Chemical Scheme Research Articles

Laminar flame speed evaluation for CH4/O2 mixtures at high pressure and temperature for rocket engine applications

Pure methane-oxygen mixtures in liquid rocket engines lead to extreme pressure and temperature conditions that are prohibitive for most of the experimental setups. Hence, there is very little data on such flames in the literature, especially concerning the laminar flame speed Su, often limited at atmospheric pressure. The recent development of methalox rocket engines, which design process often requires CFD calculations, brings this lack of data to the forefront. Indeed, the CFD simulations require valid chemical schemes in the real operating conditions. To address this problem, flame measurements have been performed in a special isochoric combustion chamber with full optical access (OPTIPRIME) developed at ICARE. An extensive database in conditions never tested before is generated for several equivalence ratios, temperature and pressure ranges. Multiple chemical mechanisms were then compared to those results, showing various levels of agreement. Hence, the best mechanism from the literature on OPTIPRIME results and other literature experimental data was selected. A sensitivity analysis was performed to identify key chemical reactions controlling the flame speed. These key reactions could later be tuned by an optimization process to perfectly match the experimental results. Finally, additional measurements were performed in order to develop a Su=f(P,T) correlation to build a future flame speed database under rocket engines relevant conditions.

A photochemical model of Triton’s atmosphere paired with an uncertainty propagation study

Context. The largest satellite of Neptune, Triton, is a likely Kuiper Belt object captured by the planet. It has a tenuous nitrogen atmosphere, similar to that of Pluto, and it may be an ocean world. The Neptunian system has only been visited once: by Voyager 2 in 1989. Over the past few years, the demand for a new mission to the ice giants and their systems has risen. Thus, a theoretical basis upon which to prepare for such a mission is needed. Aims. We aim to develop a photochemical model of Triton’s atmosphere with an up-to-date chemical scheme, as previous photochemical models date back to the post-flyby years. This purpose is to achieve a better understanding of the mechanisms governing Triton’s atmospheric chemistry and to highlight the critical parameters that have a significant impact on the atmospheric composition. We also study the model uncertainties to find what chemical studies are necessary to improve the modeling of Triton’s atmosphere. Methods. We used a model of Titan’s atmosphere and tailored it to Triton’s conditions. We first used Titan’s chemical scheme before updating it to better model Triton’s atmospheric conditions. Once the nominal results were obtained, we studied the model uncertainties with a Monte Carlo procedure, considering the reaction rates as random variables. Finally, we performed global sensitivity analyses to identify the reactions responsible for model uncertainties. Results. With the nominal results, we determined the composition of Triton’s atmosphere and studied the production and loss processes for the main atmospheric species. We highlighted key chemical reactions that are most important for the overall chemistry. We also identified some key parameters that have a significant impact on the results. The uncertainties are high for most of the main atmospheric species since the atmospheric temperature is very low. We identified key uncertainty reactions that have the greatest impact on the result uncertainties. These reactions must be studied as a priority in order to improve the significance of our results by finding ways of lowering these uncertainties.

Paleo-environmental study of the Raniganj and Barakar Formations: Implications from the Geochemical and Geomechanical Aspects of Sandstone and Shale

ABSTRACT The study considers the impact of the degree of weathered material constituting the sedimentary rocks on the strength of the Lower Gondwana coal measure rocks. The dependence of the strength of primary rocks on the alteration indices has been previously studied, but it is unknown for secondary/ sedimentary rocks. Therefore, in this paper, Lower Gondwana coal measure rocks (sandstone and shale) from the most productive coalfields of India, the Barakar and Raniganj coalfields, have been studied geochemically and geomechanically to find out their correlation. Geochemically, the study revealed that an arid, non-marine, and deltaic depositional environment prevailed during the sedimentation of Barakar and Raniganj Formations. The provenance was deduced to be mafic igneous. It was also deduced that the Lower Gondwana sandstone is clay-rich, and the sandstone samples fall in the shale field in the chemical classification scheme for terrigenous clastic sediments. The weathering indices, along with the uniaxial compressive strength (UCS) of the Barakar and Raniganj Formation coal measure rocks, have been assessed. The dependence of UCS on the weathering indices has been evaluated, and positive relationships were obtained.

