Multipass open-path Fourier-transform infrared measurements for nonintrusive monitoring of gas turbine exhaust composition

The detection limits for NO and NO2 in turbine exhausts by nonintrusive monitoring have to be improved. Multipass mode Fourier-transform infrared (FTIR) absorption spectrometry and use of a White mirror system were found from a sensitivity study with spectra simulations in the mid-infrared to be essential for the retrieval of NO2 abundances. A new White mirror system with a parallel infrared beam was developed and tested successfully with a commercial FTIR spectrometer in different turbine test beds. The minimum detection limits for a typical turbine plume of 50 cm in diameter are approximately 6 parts per million (ppm) for NO and 9 ppm for NO2 (as well 100 ppm for CO2 and 4 ppm for CO).     

Four-laser airborne infrared spectrometer for atmospheric trace gas measurements

We describe the four-laser airborne infrared (FLAIR) instrument, a tunable diode laser absorption spectrometer designed for simultaneous high-sensitivity in situ measurements of four atmospheric trace gases in the troposphere. The FLAIR spectrometer was employed during the large-scale airborne research campaign on tropospheric ozone (TROPOZ II) in 1991 and was used to measure CO, H(2) O(2), HCHO, and NO(2) in the free troposphere where detection limits below 100 parts in 10(12) by volume were achieved.     

Multipass capillary cell for enhanced Raman measurements of gases

A simple Raman multipass capillary cell (MCC) is described that gives 12- to 30-fold signal enhancements for non-absorbing gases. The cell is made by coating the inside of 2-mm inner diameter silica capillary tubes with silver. The device is very small and suitable for remote and in situ Raman measurements with optical fibers. Application of the MCC is similar to previously described liquid core waveguides but, unlike the latter devices, the MCC is generally more applicable to a wide range of non-absorbing gases.     

Pulsed-laser excitation of acoustic modes in open high-Q photoacoustic resonators for trace gas monitoring: results for C(2)H(4)

The pulsed excitation of acoustic resonances was studied with a continuously monitoring photoacoustic detector system. Acoustic waves were generated in C(2)H(4)/N(2) gas mixtures by light absorption of the pulses from a transversely excited atmospheric CO(2) laser. The photoacoustic part consisted of high-Q cylindrical resonators (Q factor 820 for the first radial mode in N(2)) and two adjoining variable acoustic filter systems. The time-resolved signal was Fourier transformed to a frequency spectrum of high resolution. For the first radial mode a Lorentzian profile was fitted to the measured data. The outside noise suppression and the signal-to-noise ratio were investigated in a normal laboratory environment in the flow-through mode. The acoustic and electric filter system combined with the averaging of the photoacoustic signal in the time domain suppressed the outside noise by a factor of 4500 (73 dB). The detection limit for trace gas analysis of ethylene in pure N(2) was 2.0 parts in 10(9) by volume (ppbV) (minimal absorption coefficient α(min) = 6.1 × 10(-8) cm(-1), pulse energy 20 mJ, 1-bar N(2)), and in environmental air, in which the absorption of other gas components produces a high background signal, we can detect C(2)H(4) to ~180 ppbV. In addition, an alternative experimental technique, in which the maximum signal of the second azimuthal mode was monitored, was tested. To synchronize the sampling rate at the resonance frequency, a resonance tracking system was applied. The detection limit for ethylene measurements was α(min) = 9.1 × 10(-8) cm(-1) for this system.     

Miniature triaxial metastable ionization detector for gas chromatographic trace analysis of extraterrestrial volatiles

Gas chromatography has found highly successful application in NASA's flight programs. Gas chromatographs have been flown to both Mars and Venus where detailed compositional measurements were made. These instruments were quite small and relatively sensitive when compared to commercially available instruments; however, they do not appear adequate for future missions currently being planned. The earlier flight GC's had incorporated thermistor bead thermal conductivity cells as the detector. This detector requires very precise temperature control and only provides about 1 ppm sensitivity. Temperature stabilization causes the detector to be quite heavy, i.e., about 200 g. Greater sensitivity will be required for measurements of trace components in extraterrestrial environments. Review of other detector types revealed the metastable ionization detector as a likely candidate because of its superior thermal stability and high sensitivity. The metastable detector, first described by Lovelock as an argon ionization detector, has been studied and somewhat modified by others. The commercial design by Hartmann and Dimick was used for comparison purposes in our work. In the past, three features of the metastable detector are prominent: it has part-per-billion sensitivity, contamination must be carefully controlled, and anomalous response is common. Since it is an ionization detector, however, temperature instabilities do not cause the major perturbations experienced by the thermal conductivity detectors. This paper describes a miniature metastable ionization detector featuring an unconventional electrode configuration, whose performance characteristics parallel those of traditional design, while its weight is quite small. The prototype has been used in our laboratories routinely for 2 years, and the concept will be incorporated into a flight GC for use in the Space Shuttle.     

