Stereoscopic flow-tagging velocimetry

A laser-based method for measuring the three components of the velocity in a plane simultaneously and instantaneously without seed particles is presented. This is achieved by combining a laser flow-tagging technique with stereoscopic detection, in which the tagged flow is viewed from two different directions. A single CCD camera is employed for this purpose by using a new optical detection system. The flow tagging is performed by two consecutive laser pulses, i.e., “write” and “read” laser pulses. The write laser creates a grid of tracer molecules (NO) by inducing a photodissociation process. The three-dimensional motion of the tracer molecules is measured by a thick read laser sheet. Received: 22 July 1999 / Revised version: 5 August 1999 / Published online: 30 September 1999     

Isotopic ratio measurement of methane in ambient air using mid-infrared cavity leak-out spectroscopy

We report on infrared laser spectroscopic measurements of the isotopic composition of methane (¹²CH₄, ¹³CH₄) in natural air samples with a cavity ring-down technique. A CO overtone sideband laser is utilized to excite a high-finesse cavity which provides an effective optical absorption path length of 3.6 km. We achieved a detection limit of 105 ppt methane in ambient air using an integration time of 20 s. This corresponds to a minimum detectable absorption of 1.9×10^-9 /cm. Rapid determination of the ¹³C/¹²Cisotopic ratio of methane in ambient air without sample preconcentration or gas processing is realized. The present system requires only few minutes for an isotopic ratio measurement with a precision of 11%o . Received: 14 July 2000 / Revised version: 25 October 2000 / Published online: 6 December 2000     

Rapid formaldehyde monitoring in ambient air by means of mid-infrared cavity leak-out spectroscopy

We report the spectroscopic detection of formaldehyde in ambient air using cavity leak-out spectroscopy, a cw variant of cavity ring-down spectroscopy. This technique proved to be suitable for a real-time quantitative analysis of polluted air without any preprocessing of the air sample. Using a tunable CO-overtone sideband laser for the λ=3 μm spectral region and a ring-down cell with R=99.95% mirrors, we achieved a detection limit of 2 parts per billion formaldehyde in ambient air, corresponding to a minimum detectable absorption coefficient of 7×10^-9/cm (sampling time: 2 s). Calibration problems arising from the polarity of the molecule and due to HITRAN database uncertainties are discussed. Received: 28 March 2002 / Revised version: 7 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +49-211/811-3121, E-mail: muertz@uni-duesseldorf.de     

Effective A-state fluorescence lifetime of formaldehyde in atmospheric pressure CH4/air flames

Using excitation pulses of ∼30-ps duration and a fast photomultiplier detector, effective fluorescence lifetimes of the A-stateof formaldehyde after excitation at 355 and 339 nm have been measured in the preheating zone of an atmospheric pressure, premixed methane/air flame. The fluorescence lifetimes were determined as a function of height above the exit of a slot burner and were thus probed in regions of varying gas temperature and composition. The fluorescence lifetimes were independent of the intensity of the excitation pulse and decreased as a function of height in the burner from ∼18±8 ns at 1.2 mm down to 7±1 ns at 3.8 mm. This trend of the effective fluorescence lifetime with composition and temperature in the flame can qualitatively be reproduced using calculated major species mole fractions and species-specific quenching cross sections for CH from the literature. Received: 13 June 2001 / Revised version: 27 September 2001 / Published online: 29 November 2001     

In situ observation of UF5 nanoparticle growth in a low-pressure mixed-flow reactor

5 nanoparticles equipped with an in situ size-monitoring system, a LPDMA (low-pressure differential mobility analyzer), was developed to experimentally investigate the nanoparticle growth mechanism. The concentration of photoproduced UF₅ molecules was controlled by changing three factors: (I) the concentration of the feed UF₆ gas, (II) the laser pulse energy of the irradiation, and (III) the repetition rate of the laser pulses. The dependence of the volumetric average diameter of the photoproduced particles on the UF₅ nascent concentration in all three cases was found to be very similar. The result strongly suggests that the reactor functions as a mixed-flow reactor under a complete mixing condition. The particle size measured by the LPDMA was found to be in the range of 6 to 11 nm, and it was approximately proportional to the power 0.3 of the initial concentration of photoproduced UF₅ molecules. Received: 11 May 1998/Accepted: 15 September 1998     

Dynamics of photon-induced degradation and fluorescence in riboflavin microparticles

