Low-limit detection of NO2 by longitudinal mode selection in a photoacoustic resonant system

The paper reports the pulsed laser-based photoacoustic (PA) spectroscopy of NO₂ in a resonant PA cavity with special filters made of stainless steel. The PA cell along with special types of sound filters are designed and fabricated to excite only the second-order longitudinal mode inside the cavity. The second harmonic, i.e. λ?= 532 nm pulse width, of 7 ns obtained from Q-switched Nd:YAG laser at 10 Hz repetition rate has been used to study the saturation behaviour of the PA signal and absorption coefficient with respect to the input laser energy. Generally, the Q-factor of longitudinal modes in the acoustic cavities is quite low. However, by modifying the design of the cell and the filter, we can achieve high value of Q = 30. The combination of special filter along with the experimental data acquisition technique helped us to achieve the minimum detection concentration of NO₂ of the order of 9 ppbV which is much better than the previous value of the same PA cell without filter [Yehya and Chaudhary, Appl. Phys. B 106, 953 (2012)].     

Fast simultaneous measurement of multi-gases using quantum cascade laser photoacoustic spectroscopy

The authors developed a fast simultaneous method in detecting multi-gases using quantum cascade laser (QCL) based photoacoustic (PA) spectroscopy. We demonstrated the simultaneous measurement of CO and SO₂ concentrations using two QCLs working at 4.56 and 7.38 μm, corresponding to the absorption bands of CO and SO₂, respectively. The modulation frequencies of the two QCLs were 234 and 244 Hz. The response time was 0.6 seconds. A computer sound card was used to process the PA signals. Fast Fourier transform was an essential step to get the amplitudes of the PA signals at different frequencies. The concentration of each gas can be obtained from the PA signal amplitude at the corresponding modulation frequency.     

Real-time measurement of nitrogen dioxide in vehicle exhaust gas by mid-infrared cavity ring-down spectroscopy

The application of pulsed cavity ring-down spectroscopy (CRDS) was demonstrated for the measurement of nitrogen dioxide (NO₂) in automotive exhaust gas. The transition of the ν ₃ vibrational band assigned to the antisymmetric stretching mode of NO₂ was probed with a thermoelectrically cooled, pulsed, mid-infrared, distributed feedback, quantum cascade laser (QCL) at 6.13 μm. The measurement of NO₂ in the exhaust gas from two diesel vehicles equipped with different aftertreatment devices was demonstrated using a CRDS-based NO₂ sensor, which employs a HEPA filter and a membrane gas dryer to remove interference from water as well as particulates in the exhaust gas. Stable and sensitive measurement of NO₂ in the exhaust gas was achieved for more than 30 minutes with a time resolution of 1 s.     

Vibrational mode assignments for bundled single-wall carbon nanotubes using Raman spectroscopy at different excitation energies

This study establishes a generic fitting approach to assignment of nanotube chiralities based on radial breathing mode frequencies (ω _RBM) of SWCNTs in as-produced bundles. Four laser lines with energies of 2.62 eV, 2.33 eV, 1.88 eV and 1.58 eV were employed. The observed RBM frequencies, ω _RBM, were plotted as a function of the possible diameters, d, as identified from the so-called Kataura plot and reported values of the parameters A and B, where ω _RBM=A/d+B, assuming that SWCNTs resonant at the respective laser frequencies dominate the spectrum. The refined values of A and B, obtained by the best fit of a linear regression between ω _RBM and 1/d, were found to vary significantly for different laser frequencies. This variation is interpreted in terms of the differences in electronic properties of SWCNTs resonant at different frequencies. The assigned nanotubes match well with those identified in the Kataura plot, falling within a resonant line width of ±0.2 eV of the respective laser lines.     

