Laser photofragmentation-fragment detection and pyrolysis-laser-induced fluorescence studies on energetic materials

Trace concentrations of energetic materials such as 2, 4, 6-trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN), and hexahydro-1, 3, 5-trinitro-s-triazine (RDX) are detected by laser photofragmentation-fragment detection (PF-FD) spectrometry. In this technique, a single laser operating near 227 nm photofragments the parent molecule and facilitates the detection of the characteristic NO fragment by means of its A (2)Sigma(+)-X (2)Sigma (0, 0) transitions near 227 nm. Fragment detection is accomplished by resonance-enhanced multiphoton ionization with miniature electrodes and by laser-induced fluorescence (LIF) with a photodetector. Experiments are also conducted in the visible region by use of 453.85-nm radiation for photofragmentation and fragment detection. Sand samples contaminated with PETN and RDX are analyzed by a pyrolysis-LIF technique, which involves pyrolysis of the energetic material with subsequent detection of the pyrolysis products NO and NO(2) by LIF and PF-LIF, respectively, near 227 nm. The application of these techniques to the trace analysis of TNT, PETN, and RDX at ambient pressure in room air is demonstrated with limits of detection (signal-to-noise ratio, 3) in the low parts-in-10(9) to parts-in-10(6) range for a 20-s integration time and 10-120 microJ of laser energy at 226.8 nm and approximately 5 mJ at 453.85 nm. An increase in detection sensitivity is projected with an increase in laser energy and an improved system design. The analytical merits of these techniques are discussed and compared with those of other laser-based techniques.     

Periodically porous top electrodes on vertical nanowire arrays for highly sensitive gas detection

Nanowires of various materials and configurations have been shown to be highly effective in the detection of chemical and biological species. In this paper, we report a novel, nanosphere-enabled approach to fabricating highly sensitive gas sensors based on ordered arrays of vertically aligned silicon nanowires topped with a periodically porous top electrode. The vertical array configuration helps to greatly increase the sensitivity of the sensor while the pores in the top electrode layer significantly improve sensing response times by allowing analyte gases to pass through freely. Herein, we show highly sensitive detection to both nitrogen dioxide (NO(2)) and ammonia (NH(3)) in humidified air. NO(2) detection down to 10 parts per billion (ppb) is demonstrated and an order-of-magnitude improvement in sensor response time is shown in the detection of NH(3).     

High-sensitivity instrument for measuring atmospheric NO2

We report on the development of a high-sensitivity detection system for measuring atmospheric NO2 using a laser-induced fluorescence (LIF) technique around 440 nm. A tunable broad-band optical parametric oscillator laser pumped by the third harmonic of a Nd:YAG laser is used as a fluorescence excitation source. The laser wavelength is tuned at peak and bottom wavelengths around 440 nm alternatively, and the difference signal at the two wavelengths is used to extract the NO2 concentration. This procedure can give a good selectivity for NO2 and avoid interferences of fluorescent or particulate species other than NO2 in the sample air. The NO2 instrument developed has a sensitivity of 30 pptv in 10 s and S/N = 2. The practical performance of the detection system is tested in the suburban area for 24 h. The intercomparisons between the LIF instrument and a photofragmentation chemiluminescence (PF-CL) instrument have been performed under laboratory conditions. The correlation between the two instruments is measured up to 1000 pptv. A good linear relationship between the LIF measurements and the PF-CL measurements is obtained.     

Passive standoff detection of SF6 at a distance of 5.7 km by differential Fourier transform infrared radiometry

Recent results are presented on the passive detection, identification, and quantification of a vapor cloud of SF6 measured at a horizontal standoff distance of 5.7 km using a dual-beam interferometer optimized for background signal suppression. The measurements were performed at Defense Research and Development Canada (DRDC)-Valcartier during a number of recent open-air experiments. The measurement approach is based on the differential passive standoff detection method that has been developed by DRDC Valcartier during the past few years. This work represents the first such measurement reported in the open literature for a standoff distance as large as 5.7 km. These results clearly demonstrate the capability of the differential radiometry approach to the detection, identification, and quantification of chemical vapor clouds located at long distances from the sensor.     