An unexpected blue-fluorescence band (around 420 nm) from both micrometer-sized dried particles and aqueous droplets of riboflavin [7,8-dimethyl-10-(D-1^′-ribityl)-isoalloxazine] is observed when the microparticles are irradiated with a pulsed UV (355- or 351-nm) laser. The intensity of the band increases quadratically with input laser energy density (fluence) and is attributable to a one-photon-excited fluorescence of lumichrome (7,8-dimethyl-alloxazine) that is produced by photo-degradation of riboflavin. The well-known greenish-yellow fluorescence band (at 560 nm for dried particles and 535 nm for aqueous droplets) from riboflavin increases sublinearly with UV-laser fluence. With a laser input fluence above 5 J/cm² the riboflavin fluorescence decays earlier and the lumichrome fluorescence reaches a maximum later than the peak of the input laser pulse. The temporal dynamics of the 420- and 535-nm fluorescence peaks are consistent with a rate-equation simulation of photon-induced conversion of riboflavin to lumichrome and the subsequent fluorescence of lumichrome. Received: 28 September 2000 / Revised version: 11 December 2000 / Published online: 21 February 2001     

Droplet velocity and acceleration measurements in dense sprays by laser flow tagging

The feasibility of liquid-phase velocity measurements in dense sprays by 2D laser-based flow tagging is demonstrated. Velocity measurements in dense sprays are difficult with conventional techniques because of the high number densities of droplets, the optical thickness of the medium, and multiple light-scattering effects. The present flow-tagging technique is based on phosphorescent tracer molecules, which are excited by a grid of pulsed ‘write’ laser beams. The motion of the tagged droplet groups can be observed by a CCD camera in this way. In addition, multiple consecutive velocity measurements are performed by ‘droplet-group tracking’. This yields the acceleration along the trajectory of individual groups of droplets in unsteady sprays. Received: 5 June 2000 / Revised version: 28 July 2000 / Published online: 6 September 2000     

In-situ monitoring of UF5 nanoparticle growth in a plug-flow reactor by a low-pressure differential mobility analyzer

The dependence of UF₅ nanoparticle size distribution on growth time was investigated for various initial concentrations of UF₅ monomers. UF₅ nanoparticles prepared by photodissociation of UF₆ in a mixed-flow reactor were allowed to pass through a plug-flow reactor (PFR), and their size distribution was measured by an in-situ size-monitoring system, namely a low-pressure differential mobility analyzer. By changing the length of the PFR, the growth time in the PFR was controlled from 0 to 30 s. An analysis using Lee’s coagulation model revealed that the growth mechanism of the UF₅ nanoparticles involved a Brownian coagulation process and that the sticking probability of the nanoparticles was approximately unity. Received: 27 August 2001 / Accepted: 6 September 2001 / Published online: 20 December 2001     

Supersonic velocimetry in a shock tube using laser enhanced ionisation and planar laser induced fluorescence

 A novel flow-tagging technique is presented which was employed to measure gas velocities in the free stream of a shock tube. This method is based on the laser spectroscopic techniques of Laser-Enhanced Ionisation (LEI) and Laser-Induced Fluorescence (LIF). The flow in the shock tube is seeded with small amounts of sodium, and LEI is used to produce a substantial depletion of neutral sodium atom concentration in a well-defined region of the flow, by using two wavelength-resonance excitation and subsequent collisional ionisation. At a specific time delay, single-laser-pulse planar LIF is utilised to produce a two-dimensional (2-D) inverse image of the depleted tagged region downstream of the flow. By measuring the displacement of the tagged region, free stream velocities in a shock tube were determined. Large variations in the concentration of sodium seeded into the flow were observed and even in the presence of these large variations accurate free-stream velocity measurements were obtained. The experimentally determined value for velocity compares very well with the predicted velocity. Received: 25 March 1996/Revised version: 8 July 1996     

Real-time monitoring of ethane in human breath using mid-infrared cavity leak-out spectroscopy

We report on spectroscopic real-time analysis of ethane traces in exhaled human breath. Ethane is considered the most important volatile marker of free-radical induced lipid peroxidation and cell damage in the human body. Our measurements were carried out by means of mid-infrared cavity leak-out spectroscopy in the 3 μm region, a cw variant of cavity ring-down spectroscopy. The spectrometer is based on a CO overtone laser with tunable microwave sidebands. The resulting system proved to be an unique tool with high sensitivity and selectivity for rapid and precise breath testing. With a 5 s integration time, we achieved a detection limit on the order of 100 parts per trillion ethane in human breath. Thus, sample preconcentration is unnecessary. Time-resolved monitoring of the decaying ethane fraction in breath after smoking a cigarette is demonstrated. Received: 13 March 2001 / Published online: 9 May 2001     