Preliminary results on the operation of a 2270 kg cryogenic gravitational-wave antenna with a resonant capacitive transducer and a d.c. SQUID amplifier

Summary In November 1985 the gravitational-wave antenna of the Rome group, installed at CERN, has started operating. It consists of a 5056 aluminium cilinder 3 m long, 2270 kg heavy, cooled at 4.2 K. The antenna vibrations are detected by means of a resonant capacitive transducer that together with the bar makes a two-coupled-oscillator system. The low-noise amplification is obtained with a d.c. SQUID amplifier. The frequencies of the two resonant modes are:v _-=907.116 Hz andv ₊=923.083 Hz, with merit factorsQ ₋=3.2·10⁶ andQ ₊=5.6·10⁶. The sensitivity to short gravitational bursts, expressed in terms of effective noise temperature, is 18 mK. This corresponds to a change in the metric tensor whose Fourier transform isH=1.1·10⁻²¹ Hz⁻¹. For monochromatic waves the antenna is sensitive (SNR=1) toh∼2·10⁻²⁵ in a band width of about 1/3 Hz, with a three months integration time.

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Riassunto Nel novembre 1985 è stata messa in funzione l'antenna gravitazionale del gruppo di Roma, installata al CERN. Questa consiste di un cilindro d'alluminio 5056 lungo 3 m e pesante 2270 kg, raffeeddato a 4.2 K. Le vibrazioni dell'antenna vengono rivelate mediante un transduttore capacitivo risonante, che assieme alla sbarra forma un sistema di due oscillatori accoppiati. L'amplificazione a basso rumore è ottenuta con un amplificatore a d.c.-SQUID. Le frequenze dei due modi risonanti sono:v _-=907.116 Hz ev ₊=923.083 Hz, con fattori di meritoQ ₋=3.2·10⁶ eQ ₊ =5.6·10⁶. La sensibilità per brevi fiotti di onde gravitazionali, espressa in termini di temperatura efficace di numore, è 18 mK. Questa corrisponde a una variazione di tensore metrico con trasformata di Fourier:H=1.1·10⁻²¹ Hz. Per le onde monocromatiche l'antenna è sensibile (SNR=1) ah∼2·10⁻²⁵ in una banda di circa 1/3 Hz, con tempo d'integrazione di tre mesi.

     

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.     

The rotational resonance Raman spectrum of nitrogen dioxide and the determination of electronic state symmetry from resonance Raman selection rules

The pure rotational Raman spectrum of nitrogen dioxide has been observed and shown to be consistent with existing determinations of molecular parameters. Upon observation at 600 Torr pressure and 0.4 cm⁻¹ resolution a well-defined rotational spectrum is obtained. This spectrum is overlaid with a number of fluorescence lines. The fluorescence lines are separated from the Raman spectrum by a comparison of Stokes and anti-Stokes branches of the rotational spectrum. Out of seven strong fluorescence lines seen with 5145 Å excitation, five probably are identifiable with vibration-rotation fluorescence progressions observed by Abe.The most striking feature of these observations is the potential use of the resonance Raman effect for the analysis of complicated electronic spectra. When this rotational spectrum is observed with excitation by 5309 Å or 5145 Å excitation, the Raman spectrum follows a-axis selection rules and the Q-branches are in the noise level or barely out of it. However, at 4880 Å the ΔK = 2Q-branches become a major feature of a spectrum, indicating that an appreciable part of the absorption at this wavelength is occurring through the operation of b- or c-axis selection rules. These findings are consistent with present notions of a ²B₂ excited state dominating absorption at longer wavelengths, while at shorter wavelengths a ²B₁ excited state becomes important. Given a tunable laser, one could map the relative importance of these two possible selection rules for NO₂ without any theoretical analysis more sophisticated than that presented in this paper.A simplified statement of the selection rules for resonance rotational Raman spectra of asymmetric tops has been developed in the course of this investigation. No attempt has been made to refine the rotational parameters of NO₂ since all of the lines seen areunresolved multiplets. Our data should be regarded as a search spectrum preliminary to investigation on a high resolution instrument.     