Quantification of nitryl chloride at part per trillion mixing ratios by thermal dissociation cavity ring-down spectroscopy

Nitryl chloride (ClNO(2)) is an important nocturnal nitrogen oxide reservoir species in the troposphere. Here, we report a novel method, thermal dissociation cavity ring-down spectroscopy (TD-CRDS), to quantify ClNO(2) mixing ratios with tens of parts-per-trillion by volume (pptv) sensitivity. The mixing ratios of ClNO(2) are determined by blue diode laser CRDS of NO(2), produced from quantitative thermal dissociation of ClNO(2) in an inlet heated to 450 °C, relative to NO(2) observed in an unheated reference channel. ClNO(2) was generated by passing Cl(2) gas over a slurry containing a 1:10 mixture of NaNO(2) and NaCl. The TD-CRDS response was evaluated using parallel measurements of ClNO(2) by chemical ionization mass spectrometry (CIMS) using I(-) as the reagent ion and NO(y) (= NO + NO(2) + HNO(3) + ΣRO(2)NO(2) + ΣRONO(2) + HONO + 2N(2)O(5) + ClNO(2) + ...) chemiluminescence (CL). The linear dynamic range extends from the detection limit of 20 pptv (1 σ, 1 min) to 30 parts-per-billion by volume (ppbv), the highest mixing ratio tested. The ClNO(2) TD profile overlaps with those of alkyl nitrates, which has implications for nocturnal measurements of total alkyl nitrate (ΣAN = ΣRONO(2)) abundances by thermal dissociation (with detection as NO(2)) in ambient air.     

应用热解吸/气相色谱技术分析食品级二氧化碳中痕量苯

引用对室内空气中微量苯和TVOC的检测原理,利用Tenax TA吸附剂吸附浓缩二氧化碳中微量苯,提高进入色谱分析系统的苯的绝对量。从而大大提高了气相色谱仪的方法检测灵敏度,实现食品级二氧化碳中痕量苯的分析,其最小的检测浓度为0.37×10^-9mol/mol。实验表明,测试方法重复性较好,相对标准偏差〈5%,线性相关系数〉0.9999。     

Photodissociation followed by laser-induced fluorescence at atmospheric pressure and 24 degrees C: a unique scheme for remote detection of explosives

A unique scheme has been applied for sensitive remote detection of 2,4,6-trinitrotoluene (TNT) vapor trace amounts at atmospheric pressure and 24 degrees C. The detection concept is based on a single laser beam inducing a tandem process: photodissociation of TNT vapor followed by highly selective detection of its photofragments vibrationally excited NO, utilizing laser-induced fluorescence with the A2Sigma+(v' = 0) <-- X2Pi(v' = 2) transition. A detection sensitivity of at least 8 parts in 10(9) of TNT vapor with a signal-to-noise ratio of approximately 10 has been experimentally verified for an unfocused approximately 5-mJ laser beam, measured at a distance of approximately 15 cm from the TNT sample.     

Remote atmospheric breakdown for standoff detection by using an intense short laser pulse

A remote atmospheric breakdown is a very rich source of UV and broadband visible light that could provide an early warning of the presence of chemical-biological warfare agents at extended standoff distances. A negatively chirped laser pulse propagating in air compresses in time and focuses transversely, which results in a rapid laser intensity increase and ionization near the focal region that can be located kilometers away from the laser system. Proof-of-principle laboratory experiments are performed on the generation of remote atmospheric breakdown and the spectroscopic detection of mock biological warfare agents. We have generated third harmonics at 267 nm and UV broadband radiation in air from the compression and focusing of femtosecond laser pulses. Fluorescence emission from albumin aerosols as they were illuminated by the femtosecond laser pulse has been observed.     

Atmospheric pressure laser ionization. An analytical technique for highly selective detection of ultralow concentrations in the gas phase

In this contribution a new analytical technique is presented for the direct mass spectrometric (MS) detection of gas-phase trace species at atmospheric pressure. Employing resonance-enhanced multiphoton ionization (REMPI) close to the inlet nozzle orifice, i.e., at high molecule densities, the sensitivity of the instrument has been increased by up to 3 orders of magnitude as compared to conventional REMPI-MS with ionization in a differentially coupled ion source. Furthermore, adiabatic cooling, resonant ionization, and mass-selective detection establish a highly selective analytical technique. Several atmospherically relevant compounds were investigated. The current detection limit for NO is 0.9 pptv, for acetaldehyde 1.7 pptv, for CO 15 pptv, and for 2,5-dichlorotoluene 12 pptv. We discuss APLI with regard to applications in medical and environmental research.     

Detection of NO and NO(2) by (2 + 2) resonance-enhanced multiphoton ionization and photoacoustic spectroscopy near 454 nm

Trace concentrations of NO and NO(2) are detected with a dye laser operating near 454 nm. NO is detected by a (2 + 2) resonance-enhanced multiphoton ionization process by means of NO A(2)Σ+-X(2)Π(0, 0) transitions with miniature electrodes, and NO(2) is detected by a one-photon absorption photoacoustic process by means of NO(2)Aˉ' (2)B(1)(0, 8, 0)- Xˉ (2)A(1)(0, 0, 0) transitions with a miniature microphone. Rotationally resolved excitation spectra show that the spectral resolution is sufficiently high to identify these species at 1 atm. The technique's analytical merits are evaluated as functions of concentration, pressure, and laser intensities. Low laser intensities favor NO(2) photoacoustic detection whereas high laser intensities favor NO ionization. Limits of detection (signal-to-noise ratio 3) of 160 parts in 10(9) for NO and 400 parts in 10(9) for NO(2) are determined at 1 atm for a 10-s integration time. Signal response and noise analyses show that three decades of NO/NO(2) mixtures can be measured with a computational relative error in concentration that is three times the relative error in measuring the NO and NO(2) signals.     

