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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Phase-field modeling of alloy oxidation at high temperatures

Oxide growth is a complex process involving transport of reactive species, heterogeneous reactions, and microstructure evolution. Predicting oxidation kinetics and especially the oxide morphological change has been a long-standing challenge. Here we develop a phase-field model for predicting the oxide growth kinetics of a multicomponent alloy during high temperature oxidation, focusing on internal oxidation (non-protective) and its transition to external oxidation (protective). In this work, the predicted kinetics and oxide morphology are analyzed and compared to the classical Wagner’s theory and an existing analytical model by Zhao and Gleeson. Some assumptions used in the analytical models and the limitation are discussed. In addition, it is demonstrated that the morphology and distribution of the initial oxide nuclei play an important role in the later stage oxide connectivity and thus the transition to external oxidation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Water Freezes at Near-Zero Temperatures Using Carbon Nanotube-Based Electrodes under Static Electric Fields

Although static electric fields have been effective in controlling ice nucleation, the highest freezing temperature ( T f ) of water that can be achieved in an electric field ( E ) is still uncertain. In this study, we performed a systematic study of the effect of an electric field on water freezing by varying the thickness of a dielectric layer and the voltage across it in an electrowetting system. Results show that T f first increases sharply with E and then reaches saturation at –3.5 °C after a critical value E of 6 × 10 6 V/m. Using classical heterogeneous nucleation theory, it is revealed that this behavior is due to saturation in the contact angle of the ice embryo with the underlying substrate. Finally, we show that it is possible to overcome this freezing saturation by controlling the uniformity of the electric field using carbon nanotubes. We achieve a T f of –0.6 °C using carbon nanotube-based electrodes with an E of 3 × 10 7 V/m. This work sheds new light on the control of ice nucleation and has the potential to impact many applications ranging from food freezing to ice production.

25 ENERGY STORAGE↗
NASA NTRS1978

Onset of condensation effects with a NACA 0012-64 airfoil tested in the Langley 0.3-meter cryogenic tunnel

A 0.137m airfoil was tested in a 0.3m transonic cryogenic tunnel at free stream Mach numbers of 0.75, 0.85, and 0.95 over a total pressure range from 1.2 to 5.0 atmospheres. The onset of condensation effects were found to correlate more with the amount of supercooling in the free stream than it did with the supercooling in the region of maximum local Mach number over the airfoil. Effects in the pressure distribution over the airfoil were generally seen to appear over its entire length at nearly the same total temperature. Both observations suggest the possibility of heterogeneous nucleation occurring in the free stream. The potential operational benefits of the supercooling realized are presented in terms of increased Reynolds number capability at a given tunnel total pressure, reduced drive fan power if Reynolds number is held constant, and reduced liquid nitrogen consumption if Reynolds number is again constant. Depending on total pressure and free stream Mach number, these three benefits are found to respectively vary from 7 to 19%, 11 to 25%, and 9 to 20%.

Hall, R. M.↗
NASA NTRS1990

Calorimetry, activity, and micro-FTIR analysis of CO chemisorption, titration, and oxidation on supported Pt

The value of in situ analysis on CO chemisorption, titration and oxidation over supported Pt catalysts using calorimetry, catalytic and micro-FTIR methods is illustrated using silica- and titania-supported samples. Isothermal CO-O and O2-CO titrations have not been widely used on metal surfaces and may be complicated if some oxide supports are reduced by CO titrant. However, they can illuminate the kinetics of CO oxidation on metal/oxide catalysts since during such titrations all O and CO coverages are scanned as a function of time. There are clear advantages in following the rates of the catalyzed CO oxidation via calorimetry and gc-ms simultaneously. At lower temperatures the evidence they provide is complementary. CO oxidation and its catalysis of CO oxidation have been extensively studied with hysteresis and oscillations apparent, and the present results suggest the benefits of a combined approach. Silica support porosity may be important in defining activity-temperature hysteresis. FTIR microspectroscopy reveals the chemical heterogeneity of the catalytic surfaces used; it is interesting that the evidence with regard to the dominant CO surface species and their reactivities with regard to surface oxygen for present oxide-supported Pt are different from those seen on graphite-supported Pt.