CFD analysis of the downdraft gasifier using species-transport and discrete phase model

In the present study, a 2-D axisymmetric steady-state computational fluid dynamics (CFD) model has been developed for biomass gasification in a fixed bed Imbert downdraft gasifier. A discrete phase model (DPM) based on the Euler-Lagrangian approach with species transport is applied to the gasifier having the capacity of ≈ 5 kW. The use of DPM for the particle-continuous phase interaction leads to capture more realistic gasification phenomena. The proposed model is an effort to carry forward the CFD technique by implementing an alternative chemical kinetic scheme to study the various gasification parameters. The model is validated at different values of equivalence ratios (0.19–0.33) for producer gas composition and found to be in better agreement with the experimental values reported in the literature. The standard estimated error for the present model is 6.64, 7.55, 2.92, and 5.28 % for carbon monoxide, hydrogen, methane, and carbon dioxide, respectively. Moreover, the calculated standard deviation is 0.44 only. The biomass feed and airflow rates vary from 3.43 to 5.82 kg/h and 2.41–8.02 Nm3/h, respectively. It has been found that an equivalence ratio in the range of 0.25 to 0.30 is the most appropriate condition in the present operating range of the gasifier. The proposed scheme allows accurate prediction under various operating conditions, which may enable the designer to optimise the operating conditions. The model predictions would help to design the process integration of gasification with any existing commercial energy-producing unit based on conventional fuels. Hence, it deliberates significant contribution and value addition in the current literature for the CFD modelling of biomass gasification. The present study not only helps to improve the overall performance of the gasifier but also provides the profiles of essential design variables across the length of the gasifier.

Impacts of Heterogeneous Chemistry on Vertical Profiles of Martian Ozone.

We show a positive vertical correlation between ozone and water ice using a vertical cross-correlation analysis with observations from the ExoMars Trace Gas Orbiter's Nadir and Occultation for Mars Discovery instrument. This is particularly apparent during L S=0°-180°, Mars Year 35 at high southern latitudes, when the water vapor abundance is low. Ozone and water vapor are anti-correlated on Mars; Clancy etal. (2016, https://doi.org/10.1016/j.icarus.2015.11.016) also discuss the anti-correlation between ozone and water ice. However, our simulations with gas-phase-only chemistry using a 1-D model show that ozone concentration is not influenced by water ice. Heterogeneous chemistry has been proposed as a mechanism to explain the underprediction of ozone in global climate models (GCMs) through the removal of HO x . We find improving the heterogeneous chemical scheme by creating a separate tracer for the HO x adsorbed state, causes ozone abundance to increase when water ice is present (30-50km), better matching observed trends. When water vapor abundance is high, there is no consistent vertical correlation between observed ozone and water ice and, in simulated scenarios, the heterogeneous chemistry has a minor influence on ozone. HO x , which are by-products of water vapor, dominate ozone abundance, masking the effects of heterogeneous chemistry on ozone, and making adsorption of HO x have a negligible impact on ozone. This is consistent with gas-phase-only modeled ozone, showing good agreement with observations when water vapor is abundant. Overall, the inclusion of heterogeneous chemistry improves the ozone vertical structure in regions of low water vapor abundance, which may partially explain GCM ozone deficits.

Yields of HONO2 and HOONO Products from the Reaction of HO2 and NO Using Pulsed Laser Photolysis and Mid-Infrared Cavity-Ringdown Spectroscopy.

