High-pressure Argon Research Articles

Properties of a continuous optical discharge sustained by short-wave infrared laser radiation in high pressure argon

Abstract The paper is devoted to the experimental study of the characteristics of continuous optical discharge (COD) sustained by high power continuous wave laser radiation at a wavelength λ = 1.08 μm in high pressure argon. New data on COD threshold laser power dependence on argon pressure in the range 20-50 bar are obtained. COD threshold laser power is shown to be in good agreement with the data obtained by other authors and theoretical evaluations provided the contribution of plasma energy loss due thermal radiation is taken into account properly. A study of the convective plume oscillations around COD in argon has been carried out. It was found that in a pressure range 25-35 bar the growth of the laser radiation power leads to a decrease in convection oscillation frequency from 33 to 29 Hz, while the radius of the convective plume grows accordingly. The oscillation frequency ν and characteristic radius of the convective plume r0 were found to obey the similarity relation previously established in experiments with COD in xenon.

Characterizing and visualizing the direct injection of hydrogen into high-pressure argon and nitrogen environments

Using argon as the working fluid in an internal combustion engine holds the potential of substantially enhancing thermal efficiency because of its high specific heat ratio. Burning hydrogen, not with air but with pure oxygen, in a closed-loop argon power cycle would lead to an emission-free exhaust composition, effectively containing only water and argon, which can be separated by condensation. One of the current challenges is the high-pressure direct injection of both fuel and oxidizer, which directly controls the combustion process. To support the development of such an injection strategy, high-pressure injections of hydrogen into pressurized argon and nitrogen are investigated using high-speed Schlieren and pressure transducers in a non-heated constant-volume chamber at varying conditions. In this work it is shown that hydrogen mass flow increases linearly with injection pressure and that it is unaffected by chamber pressure as expected based on choked flow theory, while jet penetration and cone angle are determined by the pressure ratio between the fuel line and the ambient. A correlation is presented between jet penetration and pressure ratio for argon or nitrogen environments at room temperature.

Control of growth kinetics during remote epitaxy of complex oxides on graphene by pulsed laser deposition

Remote epitaxy through 2D materials opens new opportunities for research and application, overcoming some limitations of classical epitaxy and allowing the creation of freestanding layers. However, using graphene as a 2D interlayer for remote epitaxy of metal oxides is challenging, particularly when carried out by pulsed laser deposition (PLD). The graphene layer can be easily oxidized under the typically applied high oxygen pressures, and the impact of highly kinetic particles of the plasma plume can lead to severe damages. In this study, both aspects are addressed: Argon is introduced as an inert background gas in order to avoid oxidation and to reduce the kinetic impact of the plasma species on graphene. The laser spot size is minimized to control the plasma plume and particle flux. As a model system, strontium titanate (STO) is quasi-homoepitaxially grown on graphene buffered STO single crystals. Raman spectroscopy is performed to evaluate the 2D, G, and D band fingerprints of the graphene layer and to assess the defect structure of the interlayer after the deposition. Our results prove that control of the growth kinetics by reducing the laser spot size and by using high argon pressures provides a key strategy to conserve graphene with a low defect density during PLD while allowing a layer-by-layer growth of structurally coherent oxide layers. This strategy may be generalized for the PLD remote epitaxy of many complex oxides, opening the way for integrating 2D materials with complex oxides using widely accessible PLD processes.

Spectroscopic detection of the gallium methylene (GaCH2 and GaCD2) free radical in the gas phase by laser-induced fluorescence and emission spectroscopy.

GaCH2, a free radical thought to play a role in the chemical vapor deposition of gallium-containing thin films and semiconductors, has been spectroscopically detected for the first time. The radical was produced in a pulsed discharge jet using a precursor mixture of trimethylgallium vapor in high pressure argon and studied by laser-induced fluorescence and wavelength resolved emission techniques. Partially rotationally resolved spectra of the hydrogenated and deuterated species were obtained, and they exhibit the nuclear statistical weight variations and subband structure expected for a 2A2-2B1 electronic transition. The measured spectroscopic quantities have been compared to our own abinitio calculations of the ground and excited state properties. The electronic spectrum of gallium methylene is similar to the corresponding spectrum of the aluminum methylene radical, which we reported in 2022.

