Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “phase kinetics”

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 1,315 records · Page 73
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

High-energy X-ray phase analysis of CMAS-infiltrated 7YSZ thermal barrier coatings: Effect of time and temperature

Calcium–magnesium–alumino-silicate (CMAS) particulates enter the aero-engine in a sandy environment, melt and infiltrate into 7 wt% yttria-stabilized zirconia (7YSZ) thermal barrier coatings (TBCs), reducing their lifetime. This leads to chemical degradation in 7YSZ accompanied by tetragonal to monoclinic phase transformation upon cooling. In this work, electron-beam physical vapor deposition coatings were infiltrated with a synthetic CMAS. Here, synchrotron X-ray diffraction measurements show that CMAS infiltration at 1250 °C has about 43% higher monoclinic phase volume fraction (PVF) at the coating surface compared to 1225 °C and remains consistently higher throughout the coating depth. Additionally, the increase in annealing time from 1 to 10 h results in a 31% higher monoclinic phase at the surface. Scanning electron microscopy revealed the presence of globular monoclinic phases corresponding spatially with the above findings. These results resolve the impact of time and temperature on CMAS infiltration kinetics which is important for mitigation.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Unsupervised Learning Based Interaction Force Model for Nonspherical Particles in Incompressible Flows

This project provides a neural network-based interaction force model for gas-solid flows from low to intermediate Reynolds numbers and concentration, which can be linked to MFiX-DEM. We have constructed a database of the interaction force between the irregular-shaped particles using a spherical harmonic method and the fluid phase based on the particle-resolved direct numerical simulation (PR-DNS) with immersed boundary-based gas kinetic scheme. Unsupervised learning method, i.e., variational auto-encoder (VAE) has been applied to extract the primitive shape factors determining the drag force, lifting forces, and torque. The interaction force model has been trained and validated with a simple but effective multi-layer feed-forward neural network: multi-layer perceptron (MLP), which will be concatenated after the encoder of the previously trained VAE for geometry feature extraction for single, irregular particles. We have trained transpose convolutional neural networks with the PR-DNS data to predict the velocity and pressure gradient of the single particle systems and utilized them to calculate drag force of multi-particle systems. This model can provide high computational efficiency because it does not require collecting multiparticle system data from PR-DNS.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2024

Embedded High-Temperature Sensors: Enhancing Thermoelectrical Performance with Refractory Composites Gradient Layers

To monitor the stability of various energy and manufacturing systems, sensors capable of operating at temperatures exceeding 1000 °C in diverse environments for extended durations are essential. However, under harsh conditions, degradation of sensing materials is a concern that can be controlled by embedding the sensors into refractory oxides. Doped-LaCrO3 based composites are excellent candidates for high-temperature sensing applications due to their good thermoelectrical properties. However, chemical reactivity between the conductive phase and the refractory oxides can decrease the performance of the sensors. In this work, it was devised gradient-type protective layers safeguarding conductive phases within embedded thermocouples, which were fabricated and characterized by X-Ray Diffraction for phase development analysis, Scanning Electron Microscopy and Energy-dispersive X-ray spectroscopy for microstructure and cationic interdiffusion kinetics, long-term thermoelectric testing was completed up to 1400 °C. The enhanced performance of these novel sensors addresses a critical limitation, rendering them viable for long-term high-temperature applications.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2021

Applications of Kinetic Methods in Thermal Analysis: A Review

Determining kinetic parameters such as activation energy (Ea), pre-exponential factor (A), rate constants, and reaction order (n) via thermal analysis techniques is important to material synthesis and fabrication, industrial production, biomedicals, energy storage, catalysis, etc. Various kinetic methods based on the non-isothermal techniques have been developed to obtain the kinetic parameters. In this review, we focus on introducing various kinetic methods in non-isothermal analysis and their applications in different reactions, including thermal decomposition, solid-state phase transformation, crystallization, thermal ignition, curing process, etc.

