Hydrogen leak detection using laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) is investigated as a technique for real-time monitoring of hydrogen gas. Two methodologies were examined: The use of a 100 mJ laser pulse to create a laser-induced breakdown directly in a sample gas stream, and the use of a 55 mJ laser pulse to create a laser-induced plasma on a solid substrate surface, with the expanding plasma sampling the gas stream. Various metals were analyzed as candidate substrate surfaces, including aluminum, copper, molybdenum, stainless steel, titanium, and tungsten. Stainless steel was selected, and a detailed analysis of hydrogen detection in binary mixtures of nitrogen and hydrogen at atmospheric pressure was performed. Both the gaseous plasma and the plasma initiated on the stainless steel surface generated comparable hydrogen emission signals, using the 656.28 Halpha emission line, and exhibited excellent signal linearity. The limit of detection is about 20 ppm (mass) as determined for both methodologies, with the solid-initiated plasma yielding a slightly better value. Overall, LIBS is concluded to be a viable candidate for hydrogen sensing, offering a combination of high sensitivity with a technique that is well suited to implementation in field environments.     

Quantitative analysis of deuterium in zircaloy using double-pulse laser-induced breakdown spectrometry (LIBS) and helium gas plasma without a sample chamber

A crucial safety measure to be strictly observed in the operation of heavy-water nuclear power plants is the mandatory regular inspection of the concentration of deuterium penetrated into the zircaloy fuel vessels. The existing standard method requires a tedious, destructive, and costly sample preparation process involving the removal of the remaining fuel in the vessel and melting away part of the zircaloy pipe. An alternative method of orthogonal dual-pulse laser-induced breakdown spectrometry (LIBS) is proposed by employing flowing atmospheric helium gas without the use of a sample chamber. The special setup of ps and ns laser systems, operated for the separate ablation of the sample target and the generation of helium gas plasma, respectively, with properly controlled relative timing, has succeeded in producing the desired sharp D I 656.10 nm emission line with effective suppression of the interfering H I 656.28 nm emission by operating the ps ablation laser at very low output energy of 26 mJ and 1 μs ahead of the helium plasma generation. Under this optimal experimental condition, a linear calibration line is attained with practically zero intercept and a 20 μg/g detection limit for D analysis of zircaloy sample while creating a crater only 10 μm in diameter. Therefore, this method promises its potential application for the practical, in situ, and virtually nondestructive quantitative microarea analysis of D, thereby supporting the more-efficient operation and maintenance of heavy-water nuclear power plants. Furthermore, it will also meet the anticipated needs of future nuclear fusion power plants, as well as other important fields of application in the foreseeable future.     

Highly sensitive electronically modulated photoacoustic spectrometer for ozone detection

An ozone (O(3)) gas sensor with a sensitivity of parts per 10(9) (ppb) level and a high level of selectivity based on the resonant photoacoustic effect was developed using an electronically modulated cw CO(2) laser beam. Quite different from the standard chopper modulation of a laser beam, here the laser source was electronically modulated to overcome the inherent problem of frequency instability associated with chopper modulation. With electronic modulation, in conjunction with the fast Fourier transform (FFT) of transient signals, we were able to improve significantly the sensitivity of the photoacoustic (PA) system for the detection of O(3). In addition to the improved sensitivity, our method proved that the FFT of a laser modulated PA signal could suppress the noise signal generated by spurious window diffused absorption, which in the case of most commonly used lock-in techniques is rather unavoidable. The dependence of the PA signal on various experimental parameters such as buffer gas, laser power, modulation frequency, and trace gas concentration was investigated. In the case of buffer gas, argon proved to be more suitable than nitrogen and helium in terms of enhancing the sensitivity of the system. The limits of detection of O(3) using the 9 P(14) CO(2) laser line in our PA system are 5 parts per 10(9) by volume (ppbv) and 14 ppbv with electronic and standard chopper modulation, respectively. This detection limit of O(3) is quite applicable for detection of safe levels of O(3), at ground level.     

Detection of chloride in reinforced concrete using a dualpulsed laser-induced breakdown spectrometer system: comparative study of the atomic transition lines of Cl I at 594.85 and 837.59 nm

The presence of chloride in reinforced concrete can cause severe damage to the strength and durability of buildings and bridges. The detection of chloride in concrete structures at early stages of the corrosion buildup process is, therefore, very important. However, detection of chlorine in trace amounts in concrete is not a simple matter. A dual-pulsed laser-induced breakdown spectrometer (LIBS) has been developed at our laboratory for the detection of chloride contents in reinforced concrete by using two atomic transition lines of neutral chlorine (Cl I) at 594.8 and 837.5 nm. A calibration curve was also established by using standard samples containing chloride in known concentration in the concrete. Our dual-pulsed LIBS system demonstrated a substantial improvement in the signal level at both wavelengths (594.8 and 837.5 nm). However, the new atomic transition line at 594.8 nm shows a significant improvement compared to the line at 837.5 nm in spite of the fact that the relative intensity of the former is 0.1% of the latter. This weak signal level of the 837.5 nm transition line of chlorine can be attributed to some kind of self-absorption process taking place in the case of the concrete sample.     