Source rock and reservoir qualities of middle Jurassic Lianggaoshan lacustrine shale at fuxing area, Sichuan Basin: Implication for shale-oil enrichment

The shale oil exploration, in the Middle Jurassic Lianggaoshan Formation in the Fuxing area of Sichuan Basin, is in preliminary stage, requiring further in-depth study on shale oil and gas enrichment conditions. The lithological, organic geochemical, and reservoir characteristics of the Lianggaoshan Formation shale were analyzed using a suite of tests, including common thin section observation, organic carbon determination, pyrolysis experiment, combined N 2 -high pressure mercury test and argon ion polishing-scanning electron microscope, to elucidate source rock and reservoir qualities and their variation in vertical. Results suggest that the medium-carbon argillaceous shale, medium-carbon shell calcareous-argillaceous shale, and low-carbon argillaceous shale facies were mainly developed in Member 1 and Member 2 of the Lianggaoshan Formation. The medium-carbon argillaceous shale facies in the sub-layer ④ was rich in organic matter, with abundant sapropel, chitinous and secondary organic components, which were considered as a set of medium-quality source rocks. The medium-carbon shell calcareous-argillaceous shale and low-carbon argillaceous shale in the sub-layers ② and ③ have relatively low organic matter abundance, with vitrinite and inertinite as major organic microscopic components, revealing poor hydrocarbon generation potential. The porosity of shale reservoirs in sub-layers ②‒④ was higher than 3.0%, with predominant mesopores, followed by macropores, consisting of mainly clay mineral pores, organic pores, and microfractures related to organic matter. The medium-carbon argillaceous shale facies at the Lianggaoshan Formation is high-quality source rocks and reservoirs and is thus a potential target for lacustrine shale oil exploration in the Fuxing area of the Sichuan Basin. • The medium carbon clayey shale, medium carbon shell calcareous-clayey shale, and low carbon clayey shale were mainly developed in Member 1 and Member 2 of the Lianggaoshan Formation. • The medium carbon clayey shale facies in the sub-layer ④ exhibits adequate potential as hydrocarbon source rock and reservoir. • Sub-layer ④ is thus a potential target for continental shale oil exploration in the Fuxing area of the Sichuan Basin.

Spectroscopic detection of the stannylidene (H2C=Sn and D2C=Sn) molecule in the gas phase.

The H2CSn and D2CSn molecules have been detected for the first time by laser-induced fluorescence (LIF) and emission spectroscopic techniques through the B̃1B2-X̃1A1 electronic transition in the 425-400nm region. These reactive species were prepared in a pulsed electric discharge jet using (CH3)4Sn or (CD3)4Sn diluted in high-pressure argon. Transitions to the electronic excited state of the jet-cooled molecules were probed with LIF, and the ground state and low-lying Ã1A2 state energy levels were measured from single vibronic level emission spectra. We supported the experimental studies by a variety of ab initio calculations that predicted the energies, geometries, and vibrational frequencies of the ground and lower excited electronic states. The spectroscopy of stannylidene (H2CSn) is in many aspects similar to that of silylidene (H2CSi) and germylidene (H2CGe).

Fractal Analysis and Classification of Pore Structures of High-Rank Coal in Qinshui Basin, China

