Hydrogen analysis in metal samples by selective detection method utilizing TEA CO2 laser-induced He gas plasma

When a Transversely Excited Atmospheric (TEA) CO₂ laser (energy of 1.5 J, pulse duration of 200 ns) was focused on a metal sample surface containing hydrogen (H) in He gas at 1 atm, a strong helium gas plasma was produced and only H atoms came out of the sample. The H atoms then moved into the helium gas plasma to be excited through meta-stable helium atoms. Using this technique, an excellent linear calibration curve with zero intercept was made using zircalloy-2 samples containing H (100–600 ppm), where the compensation method was made using an emission intensity of O I 777.1 nm in order to subtract the H emission intensity coming from unwanted H₂O. It should be emphasized that this technique has a possibility to realize highly sensitive analysis of H with a detection limit of less than 1 ppm because of its selective detection.     

Review of Laser-Induced Plasma,Its Mechanism,and Application to Quantitative Analysis of Hydrogen and Deuterium

Abstract

A comprehensive review of important progress achieved over the last 30 years regarding knowledge of laser-induced plasmas generated by CO₂ and Nd:YAG lasers in a variety of ambient gases is presented in this article, as well as research results on the extension of laser-induced breakdown spectroscopy (LIBS) for quantitative analysis of light elements, especially hydrogen and deuterium. First, the formation of shock wave–induced expanding secondary plasma in low-pressure ambient gases is discussed along with the dynamic characteristics of the secondary plasma expansion process. The unique advantages of low-pressure gas plasma are explained in relation to the successful detection of the sharp H and D emission lines. The experimental results using helium ambient gas are presented with emphasis on the role of He gas plasma in introducing an additional delayed excitation mechanism involving the helium metastable excited state, which resulted in the complete resolution of H and D emission lines, separated by only 0.18 nm. The development of a laser precleaning treatment and special double-pulse techniques further produced a linear calibration line with zero intercept applicable to quantitative H and D analyses of zircaloy sample, with either low- or high-pressure ambient He gas. More recent use of a transversely excited atmospheric (TEA) CO₂ laser in place of an Nd:YAG laser has demonstrated the much desired larger excited helium plasma and thereby resulted in significant emission enhancement and improved detection sensitivity.     

Analysis of sodium aerosol using transversely excited atmospheric CO2 laser-induced gas plasma spectroscopy

Taking advantages of the special characteristics of a transversely excited atmospheric (TEA) CO₂ laser, the analysis of sodium aerosol has been successfully conducted by using laser-induced gas plasma spectroscopy (LIGPS) method. In this study, the sodium aerosol was deposited on a nickel metal plate; the metal plate functions as a subtarget to initiate a gas plasma. When a pulsed TEA CO₂ laser was focused on the metal surface, a large-volume and high-temperature gas plasma was induced. The fine particles of sodium then entered into the gas plasma region to be dissociated and excited. By using this technique, a semi quantitative analysis of sodium aerosol was made. The detection limit of sodium was approximately 200 ppb.     

Surface modification of the titanium implant using TEA CO2 laser pulses in controllable gas atmospheres - Comparative study

Interaction of a TEA CO₂ laser, operating at 10.6 μm wavelength and pulse duration of 100 ns (FWHM), with a titanium implant in various gas atmospheres was studied. The Ti implant surface modification was typically studied at the moderate laser beam energy density/fluence of 28 J/cm² in the surrounding of air, N₂, O₂ or He. The energy absorbed from the TEA CO₂ laser beam is partially converted to thermal energy, which generates a series of effects, such as melting, vaporization of the molten material, shock waves, etc. The following titanium implant surface changes and phenomena were observed, depending on the gas used: (i) creation of cone-like surface structures in the atmospheres of air, N₂ and O₂, and dominant micro-holes/pores in He ambient; (ii) hydrodynamic features, most prominent in air; (iii) formation of titanium nitride and titanium oxide layers, and (iv) occurrence of plasma in front of the implant. It can be concluded from this study that the reported laser fluence and gas ambiences can effectively be applied for enhancing the titanium implant roughness and creation of titanium oxides and nitrides on the strictly localized surface area. The appearance of plasma in front of the implants indicates relatively high temperatures created above the surface. This offers a sterilizing effect, facilitating contaminant-free conditions.     