Sermon, Paul A.↗
NASA NTRS2002

Kinetics of Melting and Dissolution in Lunar Materials

An understanding of the petrogenesis of lunar magmas, particularly mare basalts and the parent magmas to the Mg-rich suite, remains an unfulfilled goal. The fact is not surprising given the complexity of the problem. On the Moon, the source region for lunar magmas is not primitive mantle but rather a series of cumulate rocks that vary widely in both minerology and major and minor element contents. The stratigraphy of the cumulate mantle is not likely to be very regular given that the culumate pile is formed initially in an unstable configuration and subsequent thermal and compositional heterogeneities on a number of length scales. These lithologic heterogeneities, the large range of pressures and temperatures over which melts are generated on the Moon, and the close juxtaposition of cumulate rock with widely varying solidii introduce significant complications to the nature of the melting relations that control melt generation. These factors, coupled with the likelihood that polybaric fractional melting of varying efficiencies ultimately control the composition of planetary progress, are ample reasons why the lunar magmas remain the enigma they are. To make progress, phase equilibria studies must be coupled with a detailed understanding of the time scales and the dynamics of crystal and melt reequilibration processes.

Hess, Paul C.↗
NASA NTRS1992

Wall to membrane linkers, stretch activated channels, and the detection of tension, voltage, temperature, auxin, and pH

Introduction. The higher plant is a heterogeneous, mechanically prestressed structure continually subject to shifting forces. When a cell grows in a plant at gravitropic equilibrium, it must create localized maxima of shear in walls of neighboring cells. Such mechanical stress and strain are likely detected in a variety of ways. However, tension-sensitive ion channels are of particular interest because it appears that they are elaborately evolved for sensory function. We hypothesize that 1) the patchy patterns of high shear are focused via wall-to-membrane linkers onto the plasma membrane, where 2) they are translated by mechanosensory cation channels into corresponding patterns of high cytosolic Ca2+, which 3) initiate local enhancement of wall expansion. Further, we hypothesize that the local promotion of enhancement is achieved at least in part by local intensification of auxin transport across the plasma membrane. By implication, when an organ is asymmetrically pressed, rubbed, or bent or when it is displaced in the gravitational field, the net asymmetry of shear stress occurring across the organ would lead to asymmetric redistribution of auxin and corrective asymmetric growth. We shall describe a representative mechanosensitive Ca(2+) -selective cation channel (MCaC) with susceptibilities to xenobiotics implicating it as a force transducer in thigmo- and gravitropism. Then, we shall consider whether a putative wall-to-membrane linker (WML) could be a key feature of the molecular architecture permitting the stress distributed in the wall system to be focused on the channels.

NASA Discipline Number 40-50↗
NASA NTRS2012

IDPs and Stardust

Interplanetary dust particles (IDPs) collected in the Earth s stratosphere and NASA Stardust mission samples constitute direct samples of diverse cometary bodies. These materials are among the least altered remnants of the original building blocks of the Solar System. Both cometary materials and primitive meteorites contain a broad diversity of organic compounds that appear to have formed in a range of environments, including the presolar cold molecular cloud, the solar nebula, asteroids and comet nuclei. Isotopic anomalies in H, C, and N are commonly observed in meteoritic organic matter, reflecting chemical processes at extremely low temperatures. These isotopic anomalies are also very heterogeneous on micrometer and even smaller spatial scales, suggesting that some presolar organic grains have survived the formation of the Solar System. Most recently, coordinated transmission electron microscopy and isotopic imaging studies have shown that isotopically anomalous organic globules having rounded and often hollow structures are abundant and widespread amongst the most primitive components of meteoritic materials. These studies suggest that such organic grains were among the most important primary building blocks of the Solar System.

Messenger, Scott R.↗
NASA NTRS1995

An Electrothermodynamic Model With Distributed Properties for Effective Permittivities of Sea Ice

This paper presents a model to calculate the temperature dependence of effective permittivities for a heterogeneous anisotropic medium containing multiphase scatters. With the strong permittivity fluctuation approach, the model is developed to account for the electrodynamic scattering effect together with the quasi-static characteristics of multiple species and subspecies of inhomogeneities with distributed orientations, sizes, and shapes.

sea↗
NASA NTRS1981

Heterogeneous decomposition of silane in a fixed bed reactor

Heterogeneous decomposition of silane in a fluidized bed offers an attractive route for the low-cost production of silicon for photovoltaic application. To obtain design data for a fluid bed silane pyrolysis reactor, deposition experiments were conducted in a small-scale fixed bed apparatus. Data on the decomposition mode, plating rate, and deposition morphology were obtained in the temperature range 600 900 C. Conditions favorable for heterogenous decomposition with good deposition morphology were identified. The kinetic rate data showed the reaction to be first order with an activation energy of 38.8 kcal/mole, which agrees well with work done by others. The results are promising for the development of an economically attractive fluid bed process.