The influence of high-rank coal’s pore characteristics on the physical properties, gas-bearing properties, and exploitation of coal reservoirs is becoming more and more prominent. How to establish the classification to describe the pore networks combining quantitative and qualitative characteristics has emerged as a major problem, which may offer a scientific foundation to deepen the understanding of this issue. In this research, the structure and fractal characteristics of reservoir pores were determined after analyzing 20 high-rank coal samples from Xinjing Coal Mine in the Qinshui Basin with the application of the high-pressure mercury intrusion method (HPMI) and argon ion polishing–field emission scanning electron microscopy (AIP–FESEM). The results show that the tested coal samples were bipolar distributed, with transitional pores and micropores dominating the pore volume, followed by macropores. The Menger sponge fractal models manifested two or three distinct straight-line segments with demarcation points of 65 nm and 1000 nm. A natural classification with three major pore types of diffusion pores (D-pores), seepage pores (S-pores), and pico pores (P-pores), demarcated by pore size intervals of 65 nm and 1 nm and seven sub-types, was established to relate pores to pore networks based on these fractal characteristics and the kinetic characteristics of methane molecules. This classification scheme can characterize the relationship between pore types and the corresponding major occurrence and transport mechanisms of the gas. In addition, P-pores and D-pores are predominately nanoscale OM pores with three major genetic types of organic constituent interparticle pores (5–200 nm), metamorphic pores (<5 nm), and intermorphic pores (<5 nm). S-pores are more complex in origin and shape features, and the major types include outgas pores, plant tissue residual pores, mineral-related pores, and microfractures. The mean radius (Pa), total pore volume (Vt), apparent porosity (Φ), and volume ratio of macro- and mesopores were positively correlated with the fractal dimension D1 of S-pores (>65 nm). Since fractal analysis is a more comprehensive characterization of reservoir structure and quantitatively reflects the pore structure, undulating state, and roughness of the inner surface, fractal parameters can be used as an important index to describe the pore structure characteristics of high-rank coal reservoirs.

Influence of unipolar pulse time offset between Ti and Zr dual cathodes in closed magnetic field high power impulse magnetron sputtering

Titanium/zirconium dual cathodes with a closed magnetic field configuration were used in unipolar high power impulse magnetron sputtering (HiPIMS). Different pulse width (pulse on time) and pulse time offset between the negative voltage pulses of two targets were applied. The target discharge current waveforms and consequent substrate current waveforms were recorded and compared. The results show that both ion fluxes emitted from the Ti and Zr cathodes increase with the argon pressure. However, the ion flux emitted from the Zr cathode increases more substantially at high argon pressure. The closed magnetic field raises the target discharge current and ion flux to the substrate when the pulses of the two targets are simultaneous synchronized, or followed closely. The TiZr film composition is influenced by the HiPIMS discharge behavior of each target material more than by the average power ratio of each target. For low working pressure and short pulse width, simultaneous synchronization of the pulses on the two targets might effectively use the electrons drifting between the dual targets to enhance the generation of ions from both targets. For high working pressure and long target pulse width, setting pulses on two targets following closely is recommended to additionally utilize the runaway ions as pre-ionized media for the follow-up pulse on the adjacent target.

Preservation of high-pressure volatiles in nanostructured diamond capsules.

High pressure induces dramatic changes and novel phenomena in condensed volatiles1,2 that are usually not preserved after recovery from pressure vessels. Here we report a process that pressurizes volatiles into nanopores of type 1 glassy carbon precursors, converts glassy carbon into nanocrystalline diamond by heating and synthesizes free-standing nanostructured diamond capsules (NDCs) capable of permanently preserving volatiles at high pressures, even after release back to ambient conditions for various vacuum-based diagnostic probes including electron microscopy. As a demonstration, we perform a comprehensive study of a high-pressure argon sample preserved in NDCs. Synchrotron X-ray diffraction and high-resolution transmission electron microscopy show nanometre-sized argon crystals at around 22.0 gigapascals embedded in nanocrystalline diamond, energy-dispersive X‑ray spectroscopy provides quantitative compositional analysis and electron energy-loss spectroscopy details the chemical bonding nature of high-pressure argon. The preserved pressure of the argon sample inside NDCs can be tuned by controlling NDC synthesis pressure. To test the general applicability of the NDC process, we show that high-pressure neon can also be trapped in NDCs and that type 2 glassy carbon can be used as the precursor container material. Further experiments on other volatiles and carbon allotropes open the possibility of bringing high-pressure explorations on a par with mainstream condensed-matter investigations and applications.

Spectroscopic identification and characterization of the aluminum methylene (AlCH2) free radical.