Zhang, Xin↗
NASA NTRS1975

Atmospheric variations - Vacillations and index cycles

Zonal indices, momentum flux, and mean and perturbation kinetic energies of the Southern Hemisphere upper troposphere, derived from the EOLE constant density balloon data set, are found to possess strong 18-23 day variations which are statistically significant to a posteriori levels. Cross-spectra and phase relationships suggest that the variation appears as a barotropic interaction between the middle latitude mean westerlies and ultra large-scale perturbations. Long-period and high-amplitude variations in energy conversion between eddy and mean kinetic energies are found which average out in the long term mean to be very small and positive, consistent with previously measured average hemispheric energetics. Furthermore, the variation is shown to possess an ultra-long wave preference. Examination of two independent data sources, time series of total ozone and stratospheric thickness data from the Selective Chopper Radiometer, suggests that the periodicity is a property of general hemispheric motion rather than just a property of the EOLE data set.

Webster, P. J.↗
NASA NTRS1989

An ion microprobe study of the intra-crystalline behavior of REE and selected trace elements in pyroxene from mare basalts with different cooling and crystallization histories

The effects of crystallization interaction on the trace element zoning characteristics of pyroxenes are analyzed using electron and ion microprobe techniques. Four pigeonite basalts with similar isochemical composition, but different cooling rates and crystallization histories are studied. Pyroxene quadrilaterals displaying crystallization trends are presented. The crystal chemical rationalization of REE zoning, pattern shapes, and abundances are examined. The data reveal that the trace element zoning characteristics in pyroxene and the partitioning of trace elements between pyroxene and the melt are related to the interaction between the efficiency of the crystallization process, the kinetics at the crystal-melt interface, the kinetics of plagioclase nucleation and the characteristics of the crystal chemical substitutions in the pyroxene and the associated crystallizing phase.

Shearer, C. K.↗
NASA NTRS1993

An augmented Young-Laplace model of an evaporating meniscus in a micro-channel with high heat flux

High flux evaporations from a steady meniscus formed in a 2 micron channel is modeled using the augmented Young-Laplace equation. The heat flux is found to be a function of the long range van der Waals dispersion force which represents interfacial conditions between heptane and various substrates. Heat fluxes of (1.3-1.6) x 10(exp 6) W/m(exp 2) based on the width of the channel are obtained for heptane completely wetting the substrate at 100 C. Small channels are used to obtain these large fluxes. Even though the real contact angle is 0 deg, the apparent contact angle is found to vary between 24.8 deg and 25.6 deg. The apparent contact angle, which represents viscous losses near the contact line, has a large effect on the heat flow rate because of its effect on capillary suction and the area of the meniscus. The interfacial heat flux is modeled using kinetic theory for the evaporation rate. The superheated state depends on the temperature and the pressure of the liquid phase. The liquid pressure differs from the pressure of the vapor phase due to capillarity and long range van der Waals dispersion forces which are relevant in the ultra think film formed at the leading edge of the meniscus. Important pressure gradients in the thin film cause a substantial apparent contact angle for a complete wetting system. The temperature of the liquid is related to the evaporation rate and to the substrate temperature through the steady heat conduction equation. Conduction in the liquid phase is calculated using finite element analysis except in the vicinity of the thin film. A lubrication theory solution for the thin film is combined with the finite element analysis by the method of matched asymptotic expansions.

Wayner, P. C., Jr.↗
NASA NTRS1996

Spectra of Baroclinic Inertia-Gravity Wave Turbulence

Baroclinic inertia-gravity (IG) waves form a persistent background of thermocline depth and sea surface height oscillations. They also contribute to the kinetic energy of horizontal motions in the subsurface layer. Measured by the ratio of water particle velocity to wave phase speed, the wave nonlinearity may be rather high. Given a continuous supply of energy from external sources, nonlinear wave-wave interactions among IG waves would result in inertial cascades of energy, momentum, and wave action. Based on a recently developed theory of wave turbulence in scale-dependent systems, these cascades are investigated and IG wave spectra are derived for an arbitrary degree of wave nonlinearity. Comparisons with satellite-altimetry-based spectra of surface height variations and with energy spectra of horizontal velocity fluctuations show good agreement. The well-known spectral peak at the inertial frequency is thus explained as a result of the inverse cascade. Finally, we discuss a possibility of inferring the internal Rossby radius of deformation and other dynamical properties of the upper thermocline from the spectra of SSH (sea surface height) variations based on altimeter measurements.