Spectroscopic observation of the plasma produced by a CO2 laser beam interacting with titanium target under helium and/or argon atmosphere

In many laser applications such as drilling, welding and cutting, the role of the plasma in the transfer of energy between the laser beam and the metal surface appears to be rather important. It depends on several parameters such as laser wavelength, irradiation time and deposited energy but especially on the buffer gas nature. In this work the plasma is initiated by a TEA-CO₂ laser beam perpendicularly focussed onto a Ti target (100 MW/cm²), in a cell containing He, Ar or a He-Ar mixture as buffer gas. The plasma is studied by time and space resolved spectroscopic diagnostics. The results show that helium allows target erosion whereas a highly absorbing breakdown plasma develops in argon shielding the target from the subsequent laser heating. With only 20% Ar in He, a strong quenching of the He plasma by Ar occurs, and the Ar plasma effect is dominant.     

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.     

Sub-target effect in film analysis using TEA CO2 laser-induced plasma

A TEA CO₂ laser beam (500 mJ, 200 ns) was focused on film samples, under low pressure surrounding gas at around 1 Torr. It has been found that to generate the laser plasma for the sample of oil or powder, the sample should be attached in the form of thin film on the surface of a metal, such as copper plate, which acts as a sub-target. The plasma has favorable characteristics for spectrochemical analysis due to its low background and sharp line spectrum, and hence an optical multichannel analyzer (OMA) without gated function can be used for spectrum acquisition. Using the sub-target effect we have performed for analyses on water molecular layer and water impurities, where the water was condensed by heating process or electrolysis process on the sub-target so that impurities in the water were attached to the metal surface. It should be emphasized that in this case the sub-target itself has never been ablated and no any damaged on its surface. Another application of the sub-target effect is used for the analysis of oil contamination in soils. We have succeeded to detect clearly the emission line of C I 247.9 nm from the carbon as a major constituent of the oil. To derive the carbon emission intensity coming only from oil, compensation was made to cancel the contribution from other organic species using the emission of Ca, which inherently contains in other organic species in soil. As result, a good linear relationship between carbon emission intensity and oil concentration was obtained.     

A miniature tunable TEA CO<Subscript>2</Subscript> laser using isotope <Superscript>13</Superscript>C<Superscript>16</Superscript>O<Subscript>2</Subscript> and <Superscript>12</Superscript>C<Superscript>16</Superscript>O<Subscript>2</Subscript>

A miniature tunable TEA CO₂ laser using isotope ¹³C¹⁶O₂ as the active medium is developed to extend the spectral range of CO₂ lasers for further application. The optimization of the energy parameters of the tunable TEA ¹³C¹⁶O₂ laser and the same laser using ¹²C¹⁶O₂ are studied. When a gas mixture (¹³C¹⁶O₂: N₂: He = 1: 1: 3) at a total pressure of 6.4 × 10⁴ Pa is used, the TEA ¹³C¹⁶O₂ laser of a 45-cm³ active volume obtains 51 emission lines in the [00⁰1–10⁰0] and [00⁰1–02⁰0] bands. The maximum pulse energy of the TEA ¹³C¹⁶O₂ laser is about 357 mJ. The same laser using the conventional gas mixture (¹²C¹⁶O₂: N₂: He = 1: 1: 3) at a pressure of 6.66 × 10⁴ Pa is measured to obtain 69 laser emission lines and the maximum pulse energy of laser radiation is about 409 mJ.     

A compact TEA CO2 laser for field-based spectrochemical analysis of geological samples

A compact capacitor-transfer TEA CO₂ laser of 180 mJ output energy and 50 ns pulse duration in half width was designed and constructed for field use. This laser is suitable for laser microprobe spectrochemical analysis on geological and mining samples. Experiments show that the use of helium as a surrounding gas suppresses the continuous emission spectrum of the plasma, thus increasing the S/N ratio. Using glass as standard samples, the minimum detectable concentrations are estimated with Zn neutral line and F ionic line to be 60 ppm and 500 ppm, respectively.     

Production of laser-heated plasma in high- pressure Ar gas and emission characteristics of vacuum ultraviolet radiation from Ar2 excimers

A new pump scheme for the realization of a practical Ar₂ excimer laser operating at 126 nm has been proposed and investigated experimentally. In this scheme, pre-ionized high-pressure Ar gas was excited by an intense transversely-excited atmospheric (TEA) CO₂ laser irradiation. A 100-mm-long line plasma was successfully produced at an argon gas pressure of 2 MPa. The vacuum ultraviolet emission at 126 nm from the Ar₂ excimers was observed and its emission characteristics were investigated under various experimental conditions. Received: 10 December 2001 / Published online: 14 March 2002     

Short delay time UV preionized TEA CO2 laser operating with binary CO2/H2 and CO2/He gas mixtures

In order to obtain short tail-free output laser pulses from a TEA CO₂ laser, parametric study of the laser operation with CO₂/H₂ and CO₂/He binary gas mixtures containing high CO₂ concentrations was carried out. A small scale UV preionized short delay time TEA CO₂ laser was employed. In terms of the maximum extractable output pulse energy and power, the more conventional CO₂/He gas mixture was found to be inferior in comparison with the CO₂/H₂ mixture proposed here.     