The AlCH2 free radical has been spectroscopically identified for the first time. This highly reactive species was produced in an electric discharge jet using trimethylaluminum vapor in high pressure argon as the precursor. The laser-induced fluorescence spectrum of the B̃2A2-X̃2B1 band system in the 513-483nm region was recorded, and the 0-0 bands of AlCH2 and AlCD2 were studied at high resolution. The fine structure splittings were found to be due primarily to the Fermi contact interaction in the excited state rather than the usual spin-rotation coupling. Rotational analysis gave the molecular constants of the combining states, and the geometries were obtained as r″A1-C=1.9591A◦,r″C-H=1.1061A◦,θHCH ″=110.41◦ and r'A1-C=1.9431A◦,r'C-H=1.0911A◦,θHCH '=115.41◦. The bond lengths correspond to an aluminum-carbon single bond in both states.

Barely fluorescent molecules. I. Twin-discharge jet laser-induced fluorescence spectroscopy of HSnCl and DSnCl.

The divalent tin transient molecules HSnCl and DSnCl have been detected for the first time by laser-induced fluorescence (LIF) spectroscopy. HSnCl/DSnCl were produced in a twin-discharge jet using separate precursor streams of SnH4/SnD4 and the discharge products from HCl/DCl, both diluted in high pressure argon. The Ã1A″-X̃1A' spectrum of HSnCl consists of a single vibronic 00 0 band with a very short fluorescence lifetime (∼30ns). In contrast, the LIF spectrum of DSnCl exhibits three bands (00 0,20 1,and20 2), whose fluorescence lifetimes decrease from 393ns (00) to less than 10ns (22). Single vibronic level emission spectra have been recorded, providing information on all three vibrational modes in the ground state. Previous detailed ab initio studies indicate that these molecules dissociate into SnCl + H on the excited state potential surface and this is the cause of the short fluorescence lifetimes and breaking off of the fluorescence. It is fortunate that the HSnCl excited state zero-point level is still fluorescent or it would not be detectable by LIF spectroscopy.

Barely fluorescent molecules. II. Twin-discharge jet laser-induced fluorescence spectroscopy of HSnBr and DSnBr.

HSnBr and DSnBr have been detected for the first time by a combination of laser-induced fluorescence (LIF), fluorescence hole-burning, and wavelength resolved emission spectroscopies. The transient molecules were produced in a twin-discharge jet using separate precursor streams of SnH4/SnD4 and HBr/DBr, both diluted in high pressure argon. The Ã1A″-X̃1A' spectrum of HSnBr only consists of the 00 0 and 20 1 cold bands that show clearly resolved subband structure with fluorescence lifetimes varying from 526 to 162ns. The DSnBr LIF spectrum exhibits four bands (00 0, 20 1, 20 2, and 10 1) whose fluorescence lifetimes decrease from 525ns (00) to 175ns (11). Single vibronic level emission spectra have provided extensive information on the ground state vibrations, including all the anharmonicities and the harmonic frequencies. Fluorescence hole-burning experiments have shown that a few higher HSnBr nonfluorescent levels are very short-lived but still detectable. The ab initio studies of Tarroni and Clouthier [J. Chem. Phys. 156, 064304 (2022)] show that these molecules dissociate into SnBr + H on the excited state potential surface and this is the cause of the short fluorescence lifetimes and breaking off of the LIF spectra. HSnBr is a barely fluorescent molecule in the sense that only vibrational levels less than or equal to 317cm-1 in the excited state emit detectable photons down to the ground state.

Control of the excited-to-ionized atoms ratio in a dense gas in the wake of an intense femtosecond laser pulse.