Frequency Spectra of Quantum Beats in Nuclear Forward Scattering of 57Fe: The Mössbauer Spectroscopy with Superior Energy Resolution

Frequency spectra of quantum beats (QB) in nuclear forward scattering (NFS) are analysed and compared to Mössbauer spectra. Lineshape, number of lines, sensitivity to minor sites, and other specific properties of the frequency spectra are discussed. The most characteristic case of combined magnetic and quadrupole interactions is considered in detail for ⁵⁷Fe. Pure magnetic Zeeman splitting corresponds to a eight-line spectrum of QB, six of which show the same energy separation as the six lines in Mössbauer spectra. Two other lines (called 2′ and 3′) are the lower-energy satellites of the lines 2 and 3. As the quadrupole interaction E _Q appears, the satellites remain unsplit in the quantum beat frequency spectra, as well as the first (zero-frequency) and the 6th (largest frequency) lines. Each of the lines 3 and 5 generates a doublet split by 2E _Q, and the lines 2 and 4 generate triplets. In QB frequency spectra (QBFS) of thin absorbers of GdFeO₃ we demonstrate the enhanced spectral resolution compared to Mössbauer spectra. Small particle size in an antiferromagnet (Fe₂O₃) was found to affect the QBFS via enhancement of the intensity around zero-frequencies. An asymmetric hyperfine field distribution mixes up into the hybridization with dynamical beats, which enlarges the frequencies of the low-lying QBFS lines and makes their shifts relatively large compared to the shift of the highest-frequency line.     

Initial operation at liquid-helium temperature of the M =2270 kg Al 5056 gravitational-wave antenna of the Rome group

Summary We report on the cooling at liquid-helium temperature of our 2270 kg 5056 Al bar at CERN. The liquid-helium container had been filled up to 1500 liters ensuring to keep the antenna cold for more than one month. The antenna is equipped with a resonant capacitive transducer operating at constant electrical charge with a FET low-noise amplifier. The transducer is tuned to the antenna within less than I Hz and the two normal-mode frequencies are ν₋=908.160 Hz and ν₊=924.234 Hz with an applied electrical field in the transducer of 10⁶ V/m. The corresponding overall merit factors areQ ₋=5.20·10⁶ andQ ₊=7.25·10⁶. The transducer has been tested up to an electrical field of 6·10⁶ V/m: in this condition we have βQ≈10⁴. The antenna has been in operation for several weeks giving, for the Brownian noise, values in agreement with the calculated values. We report also on the results of tests performed on a DC SQUID, whose input was connected to a commercial capacitor via a transformer with turn ratio of 1000. Supported in part by Japan Society for the Promotion of Science.     

Acoustic vibrations of embedded spherical nanoparticles

A solid-matrix-embedded spherical nanoparticle has acoustic vibrational frequencies which are shifted and damped relative to modes of a free sphere. Not only the longitudinal plane wave acoustic impedances, but also the Poisson ratios of nanoparticle and matrix are important in determining the Q-factor of the “breathing” mode, for which frequencies and Q-factors with different material combinations are presented. High matrix sound speed (e.g. silica, titania, alumina, diamond) increases Q.     

Thermoconductometric detection of gases and gas flows by means of SAW delay lines

Surface acoustic wave (SAW) delay lines without gas-sensitive coatings are used as thermal sensors for the thermoconductometric detection of gases and gas flows. The forced convection of 13 gases is analyzed in the linear approximation without regard for their interaction with the environment. Quartz, LiNbO₃, Bi₁₂GeO₂₀, and Bi₁₂SiO₂₀ delay lines are used to detect H₂, He, Ar, CH₄, NH₃, N₂, and O₂ at frequencies f=21–263 MHz and temperatures T=25–165 °C. The SAW “response” is measured as a function of the gas concentration n, the flow rate U, the temperature coefficient of the SAW velocity (TCV), and the working temperature T _p . The feasibility of controlling the level of the gas “response” and imparting selectivity to the choice of TCV and T _p is demonstrated. The threshold gas concentrations are 0.35% for CH₄ and 0.1% for H₂ and NH₃ in nitrogen. A linear response is obtained in the interval U=20–200 ml/min. Zh. Tekh. Fiz. 67, 119–123 (May 1997)     

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.     