Temporal extension of stable glow discharges in fluorine-based excimer laser gas mixtures by the addition of xenon

The effect of addition of xenon on the long term homogeneity of discharges in F₂and ArF excimer laser gas mixtures was investigated in a small-volume discharge chamber. The gas mixture in the discharge chamber was preionized by X-rays. A special electrical excitation circuit containing a pulse forming line provided a long, square-shaped current pumping pulse of a predetermined duration to the discharge electrodes. The initiation and the development of the discharge was monitored via its fluorescence signal with an intensified CCD camera. We found that adding Xe up to partial pressures of 0.53 mbar extended the homogeneous phase of the discharge from 80 ns to approximately 200 ns in He/F₂as well as in He/Ar/F₂and Ne/Ar/F₂excimer laser gas mixtures. Monitoring of the ArF and XeF spontaneous emission signals showed that the formation of ArF excimers remained unaffected by the addition of xenon (up to 1.3 mbar) to the laser gas mixture.     

Changes in Properties of Dielectric Barrier Discharge Plasma Jets for Different Gases and for Insulating and Conducting Transfer Plates

Dielectric barrier discharge (DBD) plasma jets have been studied extensively in recent years because of its wide range of applications. DBD plasmas can be produced using many different gases and can be applied to a broad variety of surfaces and substrates. This work provides comparisons of DBD plasmas generated using argon (Ar), helium (He), and nitrogen (N₂), as well as their mixtures with water vapor in order to know how some plasma properties are affected by the use of different gases. All plasmas were studied in two different conditions: using a transfer plate made of a conductive material and using a transfer plate made of an insulating one. It was observed that the process of Penning ionization of nitrogen molecules by direct collisions with metastable atoms and molecules is evident and significant only in plasmas that use He as the working gas, which means that He atoms in metastable states have greater ability to transfer energy to molecules of nitrogen in the plasma. The collisions of metastable He with N₂ molecules determine the vibrational temperature (T _vib) values in He plasmas, while in Ar and N₂ plasmas, the T _vib values are determined mainly by collisions of electrons with N₂ molecules. It was noticed that the use of an insulating or a conducting transfer plate as the sample holder affects the results of adhesion between poly(dimethylsiloxane) samples, and it is mainly due to the differences in the plasma power, with a higher plasma power leading to better adhesion.     

Parametric studies on generation of short CO2 laser pulses for IR-laser chemistry

Results of parametric studies on short CO₂ laser pulse generation by laser induced dielectric breakdown in a plasma shutter cell are described. From the rise time of such short pulses obtained, threshold breakdown intensity (I_th) has been estimated for different gases. The technique is further extended to obtain 40 ns pulses on two-frequency emission from a single TEA CO₂ laser. Pressure dependent studies of I_th are utilised to model the process of such laser induced plasma.     

H2， He混合稀释生长微晶硅锗薄膜

采用H₂,He混合气体稀释等离子辅助反应热化学气相沉积法生长微晶硅锗薄膜,并在生长过程中对等离子体进行光发射光谱在线监测.结果表明：混合气体稀释法可以有效提高等离子体中的原子氢数目,降低等离子体中的电子温度;用XRD和光暗电导率表征样品的微结构和光电特性时发现,通过优化混合稀释气体中He和H₂气体的比例,能够减少薄膜中的缺陷态,促进薄膜<220>择优取向生长,有效改善微晶硅锗薄膜结构,提高光电吸收性能. 关键词： 化学气相沉积 微晶硅锗薄膜 光发射光谱 X射线衍射     