We demonstrate the sensitivity of the plasma composition in the filament wake channel in a dense gas to the temporal shape of the driving femtosecond laser pulse. During the pulse, the electrons released via strong-field ionization and driven by oscillating laser field are actively engaged in collisional processes with neutral neighbor atoms, including inverse Bremsstrahlung, impact ionization, and collisional excitation. By the end of the pulse, these collisional processes produce considerable numbers of additional free electrons (or ionized atoms) and excited atoms, and these contents of the filament wake channel determine its subsequent evolution dynamics. Addressing the case of high-pressure argon gas and using a kinetic model of these competing collisional processes, we explore the sensitivity of the resulting excited-to-ionized atoms number density ratio to the envelope shape of the driving laser pulse. By considering several families of pulses, we show that asymmetric pulse envelopes skewed toward the earlier time allow for efficient control of the ratio of excited atoms to ionized atoms. The pulse-shape control of the plasma composition in the immediate wake of the laser pulse projects into control of the wake channel evolution and of the associated transient electronic and optical nonlinearities.

Comparative study of the effects of high hydrostatic pressure per se and high argon pressure on urate oxidase ligand stabilization.

The stability of the tetrameric enzyme urate oxidase in complex with excess of 8-azaxanthine was investigated either under high hydrostatic pressure per se or under a high pressure of argon. The active site is located at the interface of two subunits, and the catalytic activity is directly related to the integrity of the tetramer. This study demonstrates that applying pressure to a protein-ligand complex drives the thermodynamic equilibrium towards ligand saturation of the complex, revealing a new binding site. A transient dimeric intermediate that occurs during the pressure-induced dissociation process was characterized under argon pressure and excited substates of the enzyme that occur during the catalytic cycle can be trapped by pressure. Comparison of the different structures under pressure infers an allosteric role of the internal hydrophobic cavity in which argon is bound, since this cavity provides the necessary flexibility for the active site to function.

Analyses on the nonequilibrium transport processes in a free-burning argon arc plasma under different operating conditions

During discharges of an arc plasma, complex mass, momentum and energy exchanges exist between the arc column and the surrounding cold gas, forming a nonequilibrium region deviating from both the local thermodynamic equilibrium and local chemical equilibrium states. The nonequilibrium synergistic transport plays a crucial role not only in controlling the characteristics of the arc plasmas theoretically, but also in optimizing the plasma material processing qualities in actual applications. In this paper, the nonequilibrium transport processes in free-burning argon arc plasmas under different operating pressures and arc currents are studied based on a complete nonequilibrium fluid model, and are also validated by comparing with measured data. The energy transfer processes under various operating conditions, especially Joule heating, elastic and inelastic collisions, conductive and convective heat transfer, and energy transfer related to the temperature ratio spatial gradient, are analyzed based on the concept of the ‘energy tree.’ The revealed major energy transfer channels in the high-pressure argon arc plasmas also provide some possibilities to control the characteristics of thermal plasmas in the future.

Formation and evolution of striation plasma in high-pressure argon glow discharge

The self-organized striation phenomenon in the positive column region of glow discharge plasma is a basic problem in gas discharge physics, which involves rich physics such as electron dynamics, transport process, discharge instability and nonlinear phenomenon. It is an important topic in basic physics and practical application. In this work an argon glow discharge striation plasma at high pressure is reported. The electrical, optical and ionization wave propagation characteristics of the striation plasma, and the evolution of the striation plasma with pressure and impurity gas are investigated experimentally. The generation and quenching mechanism of argon striation plasma are analyzed. The results show that the striation length is about 1.5 mm, and decreases with pressure increasing, and the velocity and frequency of the ionization wave are estimated at 1.87 m/s and 1.25 kHz, respectively. The measurement of optical emission spectrum shows that the generation of striation plasma is probably related to the argon metastable atoms. The stepwise ionization process caused by metastable atoms triggers off an ionization instability. The instability propagates in the form of ionization wave, which leads the plasma parameters to be modulated longitudinally, thus, forming an alternating bright and dark striation plasma. The adding of nitrogen can effectively quench metastable argon atoms and change the electron energy distribution function, which destroys the instability conditions of the plasma, therefore, the striation plasma disappears. This work provides a new insight into the understanding of the formation and annihilation mechanism of glow discharge striation plasma at high pressure.