Glazman, Roman E.↗
NASA NTRS2005

Optimal Sampling of a Reaction Coordinate in Molecular Dynamics

Estimating how free energy changes with the state of a system is a central goal in applications of statistical mechanics to problems of chemical or biological interest. From these free energy changes it is possible, for example, to establish which states of the system are stable, what are their probabilities and how the equilibria between these states are influenced by external conditions. Free energies are also of great utility in determining kinetics of transitions between different states. A variety of methods have been developed to compute free energies of condensed phase systems. Here, I will focus on one class of methods - those that allow for calculating free energy changes along one or several generalized coordinates in the system, often called reaction coordinates or order parameters . Considering that in almost all cases of practical interest a significant computational effort is required to determine free energy changes along such coordinates it is hardly surprising that efficiencies of different methods are of great concern. In most cases, the main difficulty is associated with its shape along the reaction coordinate. If the free energy changes markedly along this coordinate Boltzmann sampling of its different values becomes highly non-uniform. This, in turn, may have considerable, detrimental effect on the performance of many methods for calculating free energies.

Pohorille, Andrew↗
NASA NTRS2010

A New Way that Planets can Affect the Sun

As planets orbit the Sun, the Sun also has to move to keep the total momentum of the solar system constant. The Sun's small orbital motion plus its 25 day rotation about its axis combine to invigorate some solar instabilities. Occasional convection cells at the proper phase in their short life can be strengthened by factors of two or more. This local burst of extra kinetic energy eventually reaches the surface where it can increase the intensity of solar activity. It might explain some reports in the last century of how planetary positions correlate with solar activity. This is the first effect of planets that is large enough to cause a significant response on the Sun.

Wolff, Charles↗
NASA NTRS1986

Reactions of chlorine nitrate with HCl and H2O

The kinetics of the reactions of chlorine nitrate with HCl and H2O are characterized using a static photolysis/Fourier transform infrared spectrophotometer apparatus. For the homogeneous gas-phase reaction with HCl, an upper limit for the rate constant of less than 8.4 x 10 to the -21st, and for the reaction with H2O, a limit of less than 3.4 x 10 to the -21st cu cm/molecule per s, were obtained at 296 + or - 2 K. The yield of HNO3 is almost unity in both cases, and no synergistic effect is noted between HCl and H2O. The kinetic behavior of the reaction with H2O is well described by simple first-order kinetics, while the behavior of the reaction with HCl is described in terms of the Langmuir adsorption isotherm.

Hatakeyama, Shiro↗
DOE OSTI2022

Capturing Carbonation: Understanding Kinetic Complexities through a New Era of Electron Microscopy

Cryogenic plasma focused ion beam (PFIB) electron microscopy analysis is applied to visualizing ex situ (surface industrial) and in situ (subsurface geologic) carbonation products, to advance understanding of carbonation kinetics. Ex situ carbonation is investigated using NIST fly ash standard #2689 exposed to aqueous sodium bicarbonate solutions for brief periods of time. In situ carbonation pathways are investigated using volcanic flood basalt samples from Schaef et al. (2010) exposed to aqueous CO 2 solutions by them. The fly ash reaction products at room temperature show small amounts of incipient carbonation, with calcite apparently forming via surface nucleation. Reaction products at 75° C show beginning stages of an iron carbonate phase, e.g., siderite or ankerite, common phases in subsurface carbon sequestration environments. This may suggest an alternative to calcite in carbonation low calcium-bearing fly ashes. Flood basalt carbonation reactions show distinct zonation with high calcium and calcium-magnesium bearing zones alternating with high iron-bearing zones. The calcium-magnesium zones are notable with occurrence of localized pore space. Oscillatory zoning in carbonate minerals is distinctly associated with far-from-equilibrium conditions where local chemical environments fluctuate via a coupling of reaction with transport. The high porosity zones may reflect a precursor phase (e.g., aragonite) with higher molar volume that then “ripens” to the high-Mg calcite phase-plus-porosity. These observations reveal that carbonation can proceed with evolving local chemical environments, formation and disappearance of metastable phases, and evolving reactive surface areas. Together this work shows that future application of cryo-PFIB in carbonation studies would provide advanced understanding of kinetic mechanisms for optimizing industrial-scale and commercial-scale applications.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Redox-Induced Microstructure and Phase Dynamics in Nickel: Insights from In Situ Synchrotron X-ray Diffraction