Internally excited acoustic resonator for photoacoustic trace detection

The quantum-cascade laser can be used as an infrared source for a small portable photoacoustic trace gas detector. The device that we describe uses a quantum-cascade laser without collimating optics mounted inside an acoustic resonator. The laser is positioned in the center of a longitudinal resonator at a pressure antinode and emits radiation along the length of the resonator exciting an axially symmetric longitudinal acoustic mode of an open-ended cylindrical resonator. Experiments are reported with an 8-microm, quasi-cw-modulated, room-temperature laser used to detect N2O.     

Acoustic flame detector for gas chromatography

A novel gas chromatography detector is described that uses acoustic signals from a partly premixed hydrogen-air flame burning on top of a capillary. The device, referred to as the acoustic flame detector (AFD), is based on the measurement of the frequency of acoustic transients generated at the burner under a range of operating conditions. The presence of trace amounts of analyte in the flame was found to increase the frequency of these sonic bursts from the baseline level of ～100 Hz. The response of the AFD for n-dodecane, measured as the shift in frequency, was determined to be linear over ～3 orders of magnitude, with a minimum detectable level of about 1-5 ng C/s using the current system. The sensitivity correlates roughly with carbon content, except for certain organometallics (Sn, Mn), which gave substantially enhanced signals. Some tailing was observed but became serious only for particular types of organometallics. The noise of the system was predominantly of the 1/f type. The effects of flow conditions, burner geometry, and flame gas constituents were investigated. The oscillations could be followed by acoustic, visual, electrical, and optical means. The AFD mechanism is shown to involve oscillatory chemical kinetics, in which the flame front (the inner cone) temporarily enters a few millimeters into the capillary during each cycle, thereby creating the acoustic signal.     

Bubble chamber as a trace chemical detector

A novel concept for trace chemical analysis in liquids has been demonstrated. The technique utilizes light absorption in a superheated liquid. Although a superheated liquid is thermodynamically unstable, a high degree of superheating can be dynamically achieved for a short period of time. During this time the superheated liquid is extremely sensitive to boiling at nucleation sites produced by energy deposition. Observation of bubbles in the superheated liquid in some sense provides amplification of the initial energy deposition. Bubble chambers containing superheated liquids have been used to detect energetic particles; now a bubble chamber is used to detect a trace chemical in superheated liquid propane by observing bubble formation initiated by optical absorption. Crystal violet is used as a test case and can be detected at the subpart-per-10(12) level by using a Nd:YAG laser. The mechanism for bubble formation and ideas for further improvement are discussed.     

A current mode detector array for -ray asymmetry measurements

We have built a CsI(Tl) γ-ray detector array for the NPDGamma experiment to search for a small parity-violating directional asymmetry in the angular distribution of 2.2 MeV γ-rays from the capture of polarized cold neutrons by protons with a sensitivity of several ppb. The weak pion–nucleon coupling constant can be determined from this asymmetry. The small size of the asymmetry requires a high cold neutron flux, control of systematic errors at the ppb level, and the use of current mode γ-ray detection with vacuum photodiodes and low-noise solid-state preamplifiers. The average detector photoelectron yield was determined to be 1300 photoelectrons per MeV. The RMS width seen in the measurement is therefore dominated by the fluctuations in the number of γ-rays absorbed in the detector (counting statistics) rather than the intrinsic detector noise. The detectors were tested for noise performance, sensitivity to magnetic fields, pedestal stability and cosmic background. False asymmetries due to gain changes and electronic pickup in the detector system were measured to be consistent with zero to an accuracy of 10^-9 in a few hours. We report on the design, operating criteria, and the results of measurements performed to test the detector array.     

Novel transmission detector used for total cross section measurements

A new apparatus for total cross section measurements was developed and tested at Saturne II, Sacalay. The transmission ratios are determined using a ring-counter system coded in the Gray code, involving an exclusive four-fold coincidence between 4 counters among 8. Beam rate effects are suppressed by an electronic device which permits reaching an accuracy of better than 10^?4 in any transmission ratio. The apparatus was first used at SIN for the measurements of the total polarized proton-proton cross section difference Δσ_L and of the spin correlation parameter A_00kk in pp → pp and pp → dπ⁺ reactions, and then at Saturne II for Δσ_γ and Δσ_L measurements in p-p scattering.     

Solid contact potentiometric sensors for trace level measurements

A simple procedure for the development of a range of polymeric ion-selective electrodes (ISEs) with low detection limits is presented. The electrodes were prepared by using a plasticizer-free methyl methacrylate-decyl methacrylate copolymer as membrane matrix and poly(3-octylthiophene) as intermediate layer deposited by solvent casting on gold sputtered copper electrodes as a solid inner contact. Five different electrodes were developed for Ag+, Pb2+, Ca2+, K+, and I-, with detection limits mostly in the nanomolar range. In this work, the lowest detection limits reported thus far with solid contact ISEs for the detection of silver (2.0 x 10(-9) M), potassium (10(-7) M), and iodide (10(-8) M) are presented. The developed electrodes exhibited a good response time and excellent reproducibility.     