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.     

Measurement of nitric oxide with an antimonide diode laser

An antimonide diode laser operating near 2.65 mum was used to measure absorption lines of NO gas in the first overtone band. A blended line pair of NO that is sufficiently free of interference from H(2) O to permit the selective detection of NO under reduced pressure conditions was identified. With wavelength-modulation spectroscopy, a rms noise level equivalent to an absorbance of 3.2 x 10(-5) was achieved at a measurement integration time (for a single spectral data point) of 0.1 s. The corresponding detection sensitivity (signal-to-noise ratio of 2) for NO in air at reduced pressure was ~15 ppm m (ppm is parts in 10(6)). Antimonide diode lasers show substantial promise for gas-sensing applications because they can gain access to relatively strong absorption lines of several gases of environmental interest at operating wavelengths at which cryogenic cooling is not required.     

空爆载荷作用下螺栓法兰管道的动态响应研究

螺栓法兰连接结构具有强度高、构造简单和操作便捷等优点,被广泛应用于土木工程、机械工程、核工业和国防装备等工业领域.基于ANSYS/LS-DYNA软件建立有限元模型,研究了空爆载荷作用下(爆距为100～250 cm,TNT炸药当量为1000～16000 g)螺栓法兰管道的动力学性能.研究表明:炸药当量越大,爆距越小,螺栓...     

Off-axis cavity ringdown spectroscopy: application to atmospheric nitrate radical detection

Atmospheric nitrate radicals (NO3) are detected using off-axis cavity ringdown spectroscopy (CRDS) for the first time to our knowledge with a room-temperature continuous-wave (cw) diode laser operating near 662 nm. A prototype instrument was constructed that achieved a 1sigma absorption sensitivity of 5 x 10(-10) cm(-1) Hz(-1/2), corresponding to a 1.4 part per trillion by volume 2sigma detection limit in 4.6 s at 80 degrees C. This sensitivity is a significant improvement over a recent implementation of off-axis cavity-enhanced absorption spectroscopy and comparable to that of the most advanced cw CRDS and pulsed CRDS applications for atmospheric detection of NO3. A comparison of measurements of ambient air in Fairbanks, Alaska, recorded with the off-axis CRDS instrument and a previously characterized conventional cw CRDS instrument showed good agreement (R2 = 0.97).     

Intracavity CO laser photoacoustic trace gas detection: cyclic CH(4), H(2)O and CO(2) emission by cockroaches and scarab beetles

A liquid-nitrogen-cooled CO laser and an intracavity resonant photoacoustic cell are employed to monitor trace gases. The setup was designed to monitor trace gas emissions of biological samples on line. The arrangement offers the possibility to measure gases at the 10(9) by volume (ppbv) level (e.g., CH(4), H(2) O) and to detect rapid changes in trace gas emission. A detection limit of 1 ppbv for CH(4) in N(2) equivalent to a minimal detectable absorption of 3 × 10(-9) cm(-1) can be achieved. Because of the kinetic cooling effect we lowered the detection limit for CH(4) in air is decreased to 10 ppbv. We used the instrument in a first application to measure the CH(4) and H(2) O emission of individual cockroaches and scarab beetles. These emissions could be correlated with CO(2) emissions that were recorded simultaneously with an infrared gas analyzer. Characteristic breathing patterns of the insects could be observed; unexpectedly methane was also found to be released.     

Ultrasensitive dual-beam absorption and gain spectroscopy: applications for near-infrared and visible diode laser sensors

A dual-beam detection strategy with automatic balancing is described for ultrasensitive spectroscopy. Absorbances of 2 × 10(-7) Hz(-?) in free-space configurations and 5 × 10(-6) Hz(-?) in fiber-coupled configurations are demonstrated. With the dual-beam technique, atmospherically broadened absorption transitions may be resolved with InGaAsP, AlGaAs, and AlGaInP single-longitudinal-mode diode lasers. Applications to trace measurements of NO(2), O(2), and H(2)O are described by the use of simple, inexpensive laser and detector systems. Small signal gain measurements on optically pumped I(2) with a sensitivity of 10(-5) are also reported.     

