Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “surface reactions”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

A multiscale packed-bed reactor model for sustainable ethylene production via chemical looping oxidative coupling of methane

The rising global warming concerns and shale gas discovery have prompted research in the direction of greenhouse gas (GHG), such as methane, reduction and conversion. Oxidative coupling of methane (OCM) offers a pathway to low carbon-intense valorization of methane while producing ethylene, a chemical regarded as central to the petrochemical industry. Even after decades of OCM discovery, researchers keep understanding the process and underlying chemical reactions in a pursuit to achieve industrial viability for OCM. Here, in general, OCM suffers from low C 2 selectivity, yield and reactor temperature runaways due to highly exothermic nature of its reactions. Computational Fluid Dynamics (CFD) tools help analyze spatial gradients within the reactor to deeply understand the diffusion of species, mass and heat transfer phenomena. Furthermore, challenges associated with scaling up such as hot spot formation and parametric sensitivity can be addressed without having to expend on costly experiments. The current paper presents a multiscale packed-bed reactor CFD model coupled with a chemical kinetic model for the chemical looping OCM. The CFD model includes two scales i.e., macroscale for catalyst bed and microscale for individual pellets. Moreover, a chemical kinetic model based on 10 gas-phase reactions is integrated with the CFD model. An additional surface reaction for the formation of gas-phase oxygen from catalyst surface is added to account for the absence of feed oxygen. The model is calibrated against experimental results. The calibrated model captures trends in CH 4 conversion, C 2 selectivity and C 2 yield within a ± 4.35 % range across a temperature range of 700-900 °C. Moreover, model fidelity is evaluated by varying key computational parameters such as mesh resolution and time step size. The model is also verified by varying the inlet methane concentration and the gas hourly space velocity (GHSV) and comparing the results with literature. A sensitivity analysis and scale-up of the current model is undergoing.

Chemical looping↗
DOE OSTI2026

Iron surface corrosion in supercritical CO2 at atomic scale investigated by molecular dynamics simulations

Understanding the corrosion behavior of steels in supercritical carbon dioxide (S-CO2) is essential for ensuring the safe application of S-CO2 as a heat-transfer fluid in high-temperature energy systems, including advanced nuclear reactors. In this work, molecular dynamics (MD) simulations using ReaxFF potential are performed to explore the atomic-scale corrosion mechanisms of body-centered cubic iron (BCC-Fe) in S-CO2. The results show that CO2 molecules in S-CO2 decompose at the Fe surface, generating free C and O atoms that form Fe-C and Fe-O bonds and subsequently produce oxides and carbides. Concurrently, Fe atoms dissolve from the surface and diffuse into the S-CO2 region, resulting in interdiffusion of Fe, C and O atoms at the interface. The corrosion-layer thickness calculations show that high pressure and temperature induced by S-CO2 have stronger effects than surface orientation on the corrosion process. In addition, surface Fe atoms undergo substantial displacement under S-CO2 exposure, further accelerating corrosion. When a radiation-induced void is introduced near the Fe surface, the corrosion is enhanced. The void-matrix interface expands the reaction surface area and simultaneously induces corrosion reactions inside the bulk, resulting in a deeper penetration of C and O and thicker corrosion layers. All these results indicate that high-temperature, high-pressure and radiation-induced voids can seriously affect the corrosion of Fe in S-CO2, and must be considered to better use S-CO2 in nuclear facilities.

Li, Wenhua↗
NASA NTRS1976

Atomic oxygen-metal surface studies as applied to mass spectrometer measurements of upper planetary atmospheres

The problem of atomic oxygen loss in mass spectrometer ion sources can be reduced to an understanding of the possible surface interactions between oxygen atoms and the metal surface of the ion source. Results are presented for an experimental study in which an atomic oxygen beam apparatus and a mass spectrometer were used to measure the oxygen atom reflection, recombination, general surface reaction, and occlusion probabilities on six different engineering surfaces as a function of atomic oxygen exposure. The materials studied are gold, Nichrome V, aluminum, titanium, silver, and platinum. The variation in measured reflection probability seems to occur with metals that form oxides, Nichrome V being stable in terms of reflection stability. Recombination is observed an all surfaces except aluminum and platinum. Variation in the complete set of measurements in a single experiment is the result of varying surface conditions.