The reaction of HO2 with NO is one of the most important steps in radical cycling throughout the stratosphere and troposphere. Previous literature experimental work revealed a small yield of nitric acid (HONO2) directly from HO2 + NO. Atmospheric models previously treated HO2 + NO as radical recycling, but inclusion of this terminating step had large effects on atmospheric oxidative capacity and the concentrations of HONO2 and ozone (O3), among others. Here, the yield of HONO2, φHONO2, from the reaction of HO2 + NO was investigated in a flow tube reactor using mid-IR pulsed-cavity ringdown spectroscopy. HO2, produced by pulsed laser photolysis of Cl2 in the presence of methanol, reacted with NO in a buffer gas mixture of N2 and CO between 300 and 700 Torr at 278 and 300 K. HONO2 and its weakly bound isomer HOONO were directly detected by their v1 absorption bands in the mid-IR region. CO was used to suppress HONO2 produced from OH + NO2 and exploit a chemical amplification scheme, converting OH back to HO2. Under the experimental conditions described here, no evidence for the formation of either HONO2 or HOONO was observed from HO2 + NO. Using a comprehensive chemical model, constrained by observed secondary reaction products, all HONO2 detected in the system could be accounted for by OH + NO2. At 700 ± 14 Torr and 300 ± 3 K, φHONO2 = 0.00 ± 0.11% (2σ) with an upper limit of 0.11%. If all of the observed HONO2 was attributed to the HO2 + NO reaction, φHONO2 = 0.13 ± 0.07% with an upper limit of 0.20%. At 278 ± 2 K and 718 ± 14 Torr, we determine an upper limit, φHONO2 ≤ 0.37%. Our measurements are significantly lower than those previously reported, lying outside of the uncertainty of the current experimental and recommended literature values.

Atmospherically Relevant Chemistry and Aerosol box model – ARCA box (version 1.2)

Abstract. We introduce the Atmospherically Relevant Chemistry and Aerosol box model ARCA box (v.1.2.2). It is a zero-dimensional process model with a focus on atmospheric chemistry and submicron aerosol processes, including cluster formation. A novel feature in the model is its comprehensive graphical user interface, allowing for detailed configuration and documentation of the simulation settings, flexible model input, and output visualization. Additionally, the graphical interface contains tools for module customization and input data acquisition. These properties – customizability, ease of implementation and repeatability – make ARCA an invaluable tool for any atmospheric scientist who needs a view on the complex atmospheric aerosol processes. ARCA is based on previous models (MALTE-BOX, ADiC and ADCHEM), but the code has been fully rewritten and reviewed. The gas-phase chemistry module incorporates the Master Chemical Mechanism (MCMv3.3.1) and Peroxy Radical Autoxidation Mechanism (PRAM) but can use any compatible chemistry scheme. ARCA's aerosol module couples the ACDC (Atmospheric Cluster Dynamics Code) in its particle formation module, and the discrete particle size representation includes the fully stationary and fixed-grid moving average methods. ARCA calculates the gas-particle partitioning of low-volatility organic vapours for any number of compounds included in the chemistry, as well as the Brownian coagulation of the particles. The model has parametrizations for vapour and particle wall losses but accepts user-supplied time- and size-resolved input. ARCA is written in Fortran and Python (user interface and supplementary tools), can be installed on any of the three major operating systems and is licensed under GPLv3.

Transport parameterization of the Polar SWIFT model (version 2)

Abstract. The Polar SWIFT model is a fast scheme for calculating the chemistry of stratospheric ozone depletion in the polar vortex in winter. It is intended for use in general circulation models (GCMs) and earth system models (ESMs) to enable the simulation of interactions between the ozone layer and climate when a full stratospheric chemistry scheme is computationally too expensive. In addition to the simulation of chemistry, ozone has to be transported in the GCM. As an alternative to the general schemes for the transport and mixing of tracers in the GCMs, a parameterization of the transport of ozone can be used in order to obtain the total change of ozone as the sum of the change by transport and by chemistry. One of the benefits of this approach is the easy and self-contained coupling to a GCM. Another potential advantage is that a transport parameterization based on reanalysis data and measurements can avoid deficiencies in the representation of transport in the GCMs, such as deficits in the representation of the Brewer–Dobson circulation caused by the gravity wave parameterization. Hence, we present a transport parameterization for the Polar SWIFT model that simulates the change in vortex-averaged ozone by transport in a fast and simple way without the need for a complex transport scheme in the GCM.