Multipass cell design for Stark-modulation spectroscopy

A multipass cell for absorption measurements with an additionally applied homogeneous electric field for Stark effect measurements is described. The configuration is based on two ring mirrors, where the laser beam propagates between two nested cylindrical-wall electrodes. The total optical path length achieved is 40 m. The beam pointing stability of this setup is investigated and compared to a confocal-type Herriott cell of the same base length, employing numerical simulations. The exit beam pointing stability is found to be very good. The response measurements show fast exchange times, which agree well with theoretical values.     

Room-temperature mid-infrared laser sensor for trace gas detection

Design and operation of a compact, portable, room-temperature mid-infrared gas sensor is reported. The sensor is based on continuous-wave difference-frequency generation (DFG) in bulk periodically poled lithium niobate at 4.6 mum, pumped by a solitary GaAlAs diode laser at 865 nm and a diode-pumped monolithic ring Nd:YAG laser at 1064.5 nm. The instrument was used for detection of CO in air at atmospheric pressure with 1 ppb precision (parts in 10(9), by mole fraction) and 0.6% accuracy for a signal averaging time of 10 s. It employed a compact multipass absorption cell with a 18-m path length and a thermoelectrically cooled HgCdTe detector. Precision was limited by residual interference fringes arising from scattering in the multipass cell. This is the first demonstration of a portable high-precision gas sensor based on diode-pumped DFG at room temperature. The use of an external-cavity diode laser can provide a tuning range of 700 cm(-1) and allow the detection of several trace gases, including N(2) O, CO(2), SO(2), H(2) CO, and CH(4).     

Nanofibrous PANI-based conductive polymers for trace gas analysis

Electrospun nanofibres have been confirmed to be very good candidates for ultra-sensitive gas sensors since they greatly improve surface area to volume ratios of coatings, which in turn affect two additional and crucial features for sensors: high sensitivity and fast response time. Electrospinning is a simple method for the deposition of long (up to several centimetres) nanofibres, aligned or non-woven, directly onto suitable transducers. Such a structured layer may have better properties than a compact film, providing faster adsorption and minimising some bulk effects (i.e. long diffusion-desorption time, analyte entrapment, etc.). Electrospun conductive polymers (CPs) have been specifically investigated for developing smart sensors whose electrical properties change upon interactions with the analytes. Polyaniline is one of the most interesting CPs for gas sensing, because of its conductive features, when doped, as well as its thermal stability and sensing performance. The sensing mechanisms are different, depending on the nature of both PANi and the targeting analytes. Thus, various blends of polyaniline and insulating host polymers have been planned, prepared, deposited and studied to optimise the properties of sensors consequent to the combination of the electrical conductivity of CP and of the physical properties of the host polymer. Host polymer carriers cause great modifications to the topology of the interacting surface (diameter and length of the fibres, roughness, porosity, presence of beads and grains, non-woven framework and branched junctions, adhesion, etc.), in addition to the different affinity to the analytes tested. However, they enable electrodes to function over a wider dynamic range of gas or vapour concentrations. The polymer features have been also characterised over a range of water vapour concentrations and temperatures.     

Signal-to-noise measurements utilizing a novel dual-energymultimedia detector

Dual-energy measurements are presented utilizing a novel slot-scan digital radiographic imaging detector, operating on gaseous solid state ionization principles. The novel multimedia detector has two basic functional components: a noble gas-filled detector volume operating on gas microstrip principles, and a solid state detector volume. The purpose of this study is to investigate the potential use of this multimedia detector for enhanced dual-energy imaging. The experimental results indicate that the multimedia detector exhibits a large subtracted signal-to-noise ratio. Although the intrinsic merit of this device is being explored for medical imaging, potential applications of the multimedia detector technology In other industrial areas, such as aerospace imaging, aviation security, and surveillance, are also very promising     

External photoacoustic detection of a trace vapor inside a multimode laser.

We combine highly sensitive intracavity absorption spectroscopy in a multimode laser with external photoacoustic detection, providing high detectivity. Photoacoustic measurements of the intracavity iodine concentration in a Rhodamine 6G laser are compared with simultaneous spectral recordings. They demonstrate slightly improved overall sensitivity and a greatly enhanced dynamic range of 5 orders of magnitude that may be shifted along the absolute scale of absorber density.     

Simulating primary detector function in multifactor measurements

Simulation is considered for the transformation function of the primary detector subject to a given step in the changes in the influencing factors for performing multifactor measurements by the model method. __________ Translated from Izmeritel’naya Tekhnika, No. 4, pp. 26–31, April, 2006.