Hysteresis control using a DC magnetic field in an argon inductively coupled plasma

Control of the hysteresis phenomenon in a high-pressure (250 mTorr) argon inductively coupled plasma was experimentally investigated by applying a DC magnetic field. Electron energy probability functions (EEPFs) were measured with and without DC magnetic fields to obtain electron densities. Without the magnetic field, a hysteresis loop is clearly observed during the E and H mode transitions, but surprisingly, when 20 G of DC magnetic field is applied, the hysteresis loop gets smaller, and it vanishes completely when the applied DC magnetic field is increased to over 40 G. Measured EEPFs show that there is a significant evolution of the EEPFs by DC magnetic field. The EEPF without magnetic field is a Druyvesteyn distribution, but evolves to a Maxwellian-like distribution under a strong DC magnetic field condition. This evolution of the EEPF causes significant reduction in the collisional energy loss εc in E-mode. The evolution of EEPFs is explained by a decrease in Ohmic power absorption of low-energy electrons and an increase in electron–electron collisions, and the vanishing of the hysteresis is explained by the suppression of nonlinear changes in EEPF and nonlinear changes in collisional energy loss.

Pore structural characteristics and methane adsorption capacity of transitional shale of different depositional and burial processes: a case study of shale from Taiyuan formation of the Southern North China basin

Pore structural characteristics and methane adsorption capacity are two significant aspects affecting shale gas potential, but the impact of deposition and burial processes on these two aspects is not clear. Hence, the shale samples of Taiyuan Formation deposited continuously and experienced multi-stage tectonic uplift in Fuyang-Bozhou area of Southern North China Basin were collected in this study. Based on the total organic carbon content analysis, mineral composition determination, low-pressure CO2 and N2 adsorption, high-pressure methane adsorption and argon ion polishing-field emission scanning electron microscope observation. The impact of depositional and burial processes variation on shale reservoir physical properties and adsorption performance is studied. The results display that the pore types of shale samples which were continues deposited and experienced multi-stage tectonic uplift have no obvious differences, while the pore volume as well as specific surface area (SSA) of micropores and mesopores of shale samples under multi-stage tectonic uplift are larger significantly. Meanwhile, the roughness of shale pores increases also. The decrease of loading pressure caused by multi-stage tectonic uplift may be the main factor for the pore structure changes of shale sample. Compared with the continuous deposited samples, the shale samples under multi-stage tectonic uplift have stronger methane adsorption capacity, which is relevant to the greater SSA of micropores as well as mesopores. This study provides an example and new revelation for the influence of depositional and burial processes on shale pore structure and methane adsorption capacity.

Diagnostics of a high-pressure DC magnetron argon discharge with an aluminium cathode

In this article, the plasma parameters of a direct current magnetron discharge in argon at moderate pressure (10 to 40 Pa) using an aluminium cathode are explored. The density of argon excited states, the sputtered aluminium atom density and the electron temperature are estimated using a collisional–radiative model. The electron temperature obtained using optical emission spectroscopic data agrees well with measurements taken using a Langmuir probe. The influence of the discharge parameters, namely the background argon pressure and the discharge current, are discussed.

Pulsed Discharge Plasma in High-Pressure Environment for Water Pollutant Degradation and Nanoparticle Synthesis

The application of high-voltage discharge plasma for water pollutant decomposition and the synthesis of nanoparticles under a high-pressure argon gas environment (~4 MPa) was demonstrated. The experiments were carried out in a batch-type system at room temperature with a pulsed DC power supply (15.4 to 18.6 kV) as a discharge plasma source. The results showed that the electrode materials, the pulsed repetition rates, the applied number of pulses, and the applied voltages had a significant effect on the degradation reactions of organic compounds. Furthermore, carbon solid materials from glycine decomposition were generated during the high-voltage discharge plasma treatment under high-pressure conditions, while Raman spectra and the HRTEM images indicated that titanium dioxide with a brookite structure and titanium carbide nanoparticles were also formed under these conditions. It was concluded that this process is applicable in practice and may lead to advanced organic compound decomposition and metal-based nanoparticle synthesis technologies.