The influence of various pesticide loads on the development of late blight and potato alternariоsis in the Central region of Russia

Field experiments were conducted to test three schemes for the use of drugs of different action spectra in order to reduce the chemical load on the potato biocenosis. The experiments were carried out on four varieties differing in resistance to late blight. According to the results of two-year tests, it was revealed that on resistant varieties Grand, Kumach and medium-resistant varieties Gulliver, even in epiphytotic years for late blight, it is possible to use alternating preparations, which reduces the chemical load by 33.3%. On the Northern Lights variety unstable to late blight, only a chemical scheme can be used in such years. In the years with the depressive development of late blight, the use of any schemes was not very effective. Etching of planting tubers with Edikum preparation in some years reduces the germination of Grand and Gulliver varieties by 90-70%, Kumach and Northern Lights varieties by 13-16%, which negatively affects potato yields.

The effects of surface fossil magnetic fields on massive star evolution: IV. Grids of models at Solar, LMC, and SMC metallicities

ABSTRACT Magnetic fields can drastically change predictions of evolutionary models of massive stars via mass-loss quenching, magnetic braking, and efficient angular momentum transport, which we aim to quantify in this work. We use the mesa software instrument to compute an extensive main-sequence grid of stellar structure and evolution models, as well as isochrones, accounting for the effects attributed to a surface fossil magnetic field. The grid is densely populated in initial mass (3–60 M⊙), surface equatorial magnetic field strength (0–50 kG), and metallicity (representative of the Solar neighbourhood and the Magellanic Clouds). We use two magnetic braking and two chemical mixing schemes and compare the model predictions for slowly rotating, nitrogen-enriched (‘Group 2’) stars with observations in the Large Magellanic Cloud. We quantify a range of initial field strengths that allow for producing Group 2 stars and find that typical values (up to a few kG) lead to solutions. Between the subgrids, we find notable departures in surface abundances and evolutionary paths. In our magnetic models, chemical mixing is always less efficient compared to non-magnetic models due to the rapid spin-down. We identify that quasi-chemically homogeneous main sequence evolution by efficient mixing could be prevented by fossil magnetic fields. We recommend comparing this grid of evolutionary models with spectropolarimetric and spectroscopic observations with the goals of (i) revisiting the derived stellar parameters of known magnetic stars, and (ii) observationally constraining the uncertain magnetic braking and chemical mixing schemes.

Redox oxide@molten salt as a generalized catalyst design strategy for oxidative dehydrogenation of ethane via selective hydrogen combustion

The current study demonstrates a redox oxide @ molten salt core-shell architecture as a generalized redox catalyst design strategy for chemical looping – oxidative dehydrogenation of ethane. 17 combinations of redox active oxides and molten salts were prepared, evaluated, and characterized. X-ray diffraction indicates that the redox oxides and molten salts are fully compatible, forming separate and stable phases. X-ray photoelectron spectroscopy demonstrates that the molten salts aggregate at the redox oxide surface, forming a core-shell structure to block the non-selective sites responsible for COx formation. Up to ∼74 % single-pass olefin yields were achieved using the proposed redox catalyst design strategy. Statistical analyses of the performance data indicate the potential to achieve up to 86.7 % single-pass yield by simply optimizing the operating conditions using the redox catalysts reported in this study. Meanwhile, the generalizability of the catalyst design strategy offers exciting opportunities to further optimize the composition and performance of the redox catalysts for ethane ODH under a chemical looping scheme with significantly reduced energy consumption and CO2 emissions.

Insight into the inner structure of stretched premixed ammonia-air flames

Ammonia as a fuel has sparked significant interest in the combustion community. Although, using ammonia has a lot of advantages including no carbon emissions, ammonia-air flames are characterized as thick flames with low flame speeds. It is important to understand the flame structure to know the combustion process better. Flame thickness is an important property of the flame which characterizes the reactivity of the flame. Identifying the preheat zone is necessary to determine the fresh gas surface which is used to determine flame speed. Also, understanding the behavior of the important species emitted helps to demonstrate the reaction pathway which may be implemented in chemical kinetics schemes. Further, it is interesting to know the effect of curvature on the emission of excited species which gives direct knowledge on the influence of curvature on the flame reactivity. It was seen that the change in reactivity was manifested as a change in thickness of the species. The experiments presented here were performed on a Bunsen burner at atmospheric conditions. The laminar flame speeds have been evaluated over a range of equivalence ratios by choosing the isotherm as specified by the definition of the flame speed which are slightly higher than the values obtained from the literature. Chemiluminescence from NH* and NH2* was studied for different equivalence ratios. A 1D simulation performed in Chemkin-Pro-was used to compare the behavior of the counterpart non-excited species. This comparison helps to correlate excited and non-excited species and also to define the structure of the ammonia-air flame. Both NH* and NH2* have been determined as heat release rate markers.

Investigation of the impact of NRP discharge frequency on the ignition of a lean methane-air mixture using fully coupled plasma-combustion numerical simulations

The ignition of an atmospheric pressure laminar premixed methane/air mixture by Nanosecond Repetitively Pulsed (NRP) discharges in a pin-pin configuration is studied using fully coupled plasma-combustion numerical simulations. These simulations are performed using the AVIP code specifically developed for low temperature plasma modeling and coupled to the combustion code AVBP. A reduced chemical scheme for plasma-assisted combustion previously derived and validated is used to investigate the effect of the frequency of NRP discharges and the benefits of their chemical enhancement. It is observed that the induced shock wave produced by strong discharges is of major importance for ignition and can lead to quenching of the ignition kernels through strong induced recirculation of gases. Increasing the frequency of the discharges reduces this effect by depositing less energy at each discharge and accumulating energy more homogeneously between the electrodes, leading to a faster and more stable ignition. The minimum energy necessary to ignite decreases with increasing frequency and at the highest studied frequency (100 kHz) ignition has been achieved with 30% less energy than with a single-pulse discharge.

In Vivo Degradation Studies of PGA-PLA Block Copolymer and Their Histochemical Analysis for Spinal-Fixing Application.

Polylactic acid (PLA) and polyglycolic acid (PGA) are well-known medical-implant materials. Under the consideration of the limitations of degradable polymeric materials, such as weak mechanical strength and by-product release through the biodegradation process under in vivo environments, PLA–PGA block copolymer is one of the effective alternative implant materials in the clinical field. In our previous study, two types of extremely effective PGA–PLA copolymers (multi/tri-block PGA–PLA copolymers) were synthesized. These synthesized block copolymers could overcome aforementioned issues and also showed good biocompatibility. In this study, the PGA–PLA block copolymers with large molecular weight were synthesized under the same chemical scheme, and their bio durability was confirmed through the in vivo degradation behavior and histochemical analyses (by hematoxylin and eosin and immune staining) in comparison with commercial PLGA random copolymer (medical grade). Specimens for the degradation test were investigated by SEM and X-ray diffractometer (XRD). As a result, the synthesized PGA–PLA block copolymer showed good biocompatibility and had a controlled biodegrading rate, making it suitable for use in resorbable spinal-fixation materials.

OpenIFS/AC: atmospheric chemistry and aerosol in OpenIFS 43r3

Abstract. In this paper, we report on the first implementation of atmospheric chemistry and aerosol as part of the European Centre for Medium-Range Weather Forecasts (ECMWF) OpenIFS model. OpenIFS is a portable version of ECMWF's global numerical weather prediction model. Modules and input data for model cycle CY43R3, which have been developed as part of the Copernicus Atmosphere Monitoring Service (CAMS), have been ported to OpenIFS with the modified CB05 tropospheric chemistry scheme, the bulk bin tropospheric aerosol module, and the option to use Belgian Assimilation System for Chemical ObsErvations (BASCOE)-based stratospheric ozone chemistry. We give an overview of the model, and describe the datasets used for emissions and dry deposition, which are similar to those used in the model configuration applied to create the CAMS reanalysis. We evaluate two reference model configurations with and without the stratospheric chemistry extension against standard observational datasets for tropospheric ozone, surface carbon monoxide (CO), tropospheric nitrogen dioxide (NO2), and aerosol optical depth. The results give basic confidence in the model implementation and configuration. This OpenIFS version with atmospheric composition components is open to the scientific user community under a standard OpenIFS license.

Secondary aerosol formation in marine Arctic environments: a model measurement comparison at Ny-Ålesund

Abstract. In this study, we modeled the aerosol particle formation along air mass trajectories arriving at the remote Arctic research stations Gruvebadet (67 m a.s.l.) and Zeppelin (474 m a.s.l.), Ny-Ålesund, during May 2018. The aim of this study was to improve our understanding of processes governing secondary aerosol formation in remote Arctic marine environments. We run the Lagrangian chemistry transport model ADCHEM, along air mass trajectories generated with FLEXPART v10.4. The air masses arriving at Ny-Ålesund spent most of their time over the open ice-free ocean. In order to capture the secondary aerosol formation from the DMS emitted by phytoplankton from the ocean surface, we implemented a recently developed comprehensive DMS and halogen multi-phase oxidation chemistry scheme, coupled with the widely used Master Chemical Mechanism (MCM). The modeled median particle number size distributions are in close agreement with the observations in the marine-influenced boundary layer near-sea-surface Gruvebadet site. However, while the model reproduces the accumulation mode particle number concentrations at Zeppelin, it overestimates the Aitken mode particle number concentrations by a factor of ∼5.5. We attribute this to the deficiency of the model to capture the complex orographic effects on the boundary layer dynamics at Ny-Ålesund. However, the model reproduces the average vertical particle number concentration profiles within the boundary layer (0–600 m a.s.l.) above Gruvebadet, as measured with condensation particle counters (CPCs) on board an unmanned aircraft system (UAS). The model successfully reproduces the observed Hoppel minima, often seen in particle number size distributions at Ny-Ålesund. The model also supports the previous experimental findings that ion-mediated H2SO4–NH3 nucleation can explain the observed new particle formation in the marine Arctic boundary layer in the vicinity of Ny-Ålesund. Precursors resulting from gas- and aqueous-phase DMS chemistry contribute to the subsequent growth of the secondary aerosols. The growth of particles is primarily driven via H2SO4 condensation and formation of methane sulfonic acid (MSA) through the aqueous-phase ozonolysis of methane sulfinic acid (MSIA) in cloud and deliquescent droplets.

A mini-chemical scheme with net reactions for 3D general circulation models

Context. Growing evidence has indicated that the global composition distribution plays an indisputable role in interpreting observational data. Three-dimensional general circulation models (GCMs) with a reliable treatment of chemistry and clouds are particularly crucial in preparing for upcoming observations. In attempts to achieve 3D chemistry-climate modeling, the challenge mainly lies in the expensive computing power required for treating a large number of chemical species and reactions. Aims. Motivated by the need for a robust and computationally efficient chemical scheme, we devise a mini-chemical network with a minimal number of species and reactions for H2-dominated atmospheres. Methods. We apply a novel technique to simplify the chemical network from a full kinetics model, VULCAN, by replacing a large number of intermediate reactions with net reactions. The number of chemical species is cut down from 67 to 12, with the major species of thermal and observational importance retained, including H2O, CH4, CO, CO2, C2H2, NH3, and HCN. The size of the total reactions is also greatly reduced, from ~800 to 20. We validated the mini-chemical scheme by verifying the temporal evolution and benchmarking the predicted compositions in four exoplanet atmospheres (GJ 1214b, GJ 436b, HD 189733b, and HD 209458b) against the full kinetics of VULCAN. Results. The mini-network reproduces the chemical timescales and composition distributions of the full kinetics well within an order of magnitude for the major species in the pressure range of 1 bar–0.1 mbar across various metallicities and carbon-to-oxygen (C/O) ratios. Conclusions. We have developed and validated a mini-chemical scheme using net reactions to significantly simplify a large chemical network. The small scale of the mini-chemical scheme permits simple use and fast computation, which is optimal for implementation in a 3D GCM or a retrieval framework. We focus on the thermochemical kinetics of net reactions in this paper and address photochemistry in a follow-up paper.

Optimized two-step (OTS) chemistry model for the description of partially premixed combustion

Once properly optimized, single-step chemistry models are able to recover essential characteristics of flames such as burned gases temperature, flame propagation velocity and thickness. Ignition delay values can be reproduced as well. However, an improved description of either the premixed flame inner structure or the ignition process requires the consideration of the multi-step nature of chemical kinetics. Indeed, single-step chemistry models can neither describe properly the internal structure of laminar premixed flames nor the development of ignition processes. These limitations arise because single-step chemistry does not take into account intermediate species, the importance of which is essential. Thus, the present work is aimed at extending the recently-proposed optimized single-step (OSS) framework to multi-step chemistry. To this purpose an unbranched chain reaction with only two consecutive steps relevant to chain initiation and chain termination is considered. The corresponding kinetics model does involve two fictive species, the characteristics of which are optimized together with the two-step chemical scheme parameters, e.g., pre-exponential factors and activation energies. One of this fictive species is relevant to combustion products while the other represents the whole pool of radicals. The chemistry optimization procedure makes use of a well-defined in-house genetic algorithm and the resulting optimized two-step (OTS) model is assessed through comparisons made with data obtained from detailed chemistry computations used as reference. For similar (and even lower) CPU costs, the computations performed with the OTS model put into evidence significant improvements compared to the results obtained with the OSS description.

Enhanced performance of LaFeO3 oxygen carriers by NiO for chemical looping partial oxidation of methane

Partially oxidizing methane into syngas via a two step chemical looping scheme is a promising option for methane transformation. However, providing the optimum lattice oxygen to selectively produce syngas represents the major challenge for the development of oxygen carrier materials in chemical looping processes. In this work, a NiO-modified LaFeO3 (x wt% Ni/LaFeO3, x = 0, 3, 5, 7, 9, 11) oxygen carrier is proposed to enhance the activity of lattice oxygen for chemical looping partial oxidation of methane. The results show that the methane conversion rate of 5 wt% Ni/LaFeO3 is increased by 25% compared to that of unmodified LaFeO3. It is worth noting that the methane conversion and product selectivity mainly depend on the Ni loading, and 5 wt% Ni/LaFeO3 oxygen carriers has higher CH4 conversion (95.2%) and CO selectivity (85.1%). The results demonstrate that it is feasible to active the lattice oxygen of LaFeO3 perovskite oxygen carriers by surface modification of NiO, which ultimately influences their reaction performance in chemical looping partial oxidation of methane (CL-POM) processes.

High-Density Patterning of InGaZnO by CH4: a Comparative Study of RIE and Pulsed Plasma ALE.

InGaZnO (IGZO)-based thin-film transistors and selector diodes are increasingly investigated for a broad range of applications such as high-resolution displays, high-density memories, and high-speed computing. However, its potential to be a key material for next-generation devices is strongly contingent on developing patterning processes with minimal damage at nanoscale dimensions. IGZO can be etched using CH4-based plasma. Although the etched by-products are volatile, there remains a concern that passivation─an associated effect arising from the use of a hydrocarbon etchant─may inhibit the patterning process. However, there has been limited discussion on the CH4-based etching of IGZO and the subsequent patterning challenges arising with pitch scaling (<200 nm). In this work, we systematically investigate dry chemical etching schemes to pattern an IGZO film into densely packed nanostructures using CH4. Straight IGZO lines, ∼45 nm in width at a pitch of ∼135 nm, are produced by employing the traditional reactive ion etching method. While the passivating effect of CH4 does not impede the etching process, any further shrinkage of feature and pitch dimensions amplifies reactive ion etching-induced damage in the form of profile distortion and residue redeposition. We show that this is efficiently addressed via atomic layer etching (ALE) of IGZO with CH4 using a pulsed plasma. The unique combination of ALE and plasma pulsing enables controlled reduction of ion-assisted sputtering and redeposition of residues on the patterned IGZO features. This approach is highly scalable and is successfully applied here to achieve well-separated IGZO lines, with critical dimensions down to ∼20 nm at a dense pitch of ∼36 nm. These lines exhibit steep profiles (∼80°) and no undesirable change in IGZO composition post-patterning. Finally, ALE of IGZO under pulsed plasma, reproduced on 300 mm wafers, highlights its suitability in large-scale manufacturing for the intended applications.