Iya, S. K.↗
NASA NTRS1982

Heterogeneous decomposition of silane in a fixed bed reactor

Heterogeneous decomposition of silane in a fluidized bed offers an attractive route for the low-cost production of silicon for photovoltaic application. To obtain design data for a fluid bed silane pyrolysis reactor, deposition experiments were conducted in a small-scale fixed bed apparatus. Data on the decomposition mode, plating rate, and deposition morphology were obtained in the temperature range 600-900 C. Conditions favorable for heterogeneous decomposition with good deposition morphology were identified. The kinetic rate data showed the reaction to be first order with an activation energy of 38.8 kcal/mol, which agrees well with work done by others. The results are promising for the development of an economically attractive fluid bed process.

Iya, S. K.↗
NASA NTRS1993

Homogeneous ice nucleation and supercooled liquid water in orographic wave clouds

This study investigates ice nucleation mechanisms in cold lenticular wave clouds, a cloud type characterized by quasi-steady-state air motions and microphysical properties. It is concluded that homogeneous ice nucleation is responsible for the ice production in these clouds at temperatures below about -33 C. The lack of ice nucleation observed above -33 C indicates a dearth of ice-forming nuclei, and hence heterogeneous ice nucleation, in these clouds. Aircraft measurements in the temperature range -31 to -41 C show the following complement of simultaneous and abrupt changes in cloud properties that indicate a transition from the liquid phase to ice: disappearance of liquid water; decrease in relative humidity from near water saturation to ice saturation; increase in mean particle size; change in particle concentration; and change in temperature due to the release of latent heat. A numerical model of cloud particle growth and homogeneous ice nucleation is used to aid in interpretation of our in situ measurements. The abrupt changes in observed cloud properties compare favorably, both qualitatively and quantitatively, with results from the homogeneous ice nucleation model. It is shown that the homogeneous ice nucleation rates from the measurements are consistent with the temperature-dependent rates employed by the model (within a factor of 100, corresponding to about 1 C in temperature) in the temperature range -35 deg to -38 C. Given the theoretical basis of the modeled rates, it may be reasonable to apply them throughout the -30 to -50 C temperature range considered by the theory.

Heymsfield, Andrew J.↗
NASA NTRS1982

Thermodynamic and transport combustion properties of hydrocarbons with air. Part 1: Properties in SI units

Thermodynamic and transport combustion properties were calculated for a wide range of conditions for the reaction of hydrocarbons with air. Three hydrogen-carbon atom ratios (H/C = 1.7, 2.0, 2.1) were selected to represent the range of aircraft fuels. For each of these H/C ratios, combustion properties were calculated for the following conditions: Equivalence ratio: 0, 0.25, 0.5, 0.75, 1.0, 1.25 Water - dry air mass ratio: 0, 0.03 Pressure, kPa: 1.01325, 10.1325, 101.325, 1013.25, 5066.25 (or in atm: 0.01, 0.1, 1, 10, 50) Temperature, K: every 10 degrees from 200 to 900 K; every 50 degrees from 900 to 3000 K Temperature, R: every 20 degrees from 360 to 1600 R; very 100 degrees from 1600 to 5400 R. The properties presented are composition, density, molecular weight, enthalphy, entropy, specific heat at constant pressure, volume derivatives, isentropic exponent, velocity of sound, viscosity, thermal conductivity, and Prandtl number. Property tables are based on composites that were calculated by assuming both: (1) chemical equilibrium (for both homogeneous and heterogeneous phases) and (2) constant compositions for all temperatures. Properties in SI units are presented in this report for the Kelvin temperature schedules.