Black holes with metric and fields of the same form

We present two rotating black hole solutions with axion ξ, dilaton f{\phi} and two U(1) vector fields. Starting from a non-rotating metric with three arbitrary parameters, which we have found previously, and applying the “Newman–Janis complex coordinate trick” we get a rotating metric g _μν with four arbitrary parameters namely the mass M, the rotation parameter a and the charges electric Q _E and magnetic Q _M . Then we find a solution of the equations of motion having this g _μν as metric. Our solution is asymptotically flat and has angular momentum J = M a, gyromagnetic ratio g = 2, two horizons, the singularities of the solution of Kerr, axion and dilaton singular only when r = a cos θ = 0 etc. By applying to our solution the S-duality transformation we get a new solution, whose axion, dilaton and vector fields have one more parameter. The metrics, the vector fields and the quantity l = x+ie^-2f{\lambda=\xi+ie^{-2\phi}} of our solutions and the solution of: Sen for Q _E , Sen for Q _E and Q _M , Kerr–Newman for Q _E and Q _M , Kerr, Reference Kyriakopoulos [Class. Quantum Grav. 23:7591, 2006, Eqs. (54–57)], Shapere, Trivedi and Wilczek, Gibbons–Maeda–Garfinkle–Horowitz–Strominger, Reissner–Nordstr?m, Schwarzschild are the same function of a, and two functions ρ ² = r(r + b) + a ² cos² θ and Δ = r(r + b) − 2Mr + a ² + c, of a, b and two functions for each vector field, and of a, b and d respectively, where a, b, c and d are constants. From our solutions several known solutions can be obtained for certain values of their parameters. It is shown that our two solutions satisfy the weak the dominant and the strong energy conditions outside and on the outer horizon and that all solutions with a metric of our form, whose parameters satisfy some relations satisfy also these energy conditions outside and on the outer horizon. This happens to all solutions given in the “Appendix”. Mass formulae for our solutions and for all solutions which are mentioned in the paper are given. One mass formula for each solution is of Smarr’s type and another a differential mass formula. Many solutions with metric, vector fields and λ of the same functional form, which include most physically interesting and well known solutions, are listed in an “Appendix”.     

EPR of two Cu2+ complexes showing dynamic Jahn-Teller effects

The powder electron paramagnetic resonance spectra of ∼1% Cu doped into [Zn(bipy)₂(NO₂)]NO₃ and [Zn(bipyam)₂(NO₂)]NO₃, bipy = 2,2′-bipyridyl, bipyam = 2,2′-bipyridylamine, over the temperature range 4.2–300 K are reported. For [Zn/Cu(bipy)₂(NO₂)]NO₃ a spectrum characteristic of a tetragonally elongated octahedral complex with a slight orthorhombic distortion is observed below ∼50 K, but above this temperature the signals associated with the two higherg-values gradually converge. At low temperature a spectrum similar to that of the bipy complex is observed for [Zn/Cu(bipyam)₂(NO₂)]NO₃, but between 40 and 60 K the spectrum gradually changes to one characteristic of a tetragonalg-tensor with g_∥ < g_⊥. The spectra may be interpreted satisfactorily with a model in which the temperature dependence of theg-vainlues is estimated from the vibronic wavefunctions of a copper(II) complex under the influence of second-order Jahn-Teller coupling and a ligand field of tetragonal symmetry perturbed by crystal lattice forces. The results are consistent with the crystal structures reported for the compounds at various temperatures.     

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.     