Sjolander, G. W.↗
NASA NTRS1994

Thermal desorption of CO and H2 from degassed 304 and 347 stainless steel

Thermal desorption spectroscopy (TDS), along with Auger electron spectroscopy, was used to study the desorption of H2 and CO from baked 304 and 347 stainless-steel samples exposed only to residual gases. Both 347 and 304 samples gave identical TDS spectra. The spectra for CO contained a sharp leading peak centered in the temperature range 410-440C and an exponentially increasing part for temperatures higher than 500C, with a small peak around 600C appearing as a shoulder. The leading peak followed a second-order desorption behavior with an activation energy of 28+/-2 kcal/mol, suggesting that the rate-limiting step for this peak is most likely a surface reaction that produces the CO molecules in the surface layer. The amount of desorbed CO corresponding to this peak was approximately 0.5X10(exp 14) molecules/cm(exp 2) . The exponentially rising part of the CO spectrum appeared to originate from a bulk diffusion process. The TDS spectrum for H2 consisted of a main peak centered also in the temperature range 410-440C, with two small peaks appearing as shoulders at approximately 500 and 650C. The main peak in this case also displayed a second-order behavior with an activation energy of 14+/-2 kcal/mol. The amount of desorbed H2, approximately 1.9X 10(exp 15) molecules/cm(exp 2) , appeared to be independent of the concentration of hydrogen in the bulk, indicating that the majority of the desorbed H2 originated from the surface layer.

Rezaie-Serej, S.↗
NASA NTRSDate not supplied

Pterodactyl: Aerodynamic and Aerothermal Modeling for a Symmetric Deployable Earth Entry Vehicle with Flaps

NASA’s Pterodactyl project has investigated a deployable atmospheric entry vehicle integrated with a flap control system that provides precision targeting during reentry. The control system consists of eight flaps mounted at the edge of a heatshield that can deflect in and out of the flow. An aerodynamic and aerothermodynamic analysis process was developed for preliminary vehicle design and aerodynamic database generation using engineering and CFD tools with varying levels of fidelity. The objective of this analysis was to: 1) understand the inherent aerodynamics, 2) provide an aerodynamics database for stability and control analysis, and 3) provide qualitative and quantitative aeroheating analysis for Thermal Protection System modeling of the flaps. A high fidelity Euler code, Cart3D, was used to resolve complex flow features such as secondary shocks and shock impingement. A wide range of supersonic (Mach 2) and hypersonic Mach numbers (up to Mach 40) were tested with an Earth atmosphere model. A process was developed to utilize the adaptive volume mesh generator utility of the perfect gas model of Cart3D to create meshes with high cell efficiency and numerical stability prior to running a 2nd order accurate solution with a real gas model. High-fidelity aerothermal CFD simulations were performed using US3D to further improve the aerothermal analysis on hypersonic flow around a complex entry vehicle shape including viscosity, chemical reactions of air species, vibrational energy, and catalytic surface reactions. In this process, it was found that the flap control system provided multi-axis control that can be utilized for entry precision targeting. Additionally, the Pterodactyl vehicle can achieve up to a trim L/D of 0.2. Finally, the increased fidelity of the aerothermal heating environments revealed that the shear stress contributes to increasing the heating on the flaps.

Deployable Entry Vehicle↗
NASA NTRSDate not supplied

Pterodactyl: Aerodynamic and Aerothermal Modeling for a Symmetric Deployable Earth Entry Vehicle with Flaps

NASA’s Pterodactyl project has investigated a deployable atmospheric entry vehicle integrated with a flap control system that provides precision targeting during reentry. The control system consists of eight flaps mounted at the edge of a heatshield that can deflect in and out of the flow. An aerodynamic and aerothermodynamic analysis process was developed for preliminary vehicle design and aerodynamic database generation using engineering and CFD tools with varying levels of fidelity. The objective of this analysis was to: 1) understand the inherent aerodynamics, 2) provide an aerodynamics database for stability and control analysis, and 3) provide qualitative and quantitative aeroheating analysis for Thermal Protection System modeling of the flaps. A high fidelity Euler code, Cart3D, was used to resolve complex flow features such as secondary shocks and shock impingement. A wide range of supersonic (Mach 2) and hypersonic Mach numbers (up to Mach 40) were tested with an Earth atmosphere model. A process was developed to utilize the adaptive volume mesh generator utility of the perfect gas model of Cart3D to create meshes with high cell efficiency and numerical stability prior to running a 2nd order accurate solution with a real gas model. High-fidelity aerothermal CFD simulations were performed using US3D to further improve the aerothermal analysis on hypersonic flow around a complex entry vehicle shape including viscosity, chemical reactions of air species, vibrational energy, and catalytic surface reactions. In this process, it was found that the flap control system provided multi-axis control that can be utilized for entry precision targeting. Additionally, the Pterodactyl vehicle can achieve up to a trim L/D of 0.2. Finally, the increased fidelity of the aerothermal heating environments revealed that the shear stress contributes to increasing the heating on the flaps.