Negligibility of temporal laser wing effects in saturated LIF diagnostics

The temporal influence of a laser pulse on saturated laser-induced fluorescence is investigated by means of numerical solutions of rate equations describing dynamical models of two- and four-level molecular systems. It turns out that temporal wings of the laser become negligible if the saturated fluorescence power from the entire pulse is monitored instead of the total energy obtained from the integrated fluorescence. The negligibility is evaluated relative to the saturation status obtained with temporal sampling of the fluorescence signal as is commonly adopted in the time-resolved technique. The advantages and the limitations of power measurements are discussed with reference to the experimental feasibility of pulse acquisitions for the determination of the flawless saturation degree. Received: 4 December 2002 / Revised version: 14 February 2003 / Published online: 5 May 2003 RID="*" ID="*"Corresponding author. Fax: +39-06/3048-4811, E-mail: michele.marrocco@casaccia.enea.it     

Pulsed cavity ring-down spectroscopy of NO and NO2 in the exhaust of a diesel engine

The application of pulsed cavity ring-down spectroscopy has been demonstrated for the in situ quantitative determination of NO and NO₂ in the exhaust of a diesel engine. NO absorption has been monitored at the transition from the Χ²Π ground state to the A²Σ⁺ state at 226 nm. For NO₂, absorption bands in the spectral region from 438 nm to 450 nm were used. At the selected engine conditions, concentrations of 212±22 ppm and 29±4 ppm have been measured for NO and NO₂, respectively, in good agreement with separate chemical exhaust gas analysis. The method is sensitive enough to meet the European Euro V standard directive on NO_x emissions. This communication discusses the relatively simple setup needed for this type of measurement, the problems encountered, as well as the prospects for single-stroke, simultaneous measurements of both NO and NO₂ at the sub-ppm level. Received: 30 November 2001 / Revised version: 18 February 2002 / Published online: 14 March 2002     

Planar dropsizing by elastic and fluorescence scattering in sprays too dense for phase Doppler measurement

An attempt was made to measure, non-intrusively, average droplet sizes in a dense cooling spray of water. The small droplet size and high number density presented severe problems to conventional nonintrusive measurement methodology with phase Doppler anemometry (PDA). A recently developed optical technique, with more promise for measurements in dense sprays, laser sheet dropsizing (LSD), was tried with more success. Sources of error were considered and the uncertainty of the drop sizes measured by LSD was estimated at ±7%, neglecting multiple scattering, dropsize distribution effects and the contributions of droplets at the edge of the laser beam. The greatest of the known contributions to uncertainty is the calibration of the technique against PDA. The greatest of the unknown contributions is likely to be multiple scattering in such dense sprays. Received: 1 March 2000 / Revised version: 25 May 2000 / Published online: 20 September 2000     

Fundamental noise sources in a high-sensitivity two-tone frequency modulation spectrometer and detection of CO2 at 1.6 μm and 2 μm

2 , and its sensitivity is 7(2)×10^-8 in a 1-Hz bandwidth. The corresponding minimum detectable concentration of CO₂ in air has been estimated to be 1 ppm · m. This opens the possibility of a detection at ppb levels at 2 μm, where a two orders of magnitude increase in the CO₂ absorption signal is demonstrated. Received: 06 April 1998/Revised version: 02 July 1998     

Sub-Doppler fluorescence on the atomic <Emphasis Type="Italic">D</Emphasis><Subscript>2</Subscript> line of a submicron rubidium-vapor layer

An extremely thin cell (ETC) with the thickness of a Rb atomic vapor layer in the range of 100–300 nm was fabricated. It is demonstrated that a simple laser-diode technique with a single resonant light beam is sufficient to observe separately all of the atomic hyperfine transitions of the D ₂ line of Rb (780 nm) and also allows us to measure the relative transition probabilities of the hyperfine transitions. The onset of collisional self-broadening of the hyperfine transitions as the number density of atoms increases was studied. The detrimental role of the atoms with slow longitudinal velocity in the sub-Doppler response of the Rb ETC is demonstrated by studies in which the cell is tilted from normal incidence of the laser beam. It is also shown that using an ETC allows us to resolve in a moderate external magnetic field the Zeeman splitting of the hyperfine transitions of the ⁸⁷Rb D ₁ transition F _g=1F _e=1,2. Received: 19 February 2003 / Revised version: 4 April 2003 / Published online: 2 June 2003 RID="*" ID="*"Corresponding author. Fax: +374/32-31172, E-mail: david@ipr.sci.am     

Mid-infrared laser-induced grating experiments of C2H4 and NH3 from 0.1–2 MPa and 300–800 K