Detection of hydrogen peroxide using photofragmentation laser-induced fluorescence

Photofragmentation laser-induced fluorescence (PF-LIF) is for the first time demonstrated to be a practical diagnostic tool for detection of hydrogen peroxide. Point measurements as well as two-dimensional (2D) measurements in free-flows, with nitrogen as bath gas, are reported. The present application of the PF-LIF technique involves one laser, emitting radiation of 266 nm wavelength, to dissociate hydrogen peroxide molecules into OH radicals, and another laser, emitting at 282.25 nm, to electronically excite OH, whose laser-induced fluorescence is detected. The measurement procedure is explained in detail and a suitable time separation between photolysis and excitation pulse is proposed to be on the order of a few hundred nanoseconds. With a separation time in that regime, recorded OH excitation scans were found to be thermal and the signal was close to maximum. The PF-LIF signal strength was shown to follow the same trend as the vapor pressure corresponding to the hydrogen peroxide liquid concentration. Thus, the PF-LIF signal appeared to increase linearly with hydrogen peroxide vapor-phase concentration. For 2D single shot measurements, a conservatively estimated value of the detection limit is 30 ppm. Experiments verified that for averaged point measurements the detection limit was well below 30 ppm.     

Practical high-resolution detection method for laser-induced breakdown spectroscopy

A Fabry-Perot etalon was coupled to a Czerny-Turner spectrometer to acquire high-resolution measurements in laser-induced breakdown spectroscopy (LIBS). The spectrometer was built using an inexpensive etalon coupled to a standard 0.5 m imaging spectrometer. The Hg emission doublet at 313.2 nm was used to evaluate instrument performance because it has a splitting of 29 pm. The 313.2 nm doublet was chosen due to the similar splitting seen in isotope splitting from uranium at 424.437 nm, which is 25 pm. The Hg doublet was easily resolved from a continuous-source Hg lamp with a 2 s acquisition. The doublet was also resolved in LIBS spectra of cinnabar (HgS) from the accumulation of 600 laser shots at rate of 10 Hz, or 1 min, under a helium atmosphere. In addition to the observed splitting of the 313.2 nm Hg doublet, the FWHM of the 313.1844 nm line from the doublet is reported at varying helium atmospheric pressures. The high performance, low cost, and compact footprint make this system highly competitive with 2 m double-pass Czerny-Turner spectrometers.     

Quantitative analysis of liquids from aerosols and microdrops using laser induced breakdown spectroscopy

Laser induced breakdown spectroscopy (LIBS) is shown to be capable of low volume (90 pL) quantitative elemental analysis of picogram amounts of dissolved metals in solutions. Single-pulse and collinear double-pulse LIBS were investigated using a 532 nm dual head laser coupled to a spectrometer with an intensified charge coupled device (CCD) detector. Aerosols were produced using a micronebulizer, conditioned inside a concentric spray chamber, and released through an injector tube with a diameter of 1 mm such that a LIBS plasma could be formed ~2 mm from the exit of the tube. The emissions from both the aerosols and a single microdrop were then collected with a broadband high resolution spectrometer. Multielement calibration solutions were prepared, and continuing calibration verification (CCV) standards were analyzed for both aerosol and microdrop systems to calculate the precision, accuracy, and limits of detection for each system. The calibration curves produced correlation coefficients with R(2) values > 0.99 for both systems. The precision, accuracy, and limit of detection (LOD) determined for aerosol LIBS were averaged and determined for the emission lines of Sr II (421.55 nm), Mg II (279.80 nm), Ba II (493.41 nm), and Ca II (396.84 nm) to be ~3.8% RSD, 3.1% bias, 0.7 μg/mL, respectively. A microdrop dispenser was used to deliver single drops containing 90 pL into the space where a LIBS plasma was generated with a focused laser pulse. In the single drop microdrop LIBS experiment, the analysis of a single drop, containing a total mass of 45 pg, resulted in a precision of 13% RSD and a bias of 1% for the Al I (394.40 nm) emission line. The absolute limits of detection of single drop microdrop LIBS for the emission lines Al I (394.40 nm) and Sr II (421.5 nm) were approximately 1 pg, and Ba II (493.41 nm) produced an absolute detection limit of approximately 3 pg. Overall, the precision, accuracy, and absolute LOD determined for single microdrop LIBS resulted in a typical performance of ~14% RSD, 6% bias, and 1 pg for the elements Sr II (421.55 nm), Al I(394.40 nm), Mg II (279.80), and Ba II(493.41 nm).     

Detection of chromium in wastewater from refuse incineration power plant near Poyang Lake by laser induced breakdown spectroscopy

A laser induced breakdown spectroscopy (LIBS) system was developed for determination of toxic metals Cr in wastewater collected from a refuse incineration power plant near Poyang Lake. The plasma was generated by focusing a pulsed Nd:YAG laser at 1064 nm on the surface of liquid. Experimental conditions were optimized for improving the sensitivity and repeatability of the LIBS system through a parametric dependence study in potassium bichromate (K(2)Cr(2)O(7)) aqueous solutions. Calibration curves for Cr I 425.43 and 357.87 nm lines are compared and the limit of detection is found to be 39 and 86 ppm, respectively. This calibration curve of Cr I 425.43 nm has been used for quantification of Cr in wastewater collected from a refuse incineration power plant near Poyang Lake where the concentration of Cr is found to be 97 ppm. The results between LIBS and standard analytical technique such as atomic absorption spectroscopy were compared, and the relative standard deviation was 8.5%.     

Quantitative hydrogen analysis of zircaloy-4 using low-pressure laser plasma technique

It is found in this work that variation of laser power density in low-pressure plasma spectrochemical analysis of hydrogen affects sensitively the hydrogen emission intensity from the unwanted and yet ubiquitous presence of ambient water. A special experimental setup has been devised to allow the simple condition of focusing/defocusing the laser beam on the sample surface. When applied to zircaloy-4 samples prepared with various hydrogen impurity concentrations using low-pressure helium surrounding gas, good-quality hydrogen emission lines of very high signal to background ratios were obtained with high reproducibility under weakly focused or largely defocused laser irradiation. These measurements resulted in a linear calibration line with nonzero intercept representing the residual contribution from the recalcitrant water molecules. It was further shown that this can be evaluated and taken into account by means of the measured intensity ratio between the oxygen and zirconium emission lines. We have demonstrated the applicability of this experimental approach for quantitative determination of hydrogen impurity concentrations in the samples considered.     

Influence of Er:YAG and Nd:YAG wavelengths on laser-induced breakdown spectroscopy measurements under air or helium atmosphere

Laser-induced breakdown spectroscopy (LIBS) is widely dependent on the conditions of its implementation in terms of laser characteristics (wavelength, energy, and pulse duration), focusing conditions, and surrounding gas. In this study two wavelengths, 1.06 and 2.94 microm, obtained with Nd:YAG and Er:YAG lasers, respectively, were used for LIBS analysis of aluminum alloy samples in two conditions of surrounding gas. The influence of the laser wavelength on the laser-produced plasma was studied for the same irradiance by use of air or helium as a buffer gas at atmospheric pressure. We used measurements of light emission to determine the temporally resolved space-averaged electron density and plasma temperature in the laser-induced plasma. We also examined the effect of laser wavelength in two different ambient conditions in terms of spectrochemical analysis by LIBS. The results indicate that the effect of the surrounding gas depends on the laser wavelength and the use of an Er:YAG laser could increase linearity by limiting the leveling in the calibration curve for some elements in aluminum alloys. There is also a significant difference between the plasma induced by the two lasers in terms of electron density and plasma temperature.     

Quantitative hydrogen analysis of zircaloy-4 in laser-induced breakdown spectroscopy with ambient helium gas

This experiment was carried out to address the need for overcoming the difficulties encountered in hydrogen analysis by means of plasma emission spectroscopy in atmospheric ambient gas. The result of this study on zircaloy-4 samples from a nuclear power plant demonstrates the possibility of attaining a very sharp emission line from impure hydrogen with a very low background and practical elimination of spectral contamination of hydrogen emission arising from surface water and water vapor in atmospheric ambient gas. This was achieved by employing ultrapure ambient helium gas as well as the proper defocusing of the laser irradiation and a large number of repeated precleaning laser shots at the same spot of the sample surface. Further adjustment of the gating time has led to significant reduction of spectral width and improvement of detection sensitivity to ~50 ppm. Finally, a linear calibration curve was also obtained for the zircaloy-4 samples with zero intercept. These results demonstrate the feasibility of this technique for practical in situ and quantitative analysis of hydrogen impurity in zircaloy-4 tubes used in a light water nuclear power plant.     

Comparison of nanosecond and picosecond excitation for interference-free two-photon laser-induced fluorescence detection of atomic hydrogen in flames

Two-photon laser-induced fluorescence (TP-LIF) line imaging of atomic hydrogen was investigated in a series of premixed CH4/O2/N2, H2/O2, and H2/O2/N2 flames using excitation with either picosecond or nanosecond pulsed lasers operating at 205 nm. Radial TP-LIF profiles were measured for a range of pulse fluences to determine the maximum interference-free signal levels and the corresponding picosecond and nanosecond laser fluences in each of 12 flames. For an interference-free measurement, the shape of the TP-LIF profile is independent of laser fluence. For larger fluences, distortions in the profile are attributed to photodissociation of H2O, CH3, and/or other combustion intermediates, and stimulated emission. In comparison with the nanosecond laser, excitation with the picosecond laser can effectively reduce the photolytic interference and produces approximately an order of magnitude larger interference-free signal in CH4/O2/N2 flames with equivalence ratios in the range of 0.5< or =Phi< or =1.4, and in H2/O2 flames with 0.3< or =Phi< or =1.2. Although photolytic interference limits the nanosecond laser fluence in all flames, stimulated emission, occurring between the laser-excited level, H(n=3), and H(n=2), is the limiting factor for picosecond excitation in the flames with the highest H atom concentration. Nanosecond excitation is advantageous in the richest (Phi=1.64) CH4/O2/N2 flame and in H2/O2/N2 flames. The optimal excitation pulse width for interference-free H atom detection depends on the relative concentrations of hydrogen atoms and photolytic precursors, the flame temperature, and the laser path length within the flame.     

Detection of atomic hydrogen in flames using picosecond two-color two-photon-resonant six-wave-mixing spectroscopy

We report an investigation of two-color six-wave-mixing spectroscopy techniques using picosecond lasers for the detection of atomic hydrogen in an atmospheric-pressure hydrogen-air flame. An ultraviolet laser at 243 nm was two-photon-resonant with the 2S(1/2) <-- <-- 1S(1/2) transition, and a visible probe laser at 656 nm was resonant with H(alpha) transitions (n=3 <-- n=2). The signal dependence on the polarization of the pump laser was investigated for a two- beam polarization-spectroscopy experimental configuration and for a four- beam grating configuration. A direct comparison of the absolute signal and background levels in the two experimental geometries demonstrated a significant advantage to using the four-beam grating geometry over the simpler two-beam configuration. Picosecond laser pulses provided sufficient time resolution to investigate hydrogen collisions in the atmospheric-pressure flame. Time-resolved two-color laser-induced fluorescence was used to measure an n=2 population lifetime of 110 ps, and time-resolved two-color six-wave-mixing spectroscopy was used to measure a coherence lifetime of 76 ps. Based on the collisional time scale, we expect that the six-wave-mixing signal dependence on collisions is significantly reduced with picosecond laser pulses when compared to laser pulse durations on the nanosecond time scale.     

载气种类对单壁碳纳米管管径的影响研究

单壁碳纳米管的管径对其性能、特别是储氢性能有极其重要的影响,但至今未见制备过程中系统控制单壁碳纳米管管径的报道.本文分别以氦气、氮气和氩气为载气,采用催化裂解法制备了不同直径范围的单壁碳纳米管.HRTEM和Raman光谱分析表明,以氦气、氩气为载气制得的碳管直径分布范围相对较窄,平均直径分别约为1.6和5.0nm.以氮气为载气时碳管直径分布相对较宽,约为2.0～4.5nm.氮气与碳反应生成氮化碳可能是导致单壁碳纳米管直径分布相对较宽的主要原因.分别以氦气、氮气和氩气为载气制得的单壁碳纳米管,在273K,15MPa时质量储氢分数依次为4.21%、6.30%和8.05%.     

Laser-induced breakdown spectroscopy of alkali metals in high-temperature gas

Laser-induced breakdown spectroscopy (LIBS) measurements of alkali in the high-temperature exhaust of a glass furnace show an attenuation of the Na and K LIBS signals that correlates with the stoichiometry of the bath gas surrounding the spark. The results are explained as being due to (1) a strong increase in the concentration of atomic Na and K, resulting in neutral line signal absorption by these atoms, and to (2) a change of phase of the major Na- and K-containing species from an aerosol to a gaseous phase when the gas mixture becomes fuel rich, resulting in a reduced LIBS emission intensity. LIBS sampling at lower temperatures, or in a consistently oxidizing environment, or both are suggested strategies for circumventing these difficulties.     

Microanalysis of tool steel and glass with laser-induced breakdown spectroscopy

A laser microscope system for the microanalytical characterization of complex materials is described. The universal measuring principle of laser-induced breakdown spectroscopy (LIBS) in combination with echelle optics permits a fast simultaneous multielement analysis with a possible spatial resolution below 10 pm. The developed system features completely UV-transparent optics for the laser-microscope coupling and the emission beam path and enables parallel signal detection within the wavelength range of 200-800 nm with a spectral resolution of a few picometers. Investigations of glass defects and tool steels were performed. The characterization of a glass defect in a tumbler by a micro-LIBS line scan, with use of a 266-nm diode-pumped Nd:YAG laser for excitation, is possible by simple comparison of plasma spectra of the defect and the surrounding area. Variations in the main elemental composition as well as impurities by trace elements are detected at the same time. Through measurement of the calibration samples with the known concentration of the corresponding element, a correlation between the intensity of spectral lines and the element concentration was also achieved. The change of elemental composition at the transient stellite solder of tool steels has been determined by an area scan. The two-dimensional pictures show abrupt changes of the element distribution along the solder edge and allow fundamental researches of dynamic modifications (e.g., diffusion) in steel.     

Nonlinear susceptibility interference in laser SRS-CARS diagnostics of hydrogen in gas mixtures

We have studied the possibility to measure small hydrogen concentrations in dense gas mixtures by method of coherent anti-Stokes Raman scattering (CARS) in combination with biharmonic laser pumping by means of stimulated Raman scattering (SRS). It was found that the interference of nonlinear susceptibilities of a buffer gas and hydrogen can lead to a parabolic dependence of the signal intensity on the hydrogen concentration, which makes the results of analyses uncertain. The ambiguity can be eliminated by selecting an appropriate composition and pressure of the gas mixture in the cell of the SRS generator of biharmonic laser pumping. Using this approach, hydrogen in air at atmospheric pressure can be detected by the laser SRS-CARS technique on a level of 5 ppm.     

On-line detection of heavy metals and brominated flame retardants in technical polymers with laser-induced breakdown spectrometry

The use of laser-induced breakdown spectrometry (LIBS) for the analysis of heavy metals and brominated flame retardants in end-of-life waste electric and electronic equipment (EOL-WEEE) pieces is investigated. Single- and double-pulse plasma excitation as well as the influence of detection parameters is studied to yield a parameter field with improved sensitivity and limits of detection. A LIBS analyzer was set up as an on-line measuring unit to detect heavy metals and brominated flame retardants in moving EOL-WEEE pieces in an automatic sorting line. An autofocusing unit with an adjustment range of 50 mm was incorporated to permit measurements of objects that pass by a LIBS analyzer with their surfaces at various distances from it. Tests with EOL-WEEE monitor housings on the conveyor belt of a pilot sorting system successfully demonstrated the capability of the LIBS analyzer to quantify the concentration of hazardous elements in real waste EOL-WEEE pieces.     

Laser plasma emission spectrum corrected for the quantitative analysis of alloys

A new approach to the quantitative elemental analysis of alloys by means of the laser induced breakdown spectroscopy (LIBS) is proposed and justified. The proposed correction taking into account the Prokhorov-Bunkin melt transparency wave ensures a good agreement between the relative intensities of LIBS analytical lines [(nm): Cu, 511; Zn, 472; Sn, 286; Pb, 406] and the alloy stoichiometry for five samples of bronze measured in various regimes of plasma excitation and signal detection.     

Monte Carlo simulation of the electron beam scattering under gas mixtures environment in an HPSEM at low energy

The effects of various gas environment used in high pressure SEM inside the specimen chamber were investigated using Monte Carlo simulation. In order to improve the signal to noise ratio for the electron detection, we suggest to use helium gas-based mixture. The Helium gas is well known to reduce the skirt effect due to its low elastic scattering cross-section. The addition of an ionizing gas such as hydrogen or nitrogen is proposed to increase the inelastic scattering cross section which is mainly responsible for the ionisation process taking place during the beam-gas interactions. For all the mixtures (except He-Argon), the main results show that the skirt is slightly modified with the increase of the pressure. For the BSE detection, the signal to noise can remain high and gives a good contrast in imaging. Moreover, the presence of an ionizing gas will favour the ionizing process which is very important in beam-based electron detection. In this case, an increase of the signal to noise ratio can be expected.