Deployable Entry Vehicle↗
NASA NTRS2001

Spectroscopic diagnostics of organic chemistry in the protostellar environment

A combination of astronomical observations, laboratory studies, and theoretical modelling is necessary to determine the organic chemistry of dense molecular clouds. We present spectroscopic evidence for the composition and evolution of organic molecules in protostellar environments. The principal reaction pathways to complex molecule formation by catalysis on dust grains and by reactions in the interstellar gas are described. Protostellar cores, where warming of dust has induced evaporation of icy grain mantles, are excellent sites in which to study the interaction between gas phase and grain-surface chemistries. We investigate the link between organics that are observed as direct products of grain surface reactions and those which are formed by secondary gas phase reactions of evaporated surface products. Theory predicts observable correlations between specific interstellar molecules, and also which new organics are viable for detection. We discuss recent infrared observations obtained with the Infrared Space Observatory, laboratory studies of organic molecules, theories of molecule formation, and summarise recent radioastronomical searches for various complex molecules such as ethers, azaheterocyclic compounds, and amino acids.

Ethers/analysis/chemical synthesis/chemistry↗
DOE OSTI2021

High-Performance Catalytic Four-Channel Hollow Fibers with Highly Dispersed Nickel Nanoparticles Prepared by Atomic Layer Deposition for Dry Reforming of Methane

In this study, highly dispersed nickel (Ni) nanoparticles (NPs) with an average particle size of 4.3 nm were uniformly deposited on the outer surface, the inner channel surface, and inside the pores of 20-cm long 4-channel α-Al 2 O 3 hollow fibers (HFs) by atomic layer deposition (ALD) for dry reforming of methane (DRM). Cerium oxide (CeO 2 ) was added to promote the catalytic performance of Ni/Al 2 O 3 -HF catalysts. Rationally designed filling methods, by tuning the reactor size and inert fillings, can reduce the catalyst bed voidage in a fixed bed reactor for better reactant gas distribution, effectively utilize the Ni reactive sites, and achieve excellent catalytic performance. It was found that the CeO 2 -promoted Ni/Al 2 O 3 -HF catalyst was highly active and highly stable without deactivation during an overall 400-hr DRM test at 850 ºC. CeO 2 with reversible valence states could participate in surface reactions; especially, the formation of CeAlO 3 provided sufficient surface Ce 3+ for CO 2 activation and enhanced the stability and reusability of the HF catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1973

Investigation of atomic oxygen-surface interactions related to measurements with dual air density explorer satellites

For a number of candidate materials of construction for the dual air density explorer satellites the rate of oxygen atom loss by adsorption, surface reaction, and recombination was determined as a function of surface and temperature. Plain aluminum and anodized aluminum surfaces exhibit a collisional atom loss probability alpha .01 in the temperature range 140 - 360 K, and an initial sticking probability. For SiO coated aluminum in the same temperature range, alpha .001 and So .001. Atom-loss on gold is relatively rapid alpha .01. The So for gold varies between 0.25 and unity in the temperature range 360 - 140 K.

Wood, B. J.↗
NASA NTRS1993

Computed potential energy surfaces for chemical reactions

A new global potential energy surface (PES) is being generated for O(P-3) + H2 yields OH + H. This surface is being fit using the rotated Morse oscillator method, which was used to fit the previous POL-CI surface. The new surface is expected to be more accurate and also includes a much more complete sampling of bent geometries. A new study has been undertaken of the reaction N + O2 yields NO + O. The new studies have focused on the region of the surface near a possible minimum corresponding to the peroxy form of NOO. A large portion of the PES for this second reaction has been mapped out. Since state to state cross sections for the reaction are important in the chemistry of high temperature air, these studies will probably be extended to permit generation of a new global potential for reaction.