Standoff detection of chemical and biological threats using laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) is a promising technique for real-time chemical and biological warfare agent detection in the field. We have demonstrated the detection and discrimination of the biological warfare agent surrogates Bacillus subtilis (BG) (2% false negatives, 0% false positives) and ovalbumin (0% false negatives, 1% false positives) at 20 meters using standoff laser-induced breakdown spectroscopy (ST-LIBS) and linear correlation. Unknown interferent samples (not included in the model), samples on different substrates, and mixtures of BG and Arizona road dust have been classified with reasonable success using partial least squares discriminant analysis (PLS-DA). A few of the samples tested such as the soot (not included in the model) and the 25% BG:75% dust mixture resulted in a significant number of false positives or false negatives, respectively. Our preliminary results indicate that while LIBS is able to discriminate biomaterials with similar elemental compositions at standoff distances based on differences in key intensity ratios, further work is needed to reduce the number of false positives/negatives by refining the PLS-DA model to include a sufficient range of material classes and carefully selecting a detection threshold. In addition, we have demonstrated that LIBS can distinguish five different organophosphate nerve agent simulants at 20 meters, despite their similar stoichiometric formulas. Finally, a combined PLS-DA model for chemical, biological, and explosives detection using a single ST-LIBS sensor has been developed in order to demonstrate the potential of standoff LIBS for universal hazardous materials detection.     

Using a new strategy to optimize the bump design parameters in flip chip packages

Flip chip technology has rapidly progressed in concert with the high speed and small dimension trends in electronic devices. The bump interconnects design dominates the performance of a flip chip package. This study produced a new strategy to optimize the geometric design parameters of the bump from the electrical standpoint. The first incident voltage was employed as the optimization objective function in order to reduce the response time delay in the binary command as well as maintain the chip level efficiency. Genetic algorithms were used for the search routines to evaluate the best bump geometric solutions. Two cases, 1.5 v V and 3.3 v V power supply voltage, were adopted to conduct this research in both air and underfill environments. The results show that the standoff height and the bump pitch determined in the underfill environment are greater than in the air environment. As the power supply voltage increases, the standoff height and bump pitch become more significant. A powerful optimal window for bump design parameters is thus established.     

A compact diode laser cavity ring-down spectrometer for atmospheric measurements of NO3 and N2O5 with automated zeroing and calibration

A compact rack-mounted cavity ring-down spectrometer (CRDS) for simultaneous measurements of the nocturnal nitrogen oxides NO(3) and N(2)O(5) in ambient air is described. The instrument uses a red diode laser to quantify mixing ratios of NO(3) (at its absorption maximum at 662 nm) and of N(2)O(5) following its thermal dissociation to NO(3) in a second detection channel. The spectrometer is equipped with an automated zeroing and calibration setup to determine effective NO(3) absorption cross-sections and NO(3) and N(2)O(5) inlet transmission efficiencies. The instrument response was calibrated using simultaneous measurements of NO(2), generated by thermal dissociation of N(2)O(5) and/or by titration of NO(3) with excess NO, using blue diode laser CRDS at 405 nm. When measuring ambient air, the (2σ, 10 s) precision of the red diode CRDS varied between 5 and 8 parts-per-trillion by volume (pptv), which sufficed to quantify N(2)O(5) concentrations under moderately polluted conditions. Sample N(2)O(5) measurements made on a rooftop on the University of Calgary campus in August 2010 are presented. A maximum N(2)O(5) mixing ratio of 130 pptv was observed, corresponding to a steady-state lifetime of less than 50 min. The NO(3) mixing ratios were below the detection limit, consistent with their predicted values based on equilibrium calculations. During the measurement period, the instrument response for N(2)O(5) was 70% of the theoretical maximum, rationalized by a slight mismatch of the laser diode output with the NO(3) absorption line and a N(2)O(5) inlet transmission efficiency less than unity. Advantages and limitations of the instrument's compact design are discussed.     

Dinitrobenzene detection by use of one-color laser photolysis and laser-induced fluorescence of vibrationally excited NO

Trace concentrations of 1, 4-dinitrobenzene (DNB) are detected by a combination of laser photolysis and laser-induced fluorescence. A one-color laser is applied to induce DNB photodissociation and for subsequent detection of NO photofragments by excitation and emission through A(v' =0) <-- X(v" = 0 - 2) and A(v' =0) --> X(v" = 0,1) transitions, respectively. The resulting NO rovibrational excitation spectra serve as markers for the presence of DNB. The NO is produced in vibrational ground and excited states with peak height ratios of (v" = 0):(v" = 1):(v" = 2) = 1:0.5:0.13. The limits of detection of DNB mixed with 100 or 500 Torr of air with v" = 2 excitation at 248 nm are 13 and 11 parts in 10(9) by weight, respectively, for a 30-s integration time. The application of this scheme for DNB detection has the advantage that no ambient ground state NO interferes and that the fluorescence is collected at shorter wavelengths than the exciting radiation, precluding background fluorescence.