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     

Time-resolved time-dependent photo-acoustic spectroscopy of NO2 in a high frequency multi-resonant cavity

The paper reports the pulsed laser-based time-resolved time-dependent Photo-acoustic (PA) spectroscopy of NO₂ gas in a specially designed multi mode-Resonant PA Cell which is made of Stainless Steel and has a “Q” value of the order of 79. Furthermore the designed cell allows us to excite some of the longitudinal, radial and azimuthal resonance modes of the photo-acoustic signals simultaneously in a very efficient manner. The presence of many newly excited modes occur at 7050 Hz, 10350 Hz and 14650 Hz frequencies is observed for the first time in NO₂ at room temperature. These results are obtained by employing second harmonics i.e. λ=532 nm pulses from Q-switched Nd:YAG laser having 7 ns pulse duration. Some of the new acoustic spectrum lines at higher frequencies are recorded between 0.5–10 ms data acquisition time, which also extends the frequency monitoring range of our system. The study also highlights some of the important aspects such as the decaying behavior of some of these resonant acoustic spectrum lines occur on the expense of others as well as the saturation behavior of some other modes in the NO₂ gas sample. The estimated low level detection limit of NO₂ buffered in air is of the order of 17.9 ppbV.     

Synthesis of nanostructured lean-NO x catalysts by direct laser deposition of monometallic Pt-, Rh- and bimetallic PtRh-nanoparticles on SiO2 support

Monometallic Pt and Rh and bimetallic PtRh catalysts with a highly dispersed noble metal weight loading of ca. 1 wt% were produced via the direct deposition of nanoparticles on different SiO₂ supports by means of pulsed ultra-violet (248 nm) excimer laser ablation of Pt, Rh bulk metal and PtRh alloy targets. Backscattered electron microscopy (BSE), energy dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM) were employed to characterize the deposited nanoparticles, which were found to exhibit narrow size distribution centred around 2.5 nm. The catalytic activities for lean NO _x reduction of the monometallic and bimetallic catalyst samples were investigated in a flow reactor setup in the temperature range 100–400°C using a test gas mixture representative of oxygen rich diesel engine exhaust gas. For comparison a Rh/SiO₂ reference catalyst prepared by a conventional impregnation method was also tested. Further experiments were performed in which PtRh nanoparticles were deposited on a Rh/SiO₂ reference catalyst sample to study the possibility for controlled modification of its activity. The catalytic activity measurements revealed that among the samples solely prepared by laser deposition the PtRh–SiO₂ nanoparticle catalyst showed the highest activity for NO _x reduction at low temperatures 100–300°C. In addition, it could be demonstrated that the initially low NO _x reduction activity and the N₂ selectivity of the Rh/SiO₂ reference catalyst sample for temperatures below 250°C can be enhanced by post laser deposition of PtRh nanoparticles.     

NO2 sensing properties of YSZ-based sensor using NiO and Cr-doped NiO sensing electrodes at high temperature

Nickel oxide and chromium-doped nickel oxide (Ni_0.95Cr_0.03O_1−δ ) were prepared by thermal decomposition of nitrates. The obtained NiO and Ni_0.95Cr_0.03O_1−δ samples were utilized as sensing electrodes (SEs) in yttria-stabilized zirconia (YSZ)-based sensors for detection of NO₂ at 800 °C under wet condition (5 vol.% H₂O). While the mixed-potential-type planar sensor attached with NiO-SE gave rather large NO₂ sensitivity, the sensor attached with Ni_0.95Cr_0.03O_1−δ -SE exhibited fast recovery rate with an acceptable sensitivity. The Δemf (electromotive force) of the sensors varied linearly with NO₂ concentration in the examined range of 50–400 ppm on a logarithmic scale. Based on the results of measurements for polarization, complex impedance and gas phase catalysis, the fast recovery was attributable to the high rate for the anodic reaction of O₂ at the Ni_0.95Cr_0.03O_1−δ /YSZ interface, and the lower NO₂ sensitivity was caused by both the high rate for the anodic reaction of O₂ and the high degree for the gas phase conversion of NO₂ to NO.     