Walch, Stephen P.↗
DOE OSTI2024

Insights into the Electrochemical Oxidation and Reduction of Nickel Oxide Surfaces

Surface oxidation/reduction processes, driven by varying electrochemical potentials, can substantially impact catalyst effectiveness and, consequently, electrolyzer performance. Here, this study combines theoretical and experimental approaches to explore the surface redox behavior of nickel oxides, which are cost-effective and efficient catalysts for many electrochemical reactions. Surface Pourbaix diagrams for three different phases of nickel oxides, i.e., nickel hydroxide (Ni(OH) 2 ), nickel oxyhydroxide (NiOOH), and nickel dioxide (NiO 2 ), were constructed using density functional theory-based simulations. Various experimental methods, including cyclic voltammetry, in situ Raman spectroscopy, and electrochemical titration, were employed to probe the surface redox processes of nickel oxide thin films. Our findings indicate that the ABAB stacking sequence of Ni(OH) 2 lacks stability under oxidizing conditions to host the surface oxidation (deprotonation) events, while the AABBCC stacking sequence of NiOOH is energetically favorable due to the presence of interlayer hydrogen bonding. Rapid charge transfer facilitated by interlayer hydrogen bonding accounts for the higher reactivity of partially oxidized/reduced NiOOH (001) surfaces compared to Ni(OH) 2 (001) and NiO 2 (001) surfaces with the same stoichiometry, where interlayer hydrogen bonding is absent. Insights presented in this work can offer guidelines for optimizing operational conditions and tailoring the surface structures and oxidation states of nickel oxides to enhance performance in applications such as electrocatalysis and supercapacitors.

36 MATERIALS SCIENCE↗
DOE OSTI2025

HydroGEN STCH node support: FY25 Q1 quarterly report – LLNL's input

For reducing the cost of H 2 production by enhancing the efficiency and cyclability of water splitting reactions, we aim to understand the relationship between microstructure and surface reaction performance on perovskite oxides. In this quarter, mesoscale simulations were carried with various 3D porous microstructures to characterize the microstructure-dependent H 2 production. During the water splitting process, incoming gas including steam (H 2 O) passes through porous regions, which can induce local pressure variations according to the Bernoulli’s principle. Accordingly, we developed the mesoscale simulation method to characterize the reaction kinetics with inhomogeneous local pressures within porous microstructures.

08 HYDROGEN↗
NASA NTRS1983

Interstellar ice

The 3250/cm 'ice' band observed in absorption and polarization in interstellar spectra is studied in the laboratory in low-temperature solid mixtures of H2O and other molecules. General empirical rules are derived which relate the shape and relative intensity of the H2O infrared absorptions to the degree of H2O dilution and hydrogen-bonding capacity of the dilutant. The chemical composition of mantles accreting on interstellar grains inside dense (1000-100,000/cu cm) molecular clouds has been calculated numerically. The reaction scheme comprises gas-phase as well as grain surface reactions. The results show that in most circumstances grain mantles consist of the molecules H2O, H2CO, NH3, N2, O2, CO, and CO2. The expected infrared characteristics of the calculated grain mantles are discussed with an emphasis on the observed 3250/cm 'ice' band. Grain mantles accreted at a density of about 10,000/cu cm contain large concentrations of H2O (about 60 percent) and produce a broad 3250/cm 'ice' band.

Tielens, A. G. G. M.↗
NASA NTRS2022

Development of an Effective Finite-rate Oxidation Model for NuSil-coated Charred Carbon Preform Ablators

Recently, a detailed effective finite-rate surface chemistry model was developed for the oxidation of FiberForm [1] using the molecular beam experimental data of Poovathingal et al., [2]. FiberForm is the major building block of the thermal protection system (TPS) material Phenolic Impregnated Carbon Ablator (PICA), commonly used by NASA. The surface chemistry model consists of detailed surface reaction mechanisms such as adsorption, desorption, and several types of Langmuir-Hinshelwood (LH) reactions to characterize the oxygen-carbon interactions at the surface. This model provides excellent agreement with the experimental data for oxidation product compositions and corresponding translational energy distributions. Further, an effective oxidation model was constructed that captures the equivalent interaction of oxygen inside the microstructure (including multiple surface collisions) via a modified reactivity for a smooth wall boundary condition. This enables the use of this model directly into Computational Fluid Dynamics (CFD) codes and Material Response (MR) codes to accurately simulate the gas–surface interactions within FiberForm without using the detailed micro-structure. However, this effective model is valid only for the virgin FiberForm. As the TPS material undergoes ablation, the preform carbon burns and turns into char. In addition, PICA is also coated with a protective silicon coating called NuSil for the purpose of mitigating the spread of phenolic dust, and limit contamination during clean room operations. Fig. 1 shows a X-ray microtomography image of a charred NuSil-coated PICA. The NuSil layer introduces species containing silicon into the product mixture. Further, the reactivity of the carbon within the char layer is different from the virgin FiberForm as shown in Fig. 2. Recently a new set of molecular beam experiments were performed on this NuSil-coated TPS material [3] with the same type of oxygen beam used in the previous experiments. Using the latest experimental data, the previously developed effective model will be extended to account for the charred carbon as well as the NuSil coating. Finally, this new effective model with three phases – preform carbon, char, and NuSil; will be compared and validated against the experimental product compositions.