Gordon, S.↗
DOE OSTI2022

Temperature Dependence of Structural Relaxation in Glass-Forming Liquids and Polymers

Understanding the microscopic mechanism of the transition of glass remains one of the most challenging topics in Condensed Matter Physics. What controls the sharp slowing down of molecular motion upon approaching the glass transition temperature T g , whether there is an underlying thermodynamic transition at some finite temperature below T g , what the role of cooperativity and heterogeneity are, and many other questions continue to be topics of active discussions. This review focuses on the mechanisms that control the steepness of the temperature dependence of structural relaxation (fragility) in glass-forming liquids. We present a brief overview of the basic theoretical models and their experimental tests, analyzing their predictions for fragility and emphasizing the successes and failures of the models. Special attention is focused on the connection of fast dynamics on picosecond time scales to the behavior of structural relaxation on much longer time scales. A separate section discusses the specific case of polymeric glass-forming liquids, which usually have extremely high fragility. We emphasize the apparent difference between the glass transitions in polymers and small molecules. We also discuss the possible role of quantum effects in the glass transition of light molecules and highlight the recent discovery of the unusually low fragility of water. At the end, we formulate the major challenges and questions remaining in this field.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS2016

On the Susceptibility of Cold Tropical Cirrus to Ice Nuclei Abundance

Numerical simulations of cirrus formation in the tropical tropopause layer (TTL) are used to evaluate the impact heterogeneous ice nuclei (IN) abundance on cold cloud microphysical properties. The model includes homogeneous and heterogeneous ice nucleation, deposition growthsublimation, and sedimentation. Reanalysis temperature and wind fields are used to force the simulations, with addition of high-frequency wave temperature variability based on in situ measurements. The model results are constrained by recent in situ observations of TTL cirrus and relative humidity, as well as satellite measurements of cirrus bulk properties and occurrence frequencies. Temperature variability driven by high-frequency waves has a dominant influence on TTL cirrus microphysical properties and occurrence frequencies, and inclusion of these waves is required to produce agreement between the simulated and observed cloud properties as well as the abundance of TTL cirrus. With a composition-independent supersaturation threshold for homogeneous freezing of aqueous aerosols, the model produces excessive ice concentrations compared with in situ observations. Inclusion of relatively numerous heterogeneous nuclei ( 100L) in the simulations improves the agreement with observed ice concentrations. However, when IN contribute significantly to TTL cirrus ice nucleation, the occurrence frequency of large supersaturations with respect to ice is less than indicated by in situ measurements. The simulated TTL cirrus extinction statistics agree with observations (within uncertainties) from both in situ and remote-sensing measurements. We find that the sensitivity of TTL cirrus extinction and ice water content statistics to heterogeneous ice nuclei abundance is relatively weak. Likewise, the simulated occurrence frequencies of TTL cirrus are insensitive to ice nuclei abundance, both in terms of cloud frequency height distribution and regional distribution throughout the tropics.

occurences↗
NASA NTRS1995

ZBLAN Microgravity Study

One of the greatest obstacles with the fluorozirconate ZBLAN (ZrF4-BaF2-LaF3-AIF3-NaF) is the problem of devitrification. Fluoride glasses have a narrow working range and the viscosity is a strong function of temperature. Rates of nucleation and growth of crystals in the glass depend on the viscosity, making these glasses unstable and prone to crystallization. The viscosity of ZBLAN at the drawing temperature is low, usually between two to five poise, so it is difficult to obtain fibers from their preform melts without crystallization. The preforms usually contain heterogeneous nuclei which grow into microcrystallites above the glass transition temperature, T(g). Since microcrystallites in an optical fiber cause extrinsic light scattering losses of the optical signal, fiber drawing must be completed in a short time to minimize the generation of light scattering centers. To keep these losses to a minimum and to fabricate low scattering loss fibers and other optical components, this research deals with the possibility of minimizing crystallite formation by removing the gravitational influence of solutal segregation of the ZBLAN elements. This report reviews the early work on the KC-135 aircraft, the development of the ZBLAN Rocket Experiment, preparations at the White Sands Missile Range, analysis of the flight and ground test results, lessons learned and future experimentation.

