physical factors providing the possibility of scaling of a discharged singlet oxygen generator (DSOG) in an oxygen-iodine laser, the production, and transport kinetics of metastable O₂(a ¹δ_g) and O₂(b ¹σ _g ⁺ ) molecules, as well as O(³ P) atoms, were investigated in Ar:O₂ and He:O₂ gas flows excited by a 13.56-MHz discharge in a wide range of pressures (4–40 Torr) and oxygen percentages. It is shown that the densities and transport kinetics of O₂(a ¹δ_g), O₂(b ¹σ _g ⁺ ), and O(³ P) appear similar for oxygen mixtures with argon and helium in the same conditions independent of discharge mode. Compared to pure O₂, the dilution of oxygen with an inert gas allows higher energy inputs per an oxygen molecule to achieved, especially under conditions of the homogeneous discharge mode (α-mode), which gives a higher efficiency of O₂(a ¹δ_g) excitation in Ar:O₂ and He:O₂ mixtures. But the maximum attainable yield of singlet oxygen in Ar:O₂ and He:O₂ at fixed partial O₂ pressure is found to be comparable with the O₂(a ¹δ_g) yield in pure oxygen at the same pressure. The reason for this is the increased three-body deactivation of O₂(a ¹δ_g) by atomic oxygen in the mixtures because of the greater total pressure. The estimation of the rate constant of O₂(a ¹δ_g) three-body quenching by O(³ P) in Ar:O₂ and He:O₂ mixtures as (1.5 ± 0.5) × 10^?32 cm⁶/s was carried out from the analysis of transport kinetics of singlet and atomic oxygen in the discharge afterglow at high pressures exceeding ～10 Torr. A similar analysis for the lower pressures has revealed that losses both of metastable O₂(a ¹δ_g) and O₂(b ¹σ _g ⁺ ) molecules, and of O(³ P) atoms on the surface of the discharge tube, are determined by the density of each of the components. The obtained loss probabilities of O₂(a ¹δ_g), O₂(b ¹σ _g ⁺ ), and O(³ P) on the silica surface show that the surface loss probabilities of all the species can increase noticeably under the discharge exposure. Thus, the key parameters determining the maximal O₂(a ¹δ_g) yield in the DSOG are a homogeneous volumetric mode of the discharge, energy input per oxygen molecule in this mode, and a low rate of O₂(a ¹δ_g) quenching. Just three-body quenching of O₂(a ¹δ_g) by O(³ P) limits the singlet oxygen yield with increasing pressure. The fast removal of atomic oxygen both in discharge and in the earlier afterglow could provide DSOG scaling with pressure.     

Synthesis and Characterization of New Fluorene-Based Singlet Oxygen Sensitizers

The synthesis, photophysical characterization, and determination of singlet oxygen quantum yields (Φ_Δ) for a class of fluorene derivatives with potential application in two-photon photodynamic therapy (PDT) is reported. It has been demonstrated that these compounds possess the ability to generate singlet oxygen (¹O₂) upon excitation. A photochemical method, using 1,3-diphenylisobenzofuran (DPBF) as ¹O₂ chemical quencher, was employed to determine the singlet oxygen quantum yields (Φ_Δ) of the fluorene-based photosensitizers in ethanol. Φ_Δ values ranged from 0.35 to 0.75. These derivatives may have potential application as two-photon photosensitizers when pumped via two-photon excitation in the near-IR spectral region.     

High-pressure subsonic mode operation of chemical oxygen-iodine laser

A new regime of chemical oxygen-iodine laser (COIL), high-pressure subsonic mode operation, was demonstrated using a jet-type singlet oxygen generator (SOG). The laser output power of 342 W with chemical efficiency of 20.9% was obtained at the Cl₂ flow rate of 18 mmol/s and the operating pressure of 6.4 Torr in the laser cavity. The specific energy was 3.1 J/l which was four times higher than our supersonic device, and was comparable to the highest value for the supersonic regime. The experimental results were in good agreement with the numerical simulation results. Received: 26 February 1999 / Revised version: 13 July 1999 / Published online: 30 November 1999