K Swaminathan Gopalan↗
NASA NTRS2009

Determination of Chemical Kinetic Rate Constants of a Model for Carbothermal Processing of Lunar Regolith Simulant Using Methane

We have previously developed a chemical conversion model of the carbothermal processing of lunar regolith using methane to predict the rate of production of carbon monoxide. In this carbothermal process, gaseous methane is pyrolyzed as it flows over the hot surface of a molten zone of lunar regolith and is converted to carbon and hydrogen. Hydrogen is carried away by the exiting stream of gases and carbon is deposited on the melt surface. The deposited carbon mixes with the melt and reacts with the metal oxides in it to produce carbon monoxide that bubbles out of the melt. In our model, we assume that the flux of carbon deposited is equal to the product of the surface reaction rate constant gamma and the concentration of methane adjacent to the melt surface. Similarly, the rate of consumption of carbon per unit volume in the melt is equal to the product of the melt reaction rate constant k and the concentrations of carbon and metal oxide in the melt. In this paper, we describe our effort to determine gamma and k by comparison of the predictions from our model with test data obtained by ORBITEC (Orbital Technologies Corporation). The concentration of methane adjacent to the melt surface is a necessary input to the model. It is inferred from the test data by a mass balance of methane, adopting the usual assumptions of the continuously-stirred-tank-reactor model, whereby the average concentration of a given gaseous species equals its exit concentration. The reaction rates gamma and k have been determined by a non-linear least-squares fit to the test data for the production of carbon monoxide and the fraction of the incoming methane that is converted. The comparison of test data with our model predictions using the determined chemical kinetic rate constants provides a consistent interpretation of the process over the full range of temperatures, pressures, and methane flow rates used in the tests, thereby increasing our confidence to use the model for scale-up purposes.

Balasubramaniam, R↗
NASA NTRS1977

Motion restraining device

A motion-restraining device for dissipating at a controlled rate the force of a moving body is discussed. The device is characterized by a drive shaft adapted to be driven in rotation by a moving body connected to a tape wound about a reel mounted on the drive shaft, and an elongated pitman link having one end pivotally connected to the crankshaft and the opposite end thereof connected with the mass through an energy dissipating linkage. A shuttle is disposed within a slot and guided by rectilinear motion between a pair of spaced impact surfaces. Reaction forces applied at impact of the shuttle with the impact surfaces include oppositely projected force components angularly related to the direction of the applied impact forces.

Ford, A. G.↗
NASA NTRS1985

AE and DE mass spectrometer observations relevant to the shuttle glow

Recent work suggested that NO2 may be responsible for the observed continuum glow near surfaces of the space shuttle. The observations of atomic nitrogen (N) are reported at shuttle altitudes using mass spectrometers, giving special attention to the surface reactions of N relevant to the production of NO2 on spacecraft surfaces. Data from two semi-open sources mass spectrometers, the OSS instruments on the Atmosphere Explorer-C and -D satellites, and the closed source Neutral Atmospheric Composition Spectrometer (NACS) on the Dynamic Explorer-2 satellite are presented to show the similar behavior of NO in each case and the contrasting behavior of NO2. Although signals of NO and NO2 are highly dependent on surface temperature and surface composition, it appears that direct exposure of ion source surfaces to rammed gas is a necessary condition for the production of large amounts of NO2. Evidence that elevated surface temperatures can significantly reduce the production of NO2, likely by causing more rapid desorption of NO from these surfaces, is presented.

Engebretson, M. J.↗
NASA NTRS1987

Thermochemical erosion

A quasi-steady multidimensional Stefan problem is treated by means of similarity, asymptotic methods, and numerical analysis. The continuous wearing away of a solid 'erodee' is effected by gradual consumption of a solid 'eroder'. In the process under study, the erodee melts and the (liquid) melt diffuses to the eroder, where an exothermic, indefinitely rapid, diffusion-controlled surface reaction occurs. The products of reaction convey some of the chemically-generated heat to the surface of the erodee, so that further melting may occur, and the process may proceed. The analysis seeks to estimate the quasi-steady rates of consumption of the erodee and eroder, for the (convenient) self-similar case of confocal parabolas defining the boundaries of the melt layer. The analysis is simplified by observing that the flow is of lubrication-theory type: creeping, primarily unidirectional motion owing to the thinness of the melt layer between the erodee and eroder, with diffusion of heat and mass predominantly perpendicular to the principal motion. The analysis is completed by consideration of the force balance on the eroder.

Butler, Gerald↗