Workman, Gary L.↗
DOE OSTI2025

Transformation of TiN to TiNO Films via In-Situ Temperature-Dependent Oxygen Diffusion Process and Their Electrochemical Behavior

Titanium oxynitride (TiNO) thin films represent a multifaceted material system applicable in diverse fields, including energy storage, solar cells, sensors, protective coatings, and electrocatalysis. This study reports the synthesis of TiNO thin films grown at different substrate temperatures using pulsed laser deposition. A comprehensive structural investigation was conducted by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Non-Rutherford backscattering spectrometry (N-RBS), and X-ray absorption spectroscopy (XAS), which facilitated a detailed analysis that determined the phase, composition, and crystallinity of the films. Structural control was achieved via temperature-dependent oxygen in-diffusion, nitrogen out-diffusion, and the nucleation growth process related to adatom mobility. The XPS analysis indicates that the TiNO films consist of heterogeneous mixtures of TiN, TiNO, and TiO2 phases with temperature-dependent relative abundances. The correlation between the structure and electrochemical behavior of the thin films was examined. The TiNO films with relatively higher N/O ratio, meaning less oxidized, were more electrochemically active than the films with lower N/O ratio, i.e., more oxidized films. Films with higher oxidation levels demonstrated enhanced crystallinity and greater stability under electrochemical polarization. These findings demonstrate the importance of substrate temperature control in tailoring the properties of TiNO film, which is a fundamental part of designing and optimizing an efficient electrode material.

Cherono, Sheilah↗
NASA NTRS2016

Thermophysical Properties Along Curiosity's Traverse in Gale Crater, Mars, Derived from the REMS Ground Temperature Sensor

The REMS instrument onboard the Mars Science Laboratory rover, Curiosity, has measured ground temperature nearly continuously at hourly intervals for two Mars years. Coverage of the entire diurnal cycle at 1 Hz is available every few martian days. We compare these measurements with predictions of surface atmosphere thermal models to derive the apparent thermal inertia and thermally derived albedo along the rovers traverse after accounting for the radiative effects of atmospheric water ice during fall and winter, as is necessary to match the measured seasonal trend. The REMS measurements can distinguish between active sand, other loose materials, mudstone, and sandstone based on their thermophysical properties. However, the apparent thermal inertias of bedrock dominated surfaces [approx. 350-550 J m(exp. -2) K(exp. -1 s(exp. -1/2 )] are lower than expected. We use rover imagery and the detailed shape of the diurnal ground temperature curve to explore whether lateral or vertical heterogeneity in the surface materials within the sensor footprint might explain the low inertias. We find that the bedrock component of the surface can have a thermal inertia as high as 650-1700 J m(exp. -2) K(exp. -1) s(exp. -1/2) for mudstone sites and approx. 700 J m(exp. -2) K(exp. -1) s(exp. - 1/2) for sandstone sites in models runs that include lateral and vertical mixing. Although the results of our forward modeling approach may be non-unique, they demonstrate the potential to extract information about lateral and vertical variations in thermophysical properties from temporally resolved measurements of ground temperature.

Vasavada, Ashwin R.↗
DOE OSTI2022

Dilute Alloys Based on Au, Ag, or Cu for Efficient Catalysis: From Synthesis to Active Sites

The development of new catalyst materials for energy-efficient chemical synthesis is critical as over 80% of industrial processes rely on catalysts, with many of the most energy-intensive processes specifically using heterogeneous catalysis. Catalytic performance is a complex interplay of phenomena involving temperature, pressure, gas composition, surface composition and structure over multiple length and time scales. In response to this complexity, the integrated approach to heterogeneous dilute-alloy catalysis reviewed here brings together materials synthesis, mechanistic surface chemistry, reaction kinetics, in-situ and operando characterization, and theoretical calculations in a coordinated effort to develop design principles to predict and improve catalytic selectivity. Dilute alloy catalysts—in which isolated atoms or small ensembles of the minority metal on the host metal lead to enhanced reactivity while retaining selectivity—are particularly promising as selective catalysts. Several dilute alloy materials using Au, Ag and Cu as the majority host element, including more recently introduced support-free nanoporous metals and oxide-supported nanoparticle "raspberry colloid templated (RCT)" materials, are reviewed for selective oxidation and hydrogenation reactions. Progress in understanding how such dilute alloy catalysts can be used to enhance selectivity of key synthetic reactions is reviewed, including quantitative scaling from model studies to catalytic conditions. The dynamic evolution of catalyst structure and composition studied in surface science and catalytic conditions and their relationship to catalytic function are also discussed, followed by advanced characterization and theoretical modeling that have been developed to determine the distribution of minority metal atoms at or near the surface. Furthermore, the integrated approach demonstrates the success of bridging the divide between fundamental knowledge and design of catalytic processes in complex catalytic systems, which can accelerate the development of new and efficient catalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