Surface modifications of TiN coating by pulsed TEA CO2 and XeCl lasers

Interactions of a transversely excited atmospheric (TEA) CO₂ laser and an excimer XeCl laser, pulse durations ∼2 μs (initial spike FWHM ∼100 ns) and ∼20 ns (FWHM), respectively, with polycrystalline titanium nitride (TiN) coating deposited on high quality steel AISI 316, were studied. Titanium nitride was surface modified by the laser beams, with an energy density of 20.0 J/cm² (TEA CO₂ laser) and 2.4 J/cm² (XeCl laser), respectively. The energy absorbed from the CO₂ laser beam is partially converted to thermal energy, which generates a series of effects such as melting, vaporization of the molten material, shock waves, etc. The energy from the excimer XeCl laser primarily leads to fast and intense target evaporation. The calculated maximum temperatures on the target surface were 3770 and 6300 K for the TEA CO₂ and XeCl lasers, respectively. It is assumed that the TEA CO₂ laser affects the target deeper, for a longer time than the XeCl laser. The effects of the XeCl laser are confined to a localized area, near target surface, within a short time period.Morphological modifications of the titanium nitride surface can be summarized as follows: (i) both lasers produced ablation of the TiN coating in the central zone of the irradiated area and creation of grainy structure with near homogeneous distribution; (ii) a hydrodynamic feature, like resolidified droplets of the material, appeared in the surrounding peripheral zone; (iii) the process of irradiation, in both cases, was accompanied by appearance of plasma in front of the target.Target color modifications upon laser irradiation indicate possible chemical changes, possibly oxidation.     

Laser induced breakdown spectroscopy of germane plasma induced by IR CO2 pulsed laser

Laser-induced breakdown spectroscopy (LIBS) in germane (GeH₄), initially at room temperature and pressures ranging from 2 to 10 kPa, was studied using a high-power transverse excitation atmospheric (TEA) CO₂ laser (λ=10.653 μm, τ _FWHM=64 ns and power densities ranging from 0.28 to 5.52 GW cm⁻²). The strong emission spectrum of the generated plasma is mainly due to electronic relaxation of excited Ge, H and ionic fragments Ge⁺, Ge²⁺ and Ge³⁺. The weak emission is due to molecular bands of H₂. Excitation temperatures of 8100±300 K and 23,500±2500 K were estimated by Ge atomic and Ge⁺ singly ionized lines, respectively. Electron number densities of the order of (0.7–6.2)×10¹⁷ cm⁻³ were deduced from the Stark broadening of several atomic Ge lines. The characteristics of the spectral emission intensities from different species have been investigated as functions of the germane pressure and laser irradiance. Optical breakdown threshold intensities in germane at 10.653 μm have been determined. The mechanism of initiation of the laser-induced plasma in germane has been analyzed.     

Excitation of iron atoms in a plasma of excimer emitters under transverse-discharge pumping

The optical characteristics of a transverse-discharge plasma initiated in He/Xe(Kr)/HCl(CF₂Cl₂) mixtures were studied. The mixtures contained a small amount of iron vapor due to metal cathode erosion. The iron atoms were shown to be excited by the spontaneous emission of KrCl (λ=22 nm) and XeCl (λ=308 nm) molecules in a nanosecond transverse discharge.     

Saturation spectroscopy of hydrogen 1-011-011-01lines with a multi-mode cw dye laser

With an intense, broadband multi-mode cw dye laser collisional studies of H_α fine-structure resonances with saturated absorption are extended to He buffer gas pressures larger than 30 mbar (0°C). The broadening and shift of the two prominent H_α(2P?3D) transitions are measured in a (He+4% H) gas discharge. The absolute magnitude and the differences in the width of the lines are explained theoretically by different inelastic fine-structure transfer cross sections which can also be deduced from the pressure effect data. Nuclear polarization of hydrogen atoms by H_α optical pumping and polarization transfer to the H(1S) ground state via Ly-α decay and further applications of the multimode laser are discussed.     

Ab initio study of H and He migrations in β-phase Sc, Y, and Er hydrides

Ab initio calculations based on the density functional theory have been performed to investigate the migrations of hydrogen(H) and helium(He) atoms in β-phase scandium(Sc),yttrium(Y),and erbium(Er) hydrides with three different ratios of H to metal.The results show that the migration mechanisms of H and He atoms mainly depend on the crystal structures of hydrides,but their energy barriers are affected by the host-lattice in metal hydrides.The formation energies of octahedral-occupancy H(H oct) and tetrahedral vacancy(V tet) pairs are almost the same(about 1.2 eV).It is of interest to note that the migration barriers of H increase with increasing host-lattice atomic number.In addition,the results show that the favorable migration mechanism of He depends slightly on the V tet in the Sc hydride,but strongly on that in the Y and Er hydrides,which may account for different behaviours of initial He release from ScT2 and ErT2.