Using in situ synchrotron X-ray diffraction, we interrogate the microstructural and phase evolution of polycrystalline nickel (Ni) during redox cycling in O 2 , H 2 , and H 2 O environments. Oxidation in O 2 promotes strong (111) texturing in both the NiO overlayer and the underlying Ni substrate. However, this crystallographic alignment is lost following reduction in H 2 and subsequent reoxidation, demonstrating irreversible microstructural changes. H 2 exposure leads to proton dissolution into the Ni lattice, triggering a localized phase transition from face-centered cubic (FCC) to hexagonal close-packed (HCP) Ni in hydrogen-saturated regions. In H 2 O-containing atmospheres, dissociative H 2 O adsorption produces protons that permeate the NiO layer, forming γ-NiOOH within the NiO lattice and HCP Ni beneath the NiO overlayer as protons accumulate. Kinetic analysis via the Johnson-Mehl-Avrami–Kolmogorov model uncovers distinct growth mechanisms: preoxidized Ni surfaces follow one-dimensional (1D) kinetics for NiO, γ-NiOOH, and HCP growth, whereas pristine Ni exhibits three-dimensional (3D) kinetics due to island-like nucleation and growth of NiO. Furthermore, these results highlight the critical interplay between H 2 O dissociation, hydrogen permeation, and redox-driven phase transformations, with practical implications in engineering nickel-based catalysts and hydrogen storage systems through controlled microstructural and phase evolution.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Revisiting the capacity-fading mechanism of P2-type sodium layered oxide cathode materials during high-voltage cycling

We report P2-type sodium layered oxide cathode (Na 2/3 Ni 1/3 Mn 2/3 O 2 , P2-NNMO) has attracted great attention as a promising cathode material for sodium ion batteries because of its high specific capacity. However, this material suffers from a rapid capacity fade during high-voltage cycling. Several mechanisms have been proposed to explain the capacity fade, including intragranular fracture caused by the P2-O2 phase transion, surface structural change, and irreversible lattice oxygen release. Here we systematically investigated the morphological, structural, and chemical changes of P2-NNMO during high-voltage cycling using a variety of characterization techniques. It was found that the lattice distortion and crystal-plane buckling induced by the P2-O2 phase transition slowed down the Na-ion transport in the bulk and hindered the extraction of the Na ions. The sluggish kinetics was the main reason in reducing the accessible capacity while other interfacial degradation mechanisms played minor roles. Our results not only enabled a more complete understanding of the capacity-fading mechanism of P2-NNMO but also revealed the underlying correlations between lattice doping and the moderately improved cycle performance.

25 ENERGY STORAGE↗
DOE OSTI2025

Microstructural, Oxidation, and Mechanical Behavior of NbTi-Based Refractory Alloys with 5 to 10 Pct Co, Cr, and Ni Additions

NbTi-based refractory alloys with additions of Co, Cr, and Ni represent an interesting medium-entropy alloy system with potential for protective oxide film formation, high strength, and ductility. This study investigates the microstructural evolution, oxidation behavior, and mechanical properties of NbTi-based alloys containing 5 to 10 at. pct Co, Cr, and Ni. CALPHAD predictions suggest that this composition range can be heat treated to obtain a predominantly body-centered cubic matrix phase. Mechanical properties, including microhardness, yield strength, maximum strength, and specific strength are evaluated through isothermal compression tests conducted between room temperature and 800 °C. The oxidation kinetics of these alloys are assessed through discontinuous oxidation tests. Parabolic oxidation kinetics were observed for NbTi–10Ni and NbTi–5Co, while linear oxidation kinetics were found for NbTi–10Cr and NbTi–10(CoCrNi). Microstructures and oxide layers are characterized using X-ray diffraction, electron backscatter diffraction, energy-dispersive X-ray spectroscopy, and scanning electron microscopy. All alloys exhibit significant mechanical softening between room temperature and 800 °C, with elastic-perfectly plastic flow observed at 800 °C. The addition of 10 pct Cr to NbTi resulted in two BCC phases up to 1050 °C, conflicting with CALPHAD predictions of a single-phase solid solution at this temperature, and resulting in higher flow stress at 800 °C. NbTi–10(CoCrNi) exhibited the lowest flow stress at 800 °C despite having more ‘cocktail effect’ potential and insufficient molar fractions of Co, Cr, or Ni to form a desirable protective oxide film.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Performance prediction applying different reduced turbulence models to the SMART tokamak

The SMall Aspect Ratio Tokamak (SMART) is currently being commissioned at the University of Seville and will be able to compare the performance of positive and negative triangularity plasmas at low aspect ratio. Predictive simulations have been performed for different machine scenarios and heating schemes using the TRANSP code. The objectives of these simulations are to predict the parameters expected in positive triangularity plasmas, to guide diagnostic development, and to validate transport models. Several reduced turbulence models have been used to predict electron and ion temperatures for the operational phase 2. All models provide similar results from approximately mid-radius to the separatrix but important discrepancies are found in the core region. These positive triangularity results are compared with experiments from a similar size machine like GLOBUS-M2. The multi-mode model (MMM) shows the best agreement. Simulations with different boundary conditions have been performed and no strong differences have been observed between them. The impact of neutral beam injection (NBI) on the predicted profiles has also been addressed. Rotation reduces turbulence levels so higher temperatures are achieved when included in the simulations. Studying the different contributions to the thermal diffusivities, it is observed that electron temperature gradient (ETG) turbulence dominates at the plasma core while micro-tearing modes (MTM) dominate at the edge in the electron channel. In the ion channel, the neoclassical contribution is dominant at the core and at the very edge while the Weiland component, which includes ion temperature gradient mode (ITG), trapped electron mode (TEM), kinetic ballooning mode (KBM), peeling mode (PM) and collisionless and collision dominated magnetohydrodynamic (MHD) modes governs the mid-radius region. For phase 3, two plasmas with different electron densities have been studied. The case with lower density matches well a specific discharge of GLOBUS-M2. The higher density plasma shows high performance with β N ≈ 3.8.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Discrimination of xylene isomers in a stacked coordination polymer

The separation and purification of xylene isomers is an industrially important but challenging process. Developing highly efficient adsorbents is crucial for the implementation of simulated moving bed technology for industrial separation of these isomers. Herein, we report a stacked one-dimensional coordination polymer {[Mn(dhbq)(H 2 O) 2 ], H 2 dhbq = 2,5-dihydroxy-1,4-benzoquinone} that exhibits an ideal molecular recognition and sieving of xylene isomers. Its distinct temperature-adsorbate–dependent adsorption behavior enables full separation of p -, m -, and o -xylene isomers in both vapor and liquid phases. The delicate stimuli-responsive swelling of the structure imparts this porous material with exceptionally high flexibility and stability, well-balanced adsorption capacity, high selectivity, and fast kinetics at conditions mimicking industrial settings. This study may offer an alternative approach for energy-efficient and adsorption-based industrial xylene separation and purification processes.

Science & Technology - Other Topics↗
DOE OSTI2023

Transport and Imaging of Novel Phases of Moiré Quantum Matter

Moiré materials open an entirely new platform for exploring the interplay between band structure, interactions, symmetry and topology. Strong effects of interaction can result from antiferromagnetic correlations as is commonly found in high temperature superconductors. Alternatively, the effects of interactions can be strengthened by reducing the role of kinetic energy as is commonly done in quantum Hall systems. Interestingly, moiré materials are a new class of materials where both types of effects can be present simultaneously, even at zero magnetic field, leading to a plethora of new correlated topological phases. Here we plan to harness the expertise of our groups in synthesis, fabrication, and novel measurement techniques to unravel and elucidate some of the mysteries of moiré materials. Our goal in this proposal has been to deepen our understanding of correlated phases in moiré materials using a variety of experimental tool developed in the PI’s labs. We used thermodynamic probes based on local and global electrostatic sensing to provide direct information on compressibility, entropy, magnetization and topology. Revealing the fundamental principles of correlated topological matter may pave the way towards a new class of materials with superior electronic characteristics with possible application in quantum science, engineering and energy harvesting platforms.

36 MATERIALS SCIENCE↗