Photoacoustic gas sensing employing fundamental and frequency-doubled radiation of a continuously tunable high-pressure CO2 laser

We present the first photoacoustic spectrometer for gas sensing employing both the fundamental and the frequency-doubled radiation of a continuously tunable high-pressure CO₂ laser with room temperature operation. A quasi-phase-matched diffusion-bonded GaAs crystal is used in the system for second-harmonic generation. A pulsed photoacoustic detection scheme with a non-resonant cell, equipped with an 80-microphone array, is employed. The wide continuous tuning range in the fundamental (9.2–10.7 μm) and the frequency-doubled (4.6–5.35 μm) regimes, together with the narrow linewidth of 540 MHz (0.018 cm^-1) for the 10-μm region and of 1050 MHz (0.0315 cm^-1) for the 5-μm region, allow the measurement of gas mixtures, individual species and isotope discrimination. This is illustrated with measurements on NO and CO₂. The measured isotope ratio ¹⁵ NO/¹⁴ NO=(3.58±0.55)×10^-3 agrees well with the literature (3.700×10^-3) and demonstrates the good selectivity of the system. Received: 30 April 2002 / Revised version: 10 June 2002 / Published online: 2 September 2002 RID="*" ID="*"Corresponding author. Fax: +41-1/633-1077, E-mail: sigrist@iqe.phys.ethz.ch     

Optical properties of pulsed laser heated soot

To investigate the transient change of soot optical properties resulting from pulsed laser heating of soot in a cooled exhaust plume we have simultaneously performed cw light extinction at 405 and 830 nm and elastic light scattering at 1064 nm. A reversible increase to the 830-nm light extinction of up to 7%, observed during the time period where the soot was hot, suggests a temperature-dependent light absorption refractive index function, E(m _λ ). At low fluence, small permanent increases of E(m _λ ) of <2% were also observed. 405-nm extinction measurements revealed that the soot likely contained material which continued to absorb 405-nm radiation when desorbed, thus complicating measurement interpretation. 1064-nm light scattering measurements showed a gradual decrease of scattering propensity with increasing laser fluence up to the point of material loss, which is consistent with the expected decrease of the structure factor of the soot aggregates as they expand. It is concluded that variations of the optical properties are occurring at the time of laser-induced incandescence (LII) emission, which should be accounted for in time-resolved LII measurement interpretation.     

The sensitivity and dynamic response of field ionization gas sensor based on ZnO nanorods

Field ionization gas sensors based on ZnO nanorods (50–300 nm in diameter, and 3–8 μm in length) with and without a buffer layer were fabricated, and the influence of the orientation of nano-ZnO on the ionization response of devices was discussed, including the sensitivity and dynamic response of the ZnO nanorods with preferential orientation. The results indicated that ZnO nanorods as sensor anode could dramatically decrease the breakdown voltage. The XRD and SEM images illustrated that nano-ZnO with a ZnO buffer layer displayed high c-axis orientation, which helps to significantly reduce the breakdown voltage. Device A based on ZnO nanorods with a ZnO buffer layer could distinguish toluene and acetone. The dynamic responses of device A to the NO _x compounds presented the sensitivity of 0.045 ± 0.007 ppm/pA and the response speed within 17–40 s, and indicated a linear relationship between NO _x concentration and current response at low NO _x concentrations. In addition, the dynamic responses to benzene, isopropyl alcohol, ethanol, and methanol reveals that the device has higher sensitivity to gas with larger static polarizability and lower ionization energy.     

Removal of NOx from NO2∶NO∶N2 mixture by a pulsed and dc streamer corona in a needle-to-plate reactor

The results of laboratory experiments on reduction of NO _x in the oxygen free gas mixture NO₂NON₂ simulating exhaust gas, by means of pulsed and dc streamer corona discharges generated in a needle-to-plate reactor have been presented. The results show that the dc corona discharge is more efficient in De-NO _x process than the pulsed corona discharge. This is in contrast to the results obtained in the wire-to-cylinder reactors where the pulsed corona discharge removes NO _x more efficiently. The results also lead to the conclusion that in the dc streamer corona discharge the short pulses and long interelectrode distances are recommended in order to increase the NO _x conversion rate.Presented at 17^th Symposium Plasma Physics and Technology, Prague, June 13–16, 1995.This work was financially supported by the Polish Academy of Sciences (projects IMP 3.1 and 3.3) and by the Polish Committee for Scientific Research (KBN Grant No. P40103304).     

Real-time monitoring of nitric oxide in diesel exhaust gas by mid-infrared cavity ring-down spectroscopy

We report the accurate and precise measurement of nitric oxide (NO) in automotive exhaust gas by cavity ring-down spectroscopy (CRDS) using a thermoelectrically cooled, pulsed quantum cascade laser (QCL) as a light source. A mid-infrared QCL with a 5.26 μm wavelength was used to detect fundamental vibrational transitions of NO. An effective optical path length of 2.1 km was achieved in a 50 cm long cell using high-reflectivity mirrors. In combination with a particle filter and a membrane gas dryer, stable and sensitive measurement of NO in exhaust gas was achieved for more than 30 minutes with a time resolution of 1 s. The results of this work indicate that a laser based NO sensor can be used to measure NO in exhaust gas over a dynamic range of three orders of magnitude.     

Influence of temperature and humidity on NO x removal by corona discharge

The object of this experimental investigation was the influence of temperature and humidity on the efficiency of removal of NO _x by a pulsed corona discharge from a mixture N₂ : O₂ : CO₂ : H₂O : NO simulating a combustion flue gas. The pulsed corona discharge was generated in a wire-to-cylinder reactor. It was found that removal of NO _x was most efficient when H₂O concentration corresponded with the saturated vapour pressure. In the case of the operating gas containing constant H₂O concentration removal of NO _x decreased with increasing temperature of the operating gas. Dedicated to Prof. Jan Janča on the occasion of his 60^th birthday. This work is devoted to the 60^th birthday of Professor Jan Janca, our good colleague, merited teacher, researcher and famous physicist, discussion with whom stimulated this and other our work during years.     

Incoherent broad-band cavity-enhanced absorption spectroscopy for simultaneous trace measurements of NO2 and NO3 with a LED source

In the past decade, due to a growing awareness of the importance of air quality and air pollution control, many diagnostic tools and techniques have been developed to detect and quantify the concentration of pollutants such as NO _x , SO _x , CO, and CO₂. We present here an Incoherent Broad-Band Cavity-Enhanced Spectroscopy (IBB-CEAS) set-up which uses a LED emitting around 625 nm for the simultaneous detection of NO₂ and NO₃. The LED light transmitted through a high-finesse optical cavity filled with a gas sample is detected by a low resolution spectrometer. After calibration of the spectrometer with a NO₂ reference sample, a linear multicomponent fit analysis of the absorption spectra allows for simultaneous measurements of NO₂ and NO₃ concentrations in a flow of ambient air. The optimal averaging time is found to be on the order of 400 s and appears to be limited by the drift of the spectrometer. At this averaging time the smallest detectable absorption is 2×10⁻¹⁰ cm⁻¹, which corresponds to detection limits of 600 pptv for NO₂ and 2 pptv for NO₃. This compact and low cost instrument is a promising diagnostic tool for air quality control in urban environments.     

Gain versus tuning issues to Q-switch with Yb<Superscript>3+</Superscript>:LSO and amplify broad-bandwidth pulses

We report on the development of Incoherent Broadband Cavity Enhanced Absorption Spectroscopy (IBBCEAS) using a blue light emitting diode (LED) for the detection of NO₂ in laboratory ambient air. Absorption of the oxygen collisional pair in the atmosphere was also detected in the same spectral range. The mirror reflectivity was determined using a standard gas sample mixture of NO₂, and calibrated with the help of the absorption spectrum of the oxygen collisional pair in pure oxygen at atmospheric pressure. Optimization of the experimental parameters was investigated and is discussed in detail. For the first time in IBBCEAS involving broadband absorption spectra, averaging time for signal-to-noise ratio enhancement has been optimized using Allan variance plot. 18.1 ppbv NO₂ in laboratory ambient air has been retrieved from the absorption spectra using differential fitting method over a 40 nm spectral region centered at 470 nm. A minimum detection sensitivity of about 2.2 ppbv (1σ) for NO₂ at atmospheric pressure has been achieved using the optimal averaging time of 100 s by means of a high finesse optical cavity formed with two moderate reflectivity (∼99.55%) mirrors. No purging of the cavity mirrors by high purity He or N₂ gas streams was necessary to prevent contamination of the mirror faces for the in situ measurements.     

Sensitive detection of temperature behind reflected shock waves using wavelength modulation spectroscopy of CO2 near 2.7?μm

Tunable diode-laser absorption of CO₂ near 2.7 μm incorporating wavelength modulation spectroscopy with second-harmonic detection (WMS-2f) is used to provide a new sensor for sensitive and accurate measurement of the temperature behind reflected shock waves in a shock-tube. The temperature is inferred from the ratio of 2f signals for two selected absorption transitions, at 3633.08 and 3645.56 cm⁻¹, belonging to the ν ₁+ν ₃ combination vibrational band of CO₂ near 2.7 μm. The modulation depths of 0.078 and 0.063 cm⁻¹ are optimized for the target conditions of the shock-heated gases (P∼1–2 atm, T∼800–1600 K). The sensor is designed to achieve a high sensitivity to the temperature and a low sensitivity to cold boundary-layer effects and any changes in gas pressure or composition. The fixed-wavelength WMS-2f sensor is tested for temperature and CO₂ concentration measurements in a heated static cell (600–1200 K) and in non-reactive shock-tube experiments (900–1700 K) using CO₂–Ar mixtures. The relatively large CO₂ absorption strength near 2.7 μm and the use of a WMS-2f strategy minimizes noise and enables measurements with lower concentration, higher accuracy, better sensitivity and improved signal-to-noise ratio (SNR) relative to earlier work, using transitions in the 1.5 and 2.0 μm CO₂ combination bands. The standard deviation of the measured temperature histories behind reflected shock waves is less than 0.5%. The temperature sensor is also demonstrated in reactive shock-tube experiments of n-heptane oxidation. Seeding of relatively inert CO₂ in the initial fuel-oxidizer mixture is utilized to enable measurements of the pre-ignition temperature profiles. To our knowledge, this work represents the first application of wavelength modulation spectroscopy to this new class of diode lasers near 2.7 μm.     

Mid-infrared laser-absorption diagnostic for vapor-phase measurements in an evaporating n-decane aerosol

A novel three-wavelength mid-infrared laser-based absorption/extinction diagnostic has been developed for simultaneous measurement of temperature and vapor-phase mole fraction in an evaporating hydrocarbon fuel aerosol (vapor and liquid droplets). The measurement technique was demonstrated for an n-decane aerosol with D ₅₀∼3 μ m in steady and shock-heated flows with a measurement bandwidth of 125 kHz. Laser wavelengths were selected from FTIR measurements of the C–H stretching band of vapor and liquid n-decane near 3.4 μm (3000 cm ⁻¹), and from modeled light scattering from droplets. Measurements were made for vapor mole fractions below 2.3 percent with errors less than 10 percent, and simultaneous temperature measurements over the range 300 K<T<900 K were made with errors less than 3 percent. The measurement technique is designed to provide accurate values of temperature and vapor mole fraction in evaporating polydispersed aerosols with small mean diameters (D ₅₀<10 μ m), where near-infrared laser-based scattering corrections are prone to error.     

Conductivity studies of starch-based polymer electrolytes

A proton-conducting polymer electrolyte based on starch and ammonium nitrate (NH₄NO₃) has been prepared through solution casting method. Ionic conductivity for the system was conducted over a wide range of frequency between 50 Hz and 1 MHz and at temperatures between 303 K and 373 K. Impedance analysis shows that sample with 25 wt.% NH₄NO₃ has a smaller bulk resistance (R _b) compared to that of the pure sample. The amount of NH₄NO₃ was found to influence the proton conduction; the highest obtainable room temperature conductivity was 2.83 × 10⁻⁵ S cm⁻¹, while at 100 °C, the conductivity in found to be 2.09 × 10⁻⁴ S cm⁻¹. The dielectric analysis demonstrates a non-Debye behavior. Transport parameters of the samples were calculated using the Rice and Roth model and thus shows that the increase in conductivity is due to the increase in the number of mobile ions.     

Raman and fluorescence lidar measurements of aircraft engine emissions

Laser induced Raman and fluorescent measurements were made in the exhaust of a gas turbine engine with a new field portable instrument devised specifically for gas turbine exhaust measurements. The gas turbine exhaust was analyzed by conventional instruments for CO, CO₂, NO, NO_x, total hydrocarbons, smoke and temperature, and these data were used as a ‘calibration’ standard for the evaluation of the laser Raman instrument. Results thus far indicate good correlations for CO₂, O₂, smoke, hydrocarbons and temperature. The instrument was not sensitive enough for NO detection but the data analysis indicates that 100 ppm may be detectable with instrument improvements. CO analysis was not attempted, but it is expected that CO could be detected with further research. NO₂ (or NO_x) was not attempted because theoretical and experimental laboratory analysis indicated severe interference with CO₂. The conclusion was that laser Raman shows a good potential for aircraft gas turbine emission analysis.     

Photoluminescence measurements in the phase transition region of Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>S films

Thin films of Zn_1−x Cd _x S (0.1 ≤ x ≤ 0.5) were prepared by using pulsed laser ablation technique on corning glass substrates. Phase transition from cubic to hexagonal in Zn_1−x Cd _x S films is determined by X-ray diffraction analysis. We observed a lowering in the phase transition temperature with increase in the cadmium concentration. Transmission electron microscopy suggests the crystalline nature of thin films with average particle size of 15 nm. The grown Zn_1−x Cd _x S samples show the high peak intensity ratio of the near band edge emission to the defect center luminescence even at room temperature, which indicates the small concentration of complex defects in the samples. Photoluminescence measurement show stoichiometric dependence of the energy band gap and is found to have quadratic dependence on x.     

Field-induced valence transition in EuPtP<Subscript>1−x</Subscript>As<Subscript>x</Subscript>

The ternary compound EuPtP exhibits two valence transitions at T ₁ = 235 K and T ₂ = 190 K. In order to examine a field-induced valence transition of Eu, we synthesized EuPtP_1−x As _x compounds with 0.05 ≤ x ≤ 0.5 and studied the magnetic and valence behavior. The substitution of As for P increases the lattice volume linearly and decreases both valence transition temperatures, T ₁ and T ₂, in contrast to the behavior under external pressures. The magnetization process in a pulsed magnetic field revealed that EuPtP_0.5As_0.5 exhibits an onset of metamagnetic transition above 50 T with a large hysteresis, which evidences a first-order field-induced valence transition. The analysis of the magnetization curves of x = 0.5 at various temperatures has demonstrated that the field-induced transition is essentially the same as the transition induced by temperature at T ₁.     

In situ sensor for cycle-resolved measurement of temperature and mole fractions in IC engine exhaust gases

We present a multi-species mole fraction and temperature sensor for in situ exhaust gas diagnostic of internal combustion (IC) engines. The sensor is based on Tunable Diode Laser Absorption Spectroscopy (TDLAS) and incorporates four optical channels - two miniature White cells and two double-traversal cells - with base lengths of 6?cm. It has been demonstrated at a hot air test stand and in the exhaust manifold of a single-cylinder research engine, with measured temperatures of up to 1000?K. Stable operation was achieved with absorption lengths of up to 192?cm (test stand) and 97?cm (engine). Employing time-division multiplexed detection, six species were measured simultaneously in the engine exhaust, at wavelengths ranging from 1.4?µm to 5.2 µm: water vapor (H₂O), carbon dioxide (CO₂), carbon monoxide (CO), methane (CH₄), nitrogen dioxide (NO₂) and nitric oxide (NO). The effective measurement rate was as high as 1?kHz, and cycle-to-cycle variations were clearly detected. We show the correlation of the air-fuel equivalence ratio with the spectroscopically measured mole fraction of each species. At a cycle-resolved rate, detection limits for the legally regulated species NO and NO₂ were 1?ppm and 4?ppm, respectively. The sensor is intended to help improve the understanding of IC engine emission behavior during fast transients.     

Adsorption of pairs of NOx molecules on single-walled carbon nanotubes and formation of NO + NO3 from NO2

The adsorption of NO_x(x = 1, 2, 3) molecules on single-walled carbon nanotubes (SWCNTs) is investigated using first-principle calculations. Single NO, NO₂ and NO₃ molecules are found to physisorb on SWCNTs, but molecules can be chemisorbed in pairs on the top of carbon atoms at close sites of SWCNTs. The adsorption energy for pairs of NO or NO₃ molecules is larger than for pairs of NO₂ molecules. The local curvature is found to have a sizable effect on adsorption energies. The possibility of a surface reaction NO₂ + NO₂ → NO + NO₃ is examined and the relative pathway and barrier is calculated. The results are discussed with reference to available experimental results.