Laser-induced thermal gratings (LITG) were generated in mixtures of ethylene and ammonia in nitrogen using mid-infrared laser radiation from a grating-tuned, low-pressure, pulsed (5 ms pulse width) CO₂ laser, and read out with a continuous wave Nd:YLF laser. The LITG signal intensity was measured as a function of pressure (0.1–2 MPa) and temperature (300–800 K, at 0.1 and 1 MPa) by tuning the laser to the accidental coincidences of the 10P(14) and 10R(6) emission lines with molecular absorption transitions of C₂H₄ and NH₃, respectively. Comparisons are made with theoretical predictions for the grating efficiency from a simple thermalization model. A theoretical comparison of the temporal LITG signal response for three excitation pulse shapes – a delta function, a realistic pulse, and a square wave is presented. Furthermore, it is shown that for NH₃, most of the decrease of the LITG signal intensity with increasing temperature is due to the corresponding decrease in fractional molecular absorption of the pump beam radiation. The diagnostic capabilities of the mid-infrared LITG experiment is demonstrated for spatially resolved ethylene measurements with long laser pulses in a premixed stoichiometric CH₄–air flame at atmospheric pressure. Received: 17 March 2000 / Revised version: 23 March 2000 / Published online: 13 September 2000     

Exhaust-gas imaging via planar laser- induced fluorescence of sulfur dioxide

The potential use of planar laser-induced fluorescence (PLIF) of sulfur dioxide (SO₂) for visualization of exhaust-gas distributions is outlined and demonstrated. Strong absorption features in the UV spectral range allow excitation of SO₂ with the fourth harmonic of a Nd:YAG laser at 266 nm. Fluorescence emissions are mostly red-shifted and can be easily detected in single-shot imaging arrangements with a good signal-to-noise ratio. This study uses a premixed methane/air flame that is doped with SO₂ to demonstrate the technique. The signal strength has a pronounced temperature dependence for excitation at 266 nm. Received: 14 January 2002 / Revised version: 30 January 2002 / Published online: 14 March 2002     

Real-time measurements of trace gases using a compact difference-frequency-based sensor operating at 3.5 μm

3 for on-line absorption measurements of H₂CO, CH₄, and H₂O near 3.5 μm is reported. Formaldehyde levels of 30 ppb, corresponding to absorptions of 2×10^-4 have been measured using absorption spectroscopy. In this paper we report specifically the performance of this sensor as part of the 1997 Lunar–Mars Life Support Test program at the NASA Johnson Space Center. Received: 1 April 1998     

High-resolution cavity leak-out absorption spectroscopy in the 10-μm region

2 laser. After excitation, the laser power is turned off for a short time and the subsequent decay of the radiation stored in the cavity is observed via detection of the light leaking out through one of the cavity mirrors. Measurement of the decay time allows one to determine the photon losses und thus to detect weakly absorbing species inside the cavity. Since the cavity is frequency-locked to the laser the decay time can be probed with a high repetition rate, basically limited by the sampling rate of the analog-to-digital converter. This approach is closely related to cavity ring-down spectroscopy with pulsed lasers, but exhibits several advantages concerning spectral resolution and detection sensitivity. As a practical example we demonstrate monitoring of trace amounts of ethylene. Using R=99.5% mirrors we achieve a detection limit of 1 ppb ethylene (integration time: 100 s) corresponding to absorption losses of 3×10^-8 /cm. Further improvement is feasible when mirrors with higher reflectivity become available. Received: 2 July 1998     

Portable difference-frequency laser-based cavity leak-out spectrometer for trace-gas analysis

We report a portable mid-infrared spectrometer for trace-gas analysis which is based on an all-solid-state difference-frequency-generation laser. The spectrometer provides in situ absorption path lengths of more than 3 km by means of the cavity leak-out method, a cw variant of the cavity ring-down technique. The design, performance, and application of this spectrometer are presented. The light source utilizes difference-frequency generation in a periodically poled lithium niobate (PPLN) crystal pumped by two single-frequency solid-state lasers. A maximum power of 27 μW in the wavelength region near 3.3 μm is achieved using a pump power of 20 mW at 808 nm, a signal power of 660 mW at 1064 nm, and a 50-mm-long PPLN crystal. This corresponds to a conversion efficiency of 0.42 mW/(W² cm). We demonstrate that this portable laser system is suitable as a light source in a cavity leak-out spectrometer. We achieved a minimum detectable absorption coefficient of 1×10^-8/cm (integration time: 2 s), corresponding, for example, to a detection limit of 1 part per billion ethane. This compact trace-gas analyzer with high sensitivity and specificity is promising for various environmental and medical applications. Received: 8 April 2002 / Revised version: 28 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +49-211/811-3121, E-mail: muertz@uni-duesseldorf.de