Renormalization of a Hard-Core Guest Charge Immersed in a Two-Dimensional Electrolyte

This paper is a continuation of a previous one [L. Šamaj, J. Stat. Phys. 120:125 (2005)] dealing with the renormalization of a guest charge immersed in a two-dimensional logarithmic Coulomb gas of pointlike ± unit charges, the latter system being in the stability-against-collapse regime of reduced inverse temperatures 0 ≤ β < 2. In the previous work, using a sine-Gordon representation of the Coulomb gas, an exact renormalized-charge formula was derived for the special case of the pointlike guest charge Q, in its stability regime β |Q| < 2. In the present paper, we extend the renormalized-charge treatment to the guest charge with a hard core of radius σ, which allows us to go beyond the stability border β|Q| = 2. In the limit of the hard-core radius much smaller than the correlation length of the Coulomb-gas species and at a strictly finite temperature, due to the counterion condensation in the extended region β|Q| > 2, the renormalized charge Q _ren turns out to be a periodic function of the bare charge Q with period 1. The renormalized charge therefore does not saturate at a specific finite value as |Q| →∞, but oscillates between two extreme values. In the high-temperature Poisson-Boltzmann scaling regime of limits β→ 0 and Q→∞ with the product β Q being finite, one reproduces the Manning-Oosawa type of counterion condensation with the uniform saturation of β Q _ren at the value 4/π in the region β|Q| ≥ 2. The obtained results disprove the “regularization hypothesis” of the previous work about the possibility of an analytic continuation of the formula for Q _ren from the stability region β |Q| < 2 to β |Q| ≥ 2.     

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.     

Spectral anomalies of waveguide electromagnetic modes in layered structures

A theoretical study of electromagnetic guided eigenwaves in two-and three-layered plates with metallized surfaces is accomplished. The appropriate dispersion equations are explicitly analyzed using the discretization first introduced by Mindlin in the theory of Lamb acoustic waves. It is shown that the dispersion branches of independent eigenmode families cross each other in the nodes of a grid formed by two infinite series of bond lines. The latter represent the dispersion curves for homogeneous plates with permittivities ɛ₂ or ɛ₂ coinciding with those for the layers of the waveguide. It is proved that, beyond nodes of the grid, the dispersion curves do not intersect bond lines, which thus provides definite “corridors” for these curves. The dispersion lines have a wavy (“zigzag”) form in the grid zone and remain smooth beyond the grid. The crossing branches have coinciding cutoff frequencies. In dimensionless coordinates “slowness (S) vs. frequency (f),” the branches S _l (f) have two asymptotic levels: S = √ɛ₁ and S = √ɛ₂. At the lower level, the spectrum forms a steplike terracing pattern with a progressive closing to the asymptote of a succession of dispersion curves, which change each other at this level with further going up to the next asymptote. An extension to anisotropic waveguides with layers made of uniaxial crystals is considered. The text was submitted by the authors in English.     

Spectroscopic investigation on the lattice dynamics of different cut quartz samples irradiated by neutrons

A spectroscopic study of the effect of neutron radiation on the lattice dynamics of different cut crystalline and glassy quartz (SiO₂) has been performed. The IR spectroscopy method is used to determine the mechanisms by which the spectral characteristics of deformation and valence vibrations vary by radiation-induced alteration of the lattices in two types of modified quartz (α-SiO₂ and ν-SiO₂) as a function of the neutron fluence at low and high frequencies. It has been established that nonlinear changes in the dose dependences between the spectral characteristics of the fundamental modes occur in two types of crystals, with different orientations, and in glass, and the features of the spectrum modifications exist near 300–550 and 700–1400 cm⁻¹ and at higher frequencies. The derived dose dependences are compared to those of the degenerate vibration parameters in ν-SiO₂, and the extreme kinetics of the force coefficients is determined. A conclusion is made that the accumulation of radiation damages, changes in the force field around the bridge bonds, and the phase states of SiO₂ affect the observed specific behavior of the radiation-modified spectral and force parameters of the degenerate and deformation modes in quartz samples of different types.     

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.