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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.
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Acoustic interferometric determination of sound velocity in saturated carbon dioxide vapors with ultrasonic frequency of 500 kHz
Evidence from carbonaceous chrondrites points to refractory oxides in the system CaO-MgO-Al2O3-TiO2-SiO2-Fe-O as being among the earliest phases to condense from the solar nebula. It is necessary to establish the equilibrium relationships between the relevant crystalline and amorphous phases before the chemical constraints can be meaningfully applied to models of solar system history. Preliminary experiments on earth show that such experiments are feasible. Earth-based experiments suffer from several unavoidable problems. These problems can be overcome by experimentation in the Space Station where the experiments can be conducted under near static pressure conditions and where total pressure equals the sum of controlled hydrogen and oxygen pressures and can be controlled for periods exceeding several hours.
Many MgO-rich shergottites have olivine phenocrysts and a natural question to ask is if any of these represent primary melts from the martian mantle. To answer this requires knowledge of olivine liquid equilibrium in appropriate magma compositions. Because olivine-phyric shergottites represent either primary liquids or liquids that have been modified by fractionation or accumulation of olivine (or other phases), the equilibrium (and its Kd) 2MgO (liq) + Fe2SiO4 (olivine) = 2FeO (liq) + Mg2SiO4 (olivine), can be used to evaluate whether the olivine-bearing rocks represent liquids.
Here, this article explores technical challenges and potential methodologies for understanding electrochemical Reactive CO 2 Capture (RCC) mechanisms. RCC offers potential energy cost advantages by directly converting captured CO 2 into fuels and chemicals, unlike traditional carbon capture and utilization (CCU) processes that require sequential capture, concentration, and compression. However, direct conversion of captured CO 2 introduces complexity due to additional equilibrium buffer reactions, making it challenging to identify active species for reduction in electrochemical studies. This article discusses methods to integrate transport, thermodynamics, and kinetics concepts to identify active carbon sources in RCC. Vapor‐Liquid Equilibrium (VLE) and transport models are validated against experimental results obtained in a gastight rotating cylinder electrode reactor and are shown as useful tools for studying RCC in heterogeneous electrocatalysts across different capture agents, solvents, and temperatures. This article establishes an experimental framework for advancing research in electrochemical RCC.
Some experimental spacecraft use superconducting sensors for gyro read-out and so must be maintained at a very low temperature. The boil-off from the cryogenic liquid used to cool the sensors can also be used, as the Gravity Probe B (GP-B) spacecraft does, as propellant to maintain attitude control and drag-free operation of the spacecraft. The cryogenic liquid for such spacecraft is, however, susceptible to both slosh-like motion and non-axisymmetric configurations under the influence of various kinds of gravity jitter and gravity gradient accelerations. Hence, it is important to quantify the magnitude of the liquid-induced perturbations on the spacecraft. We use the example of the GP-B to investigate such perturbations by numerical simulations. For this spacecraft disturbances can be imposed on the liquid by atmospheric drag, spacecraft attitude control maneuvers, and the earth's gravity gradient. More generally, onboard machinery vibrations and crew motion can also create disturbances. Recent studies suggest that high frequency disturbances are relatively unimportant in causing liquid motions in comparison to low frequency ones. The results presented here confirm this conclusion. After an initial calibration period, the GP-B spacecraft rotates in orbit at 0.1 rpm about the tank symmetry axis. For this rotation rate, the equilibrium liquid free surface shape is a 'doughnut' configuration for all residual gravity levels of 10(exp -6) g(sub 0) or less, as shown by experiments and by numerical simulations; furthermore, the superfluid behavior of the 1.8 K liquid helium used in GP-B eliminates temperature gradients and therefore such effects as Marangoni convection do not have to be considered. Classical fluid dynamics theory is used as the basis of the numerical simulations here, since Mason's experiments show that the theory is applicable for cryogenic liquid helium in large containers. To study liquid responses to various disturbances, we investigate and simulate three levels of gravity jitter (10(exp -6), 10(exp -7), and 10(exp -8) g(sub 0)) each at three predominant frequencies (0.1, 1.0, and 10 Hz), combined with a gravity gradient appropriate for the GP-B orbit. Dynamical evolution of sloshing dynamics excited fluid forces and torque fluctuations exerted on the dewar container driven by the combined gravity gradient and jitter accelerations are also investigated and simulated.
An experimental investigation was conducted to determine the damping of the fundamental antisymmetric mode of oscillation of liquids contained in an oblate spheroidal tank. The decay of the fundamental mode was studied for a range of liquid depths in tanks with and without baffles. In the investigation of baffle effects, ring and cruciform baffles of various sizes were fixed at different locations within the tank. Data presented show the variation of the damping factor with tank fullness and with baffle type, width, location, and orientation as well as the effects of the amplitude of the liquid oscillations and of small variations in the liquid kinematic viscosity on the damping factor. The results of the investigation indicate that the addition of ring baffles to the tank results in an increase in the available effective damping when the baffle plane is in a region near the equilibrium liquid surface, and that cruciform baffles are effective in the damping of the fundamental mode in the near-empty tank. No apparent changes in damping for the tanks having ring baffles were observed as the kinematic viscosity of the liquid was varied over a small range.
In this work, we use state-of-the-art X-ray scattering and molecular dynamics to analyze amine-water mixtures that show the unusual lower critical solution temperature (LCST) behavior. The goal is to provide direct experimental evidence for the entropy-lowering molecular cluster formation hypothesized as necessary for LCST behavior. Differential wide-angle X-ray scattering and pair distribution analysis and small-angle X-ray scattering measurements were combined with molecular modeling and liquid-liquid equilibrium measurements, revealing direct experimental evidence for the hypothesis. However, the response of the amine phase to accommodating water is even more subtle than the simple hypothesis suggests, with the formation of robust nanoscale reverse micelles. The techniques developed in this paper can be expected to yield insights in the use of temperature-switchable liquids in solvent extraction and other separations, and the stabilization of organelles in living cells that do not have physical membranes but do require compositional gradients to operate.
Aerosol jet printing (AJP) is a digital additive manufacturing technique for hybrid and conformal electronics, where its contactless deposition readily enables patterning over 3D surface topography. However, the complexity of aerosol transport physics makes deposition rate sensitive to process variability, hindering widespread industry adoption. Light scattering measurements have recently been demonstrated as a capable tool for measuring deposition rate in real time, enabling closed-loop control and in-situ qualification frameworks. These inline optical measurements present further opportunity as a diagnostic tool to understand the effects of secondary process parameters affecting vapor–liquid equilibrium and heat and mass transport during deposition. Downstream of the optical measurement cell, changing the sheath gas flow rate, increasing temperature via an inline heater, and adding solvent vapor via a sheath gas bubbler were observed to alter drying physics during sheath-collimation, and thereby impaction efficiency. Further upstream, the introduction of solvent vapor via a carrier gas bubbler and liquid build-up in the printhead were seen to affect the quantitative relationship between the light scattering data and the true deposition rate. Using this information, tightened controls of meaningful secondary parameters were implemented to improve the batch-to-batch consistency for printing a dielectric ink. In addition to advancing AJP process reliability for production, this work demonstrates the capability of inline optical measurements to provide insight into process physics and deconvolute competing mechanisms that underly variability.
Based on the activity coefficient – fugacity coefficient approach, a rigorous thermodynamic modeling study is presented for accurate correlation of vapor-liquid equilibrium data of aqueous solutions of acetic acid (293 to 391 K), butyric acid (325 to 436 K), lactic acid (378 to 409 K), and acetic acid + butyric acid binary mixture (358 to 421 K). In addition, the pH data of the three aqueous, single carboxylic acid solutions were measured at 298 to 328 K and successfully correlated. Given that these aqueous carboxylic acid solutions exhibit various degrees of association behavior in both vapor and liquid phases, the thermodynamic models considered for this study include the Redlich-Kwong equation of state (RK-EoS) and the Hayden-O’Connell equation of state (HOC-EoS) for the vapor phase fugacity coefficients and the electrolyte non-random two-liquid model (eNRTL) and the association electrolyte non-random two-liquid model (AeNRTL) for the liquid phase activity coefficients. The combination of the HOC-EoS for the vapor phase and the AeNRTL model for the liquid phase is found to provide the best correlation results, consistent with the fact that the HOC-EoS and the AeNRTL model explicitly account for association behaviors in the vapor phase and the liquid phase, respectively.
Rapid and robust convergence of a process flowsheet is critical to enable large-scale simulations that address core scientific questions related to process design, optimization, and sustainability. However, due to the highly coupled and nonlinear nature of chemical processes, efficiently solving a flowsheet remains a challenge. In this work, we show that graph representations of the underlying physical phenomena in unit operations may help identify potential avenues to systematically reformulate the network of equations and enable more robust topology-based convergence of flowsheets. To this end, we developed graph abstractions of the governing equations of vapor-liquid and liquid-liquid equilibrium separation equipment. These graph abstractions consist of a mesh of interconnected variable nodes and equation nodes that are systematically generated through PhenomeNode, a new open-source library in Python developed in this study. We show that partitioning the graph into separate mass, energy, and equilibrium subgraphs can help decouple nonlinearities and guide decomposition algorithms. By employing the graph abstraction on an industrial separation process for separating glacial acetic acid from water, we implemented a new block decomposition scheme in BioSTEAM and demonstrated that this can accelerate convergence over a traditional sequential modular approach.
Liquid–liquid extraction (LLE) is a widely used technique for the separation and purification of liquid-phase products with applications in various industries, including pharmaceuticals, petrochemicals, and renewable chemistry. A critical step in the design of an LLE process is the selection of appropriate solvents. This study presents a new methodology for identifying solvent mixtures for bioproduct separation using Bayesian experimental design (BED). Motivated by the need for environmentally friendly and effective separation methods, we address the challenge of selecting solvent systems that balance separation efficiency, selectivity, and environmental impact while also tackling the difficulty of separating multiple bioproducts using complex solvent systems. Our approach specifically seeks to predict product partition coefficients (log10 Kp values) as thermodynamic parameters underlying solvent selection. The iterative approach integrates Bayesian optimization with experimental measurements to guide solvent selection and leverages COSMO-RS simulations to enhance high-throughput experimentation. Using the design of solvent systems for the separation of lignin-derived aromatic products via centrifugal partition chromatography (CPC) as a case study, we show that within seven iterations/cycles of the methodology, we can identify new mixtures of green solvents that align with CPC design principles. Furthermore, these results demonstrate the efficacy of the BED framework in optimizing green solvent systems for complex separations, highlighting the potential of this method to advance the field of green chemistry and contribute to the development of sustainable industrial processes.
The activity of aqueous-based carbon dioxide reduction (CO 2 R) reactions is often limited by the solubility of CO 2 . The addition of amines can increase the total dissolved carbon in water through the formation of bicarbonate and carbamate species, which has been used to a great effect to capture CO 2 from dilute streams. Here, in this study, we explore the effect of 12 primary and secondary amines of varying Brønsted basicity, steric profile, and hydrogen-bonding capabilities on the aqueous CO 2 R to CO activity of a molecular Ni(cyclam)Cl 2 catalyst with a Hg electrode. Addition of some of the amines results in greater activity and selectivity for CO production compared to equivalent aqueous solutions without added amines. Under optimal conditions (0.4 M 3-amino-propionitrile), there is an over sevenfold increase in partial current density and greater selectivity for CO compared to equivalent conditions with no amine. Interestingly, the increase in activity did not correlate to any single property across the 12 amines. To elucidate the effect of the amine additives on catalysis, we used vapor–liquid equilibrium modeling (VLE), 13 C NMR spectroscopy, and computational analysis to determine the carbon speciation of the solutions. These results indicate that for amines without ethylalcohol functionalities, CO 2 R activity correlates with carbamate concentration, which is in turn governed by amine basicity and steric effects. However, this correlation does not persist for amines with ethylalcohol functionalities, which can form more stable carbamates through intramolecular-hydrogen bonding. These studies demonstrate that amine additives can enhance aqueous CO 2 R activity and selectivity and describe amine properties that lead to these higher performance metrics.
Achieving atomic-level understanding of crