Hydrogen and Deuterium Analysis Using Laser‐Induced Plasma Spectroscopy

Abstract

Hydrogen emission in laser plasma has been studied by focusing a TEA CO₂ laser and Nd‐YAG lasers on various types of samples, such as glass, quartz, and zircaloy pipes doped with hydrogen. It was found that H_α emission with a narrow spectral width occurs with high efficiency when the laser plasma is produced in low‐pressure host gas. In contrast, the conventional well‐known laser‐induced breakdown spectroscopy (LIBS), which operates at atmospheric air pressure, cannot be applied for the analysis of hydrogen as impurity. The specific characteristic of hydrogen emission in low‐pressure plasma is interpreted on the basis of our shock wave model, taking account of the fact that the hydrogen mass is extremely light compared to that of the host target. Another experimental study on gas analysis was conducted using an Nd‐YAG laser and helium host gas at atmospheric pressure on a sample of mixed water (H₂O) and heavy water (D₂O) in vapor form. It was shown that completely resolved hydrogen (H_α) and deuterium (D_α) emission lines that are separated by only 0.179 nm could be obtained at a properly delayed detection time when the charged particles responsible for the strong Stark broadening effect in the plasma have mostly disappeared. It is argued that a helium metastable excited state plays the important role in the hydrogen excitation process.     

Initiation of combustion of a methane-air mixture in a supersonic flow behind a shock wave during laser excitation of O<Subscript>2</Subscript> molecules

The possibility of initiating detonation of CH₄ + air in a supersonic flow behind an oblique shock wave under the exposure of the mixture to laser radiation with wavelengths λ_I=1.268 μm and 762 nm is analyzed. It is shown that this irradiation leads to excitation of O₂ molecules to the a ¹Δ_g and b ¹Σ _g ⁺ states, which intensifies the chain mechanism of combustion of CH₄/O₂ (air) mixtures. Even for a small value of the laser radiation energy absorbed by an O₂ molecule (∼0.05–0.1 eV), detonation mode of combustion in a poorly inflammable mixture such as CH₄/air can be realized at a distance of only 1 m from the primary shock wave front for relatively small values of temperature (∼1100 K) behind the front under atmospheric pressure.     

Non-invasive determination of shock wave pressure generated by optical breakdown

Shock waves generated by a laser-induced plasma were investigated using a pump-and-probe technique. Both 7-ns and 40-ps laser pulses at 1.06 m were employed to initiate breakdown in water. Two He-Ne laser beams were used as a velocity probe, allowing the accurate measurement of the shock velocity around the plasma. The maximum shock pressure was determined from the measured shock velocities, the jump condition and the equation of state for water. The conservation of the total momentum of the shock front was used to derive expressions for the shock velocity, particle velocity and shock pressure vs. the distance (r) from the center of the plasma. For a shock wave of spherical symmetry, the shock pressure is proportional to 1/r ². Our work shows that the expanding plasma initially induces a shock wave; the shock wave dissipates rapidly becoming an acoustic wave within 300–500 m.     

Shock wave structure in simple liquids

The shock wave structure in a liquid is studied by a molecular dynamics simulation method. The interaction between atoms is described by the Lennard-Jones (6–12) potential. In contrast to earlier works, the simulation is performed in a reference frame tied to the shock wave front. This approach reduces non-physical fluctuations and makes it possible to calculate the distribution functions of the kinetic and potential energy for several cross sections within the shock layer. The profiles of flow variables and their fluctuations are found. The surface tension connected with pressure anisotropy within the shock front is calculated. It is shown that the main contribution to the surface tension coefficient comes from the mean virial. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 9, 722–727 (10 May 1997) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Calculation of shock wave propagation in water containing reactive gas bubbles

The entry of a shock wave from air into water containing reactive gas (stoichiometric acetylene–oxygen mixture) bubbles uniformly distributed over the volume of the liquid has been numerically investigated using equations describing two-phase compressible viscous reactive flow. It has been demonstrated that a steady-state supersonic self-sustaining reaction front with rapid and complete fuel burnout in the leading shock wave can propagate in this bubbly medium. This reaction front can be treated as a detonation-like front or “bubble detonation.” The calculated and measured velocities of the bubble detonation wave have been compared at initial gas volume fraction of 2 to 6%. The observed and calculated data are in satisfactory qualitative and quantitative agreement. The structure of the bubble detonation wave has been numerically studied. In this wave, the gas volume fraction behind the leading front is approximately 3–4 times higher than in the pressure wave that propagates in water with air bubbles when the other initial conditions are the same. The bubble detonation wave can form after the penetration of the shock wave to a small depth (~300 mm) into the column of the bubbly medium. The model suggested here can be used to find optimum conditions for maximizing the efficiency of momentum transfer from the pressure wave to the bubbly medium in promising hydrojet pulse detonation engines.     

Acoustic emission monitoring during laser shock cleaning of silicon wafers

A laser shock cleaning is a new dry cleaning methodology for the effective removal of submicron sized particles from solid surfaces. This technique uses a plasma shock wave produced by laser-induced air breakdown, which has applied to remove nano-scale silica particles from silicon wafer surfaces in this work. In order to characterize the laser shock cleaning process, acoustic waves generated during the shock process are measured in real time by a wide-band microphone and analyzed in the change of process parameters such as laser power density and gas species. It was found that the acoustic intensity is closely correlated with the shock wave intensity. From acoustic analysis, it is seen that acoustic intensity became stronger as incident laser power density increased. In addition, Ar gas has been found to be more effective to enhance the acoustic intensity, which allows higher cleaning performance compared with air or N₂ gas.     

Shock waves and formation of carbon dioxide hydrate at an increased pressure in the gas-liquid medium

The processes of breaking, solution, and formation of hydrates behind a shock wave of moderate amplitude were studied experimentally in water with carbon dioxide bubbles under different initial static pressures. It is shown that an increase in the static pressure in a gas-liquid medium leads to reduction of critical relative amplitude of the shock wave, corresponding to starting development of Kelvin — Helmholtz instability and bubble splitting into small gas inclusions behind the shock wave front. It is shown that the rates of carbon dioxide solution and hydrate formation behind the shock wave front are close by the value; their dependences on medium and wave parameters are determined. Calculations by the model of gas hydration behind the shock wave are presented. The work was financially supported by the Russian Foundation for Basic Research (grants Nos. 06-01-00142 and 06-08-00657).     

Effect of multiple ion reflections on the structure of an ion-sound shock wave

It is shown that multiple ion reflection, arising as a result of collisional dissipation, from a shock front can produce an ion-sound shock wave with an arbitrarily large Mach number. For an exponentially small number of reflected ions, the ion-sound shock wave “degenerates” into a collisionless quasishock wave. The comparative role of viscosity and sound dispersion with different initial nonisothermality of the plasma is discussed. Zh. Tekh. Fiz. 69, 52–56 (December 1999)     

Pulsed discharge in nitrogen and argon under an elevated pressure in a nonuniform electric field

The characteristics of a discharge and radiation in nitrogen and argon under pressures of 10–760 Torr and the discharge formation without pre-ionization of the gap from an auxiliary source are considered. A peak is detected on the pressure dependence of the radiation power of the second positive system of nitrogen for E ₀/p ～ 270 V/cm Torr and nitrogen pressure p ～ 70 Torr. In the pressure range 10–760 Torr and for a voltage pulse leading front duration of ～ 10 ns, an electron beam is formed behind the grid anode with various half-amplitude pulse durations. It is shown that, under the given conditions, the electron beam is formed at the voltage pulse front both in the case of a discharge gap breakdown and in the absence of a clearly manifested breakdown, as well as for a 10-ns delay of breakdown at the leading front of a discharge current pulse.     

The Self-Similarity Index of the Convergence of Strong Cylindrical Shock Waves in a Gas with a Uniform Density

A model of the convergence of cylindrical shock waves (SWs) in a gas with a uniform density has been considered. The partial differential equations of this model have been reduced to ordinary differential equations, from which the law of convergence of such shock waves and the dependence α = f(γ, γ_eff) of their self-similarity index α on the heat-capacity ratio in front of the shock wave (γ) and behind the shock wave front (γ_eff) of the gas have been found. This dependence for cylindrical shock waves has been shown to agree with the experimental data within the measurement error.     

Behavior of point defects under impulsive dynamical loading

The behavior of point defects (interstitial atoms and vacancies) is examined in the front of a plane shock wave. The wave is modeled by a soliton pulse. It is shown that in high-pressure shock waves with a narrow loading wave front an unactivated motion of the point defects is possible, and for a pressure P_o 50 GPa and x_o 10^–8 m, a dragging of the interstitial atoms by the front of the shock wave can be observed. The vacancies are displaced in the field of the shock pulse in the opposite direction to the motion of the pulse. Here the mobility of the vacancies is significantly lower than that of the interstitial atoms.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 49–52, June, 1985.     

Influence of Small Xe Additives on the Detonation Threshold for O<Subscript>2</Subscript>−H<Subscript>2</Subscript>−He Mixtures

The effect of a small Xe additive on the conditions of detonation initiation in incident shock waves of various intensities is studied. The experiments are carried out on a shock tube facility with 10% H₂ + 5% O₂ + 85% He, 10% H₂ + 5% O₂ + 84.75% He + 0.25% Xe, and 10% H₂ + 5% O₂ + 84.5% He + 0.5% Xe mixtures. The addition of Xe led to a shift in the detonation threshold toward weaker shock waves. This effect is probably due to a significant increase in the frequency of high-energy collisions between O₂ and Xe molecules in the shock wave front in comparison with that characteristic of the equilibrium behind the wave, a factor that significantly accelerates the chemical reaction between O₂ and H₂ behind the front. The effect is a consequence of the formation of a specific translational nonequilibrium in the wave front. A previously performed numerical study of the distributions of pairs of O₂ and Xe molecules in the shock wave front shows that this effect can be enhanced by decreasing the Xe concentration from 0.5 to 0.25%. The experiment performed indirectly confirms this conclusion. It turns out that, for the mixture with 0.25% Xe, the detonation threshold shifts more strongly to the region of weaker shock waves than for the mixture with 0.5% Xe. This result gives additional arguments in favor of the assumption that this effect is due to the specifics of the translational nonequilibrium in the wave front.     

Problems of interpretation of holographic interferograms near shock wave fronts

A method of avoiding ambiguity in the interpretation of interferograms near a shock wave front is proposed. The method is based on combining the double-exposure schlieren method and holographic interferometry. Relations for calculating, on the basis of data obtained by analyzing double-exposure schlieren photographs, both the density at the shock wave front and the gradient of the density directly behind the front, which is necessary for calculating the shifts of the interference fringes near the shock wave front, are presented. Zh. Tekh. Fiz. 68, 88–91 (September 1998)     

Shock wave working of high-TC superconductors

Abstract

The results of investigating the processes of explosive compaction of Y-Ba-Cu-O and Bi-Sr-Ca-Cu-O powdered ceramic high temperature superconducting materials and the shock-induced variation of their properties are presented. The possibility for obtaining metal-ceramic cylinder and spiral-shaped articles is illustrated. The shock wave loading of sintered ceramics is shown to result in degrading its superconducting properties up on R(T), which are subsequently restored by low-temperature annealing. The loss of superconducting properties is demonstrated to correlate with the X-ray lines width. In case of Bi-4334 ceramic, we have observed the improving SP-properties on susceptibility just after shocking it. The effect of the compaction pressure, initial particle size, atmosphere (air, O₂, N₂), initial temperature on material properties is studied.     

Ionization effect in the front of a weak shock wave propagating in an inert gas diluted by a small amount of Mo(CO)6

The propagation of shock waves in He and Ar containing 0.01% of molybdenum hexacarbonyl Mo(CO)₆ as a heavy component of the mixture has been investigated with the use of the method of multichannel emission spectroscopy and an electrostatic probe with a spatial resolution of 0.2 mm placed in the core of a flow. The measurements have been carried out in incident shock waves with a high-vacuum shock tube in a Mach number range of 2.5–3.4. The equilibrium parameters behind the shock front are P ₂ = 0.109–1.124 atm and T ₂ = 853–1280 K, the concentration of Mo(CO)₆ is specially controlled, and high-purity He and Ar are used. The experiments are carried out under conditions when collisions between heavy molecules can be disregarded. It has been found that a narrow conduction band with a carrier density of more than 10⁵ cm^?3 appears in the shock front. The carrier density and its time characteristics have been measured. A correlation has been found between the conduction band and peaks of the nonequilibrium radiation in the visible and ultraviolet spectral ranges. This radiation disappears when the equilibrium parameters are reached behind the shock wave. The arrival of the conduction band and radiation band in the shock front at the measurement section advances the arrival of the density gradient of the shock front in most regimes. It has been found that the maximum conduction increases as the square of the Mo(CO)₆ concentration and decreases with increasing pressure. The effective threshold of the appearance of charges in the shock front has been determined as 1.35 ± 0.15 eV. A qualitative mechanism of the effect has been proposed with allowance for possible separation of charges in the shock front and with the inclusion of the “hot” wing of the energy distribution function of pair collisions.     

Influence of air pressure on the performance of plasma synthetic jet actuator

Plasma synthetic jet actuator(PSJA) has a wide application prospect in the high-speed flow control field for its high jet velocity.In this paper,the influence of the air pressure on the performance of a two-electrode PSJA is investigated by the schlieren method in a large range from 7 k Pa to 100 k Pa.The energy consumed by the PSJA is roughly the same for all the pressure levels.Traces of the precursor shock wave velocity and the jet front velocity vary a lot for different pressures.The precursor shock wave velocity first decreases gradually and then remains at 345 m/s as the air pressure increases.The peak jet front velocity always appears at the first appearance of a jet,and it decreases gradually with the increase of the air pressure.A maximum precursor shock wave velocity of 520 m/s and a maximum jet front velocity of 440 m/s are observed at the pressure of 7 k Pa.The averaged jet velocity in one period ranges from 44 m/s to 54 m/s for all air pressures,and it drops with the rising of the air pressure.High velocities of the precursor shock wave and the jet front indicate that this type of PSJA can still be used to influence the high-speed flow field at 7 k Pa.     

Model of pulsed electric discharge expansion in dense gas taking into account electron and radiative thermal conductivities. I. Expansion mechanism

Using an ionization sensor, it was found that weakly ionized plasma with an ionization degree larger than 10^?6 is formed under exposure to UV radiation of a high-current pulsed electric discharge in gas (air, nitrogen, xenon, and krypton) at atmospheric pressure at a distance of ～1.2–2.5 cm from the discharge boundary. It was shown that the structure of such discharge includes, in addition to the discharge channel, a dense shell and a shock wave, also a region of weakly ionized and excited gas before the shock wave front. The mechanism of discharge expansion in dense gas is ionization and heating of gas involved in the discharge due to absorption of the UV energy flux from the discharge channel and the flux of the thermal energy transferred from the discharge channel to the discharge shell due to electron thermal conductivity.     

Abnormal polarity effect in nanosecond-pulse breakdown of SF6 and nitrogen

The breakdown of gas gaps in an inhomogeneous electric field at subnanosecond and nanosecond voltage pulse rise times are studied, and the famous polarity effect in point-to-plane gaps is investigated. It is shown that at a voltage pulse rise time of ∼0.5 ns, the inversion of polarity effect takes place not only in electronegative gases such as SF₆, but also occurs in electropositive nitrogen. The inversion of polarity effect is related to a delay of electron emission from the plane cathode on arrival of the ionization wave front anode to the cathode. It is found that with a voltage pulse rise time of ∼0.5 ns, the inversion of polarity effect occurs at SF₆ and SF₆–N₂ pressures of 0.25 MPa and lower, and with a voltage pulse rise time of 15 ns, at a SF₆ pressure lower than 0.12 MPa.     

Intensification of shock-induced combustion by electric-discharge-excited oxygen molecules: numerical study

Mechanisms of combustion enhancement in a supersonic H₂–O₂ reactive flow behind an oblique shock wave front are investigated when vibrational and electronic states of O₂ molecule are excited by an electric discharge. The analysis is carried out on the base of updated thermally nonequilibrium kinetic model for the H₂–O₂ mixture combustion. The presence of vibrationally and electronically excited O₂ molecules in the discharge-activated oxygen flow allows to intensify the chain mechanism and to shorten significantly the induction zone length at shock-induced combustion. It makes possible, for example, to ignite the atmospheric pressure H₂–O₂ mixture at the distance shorter than 1 m behind the weak oblique shock wave at a small energy E_s = 1.2 × 10^–2 J · cm^–3 input to O₂ molecules. At higher pressure it is needed to put greater specific energy into the gas in order to ignite the mixture at appropriate distances. It is shown that excitation of O₂ molecules by electric discharge is much more effective for accelerating the hydrogen–oxygen mixture combustion than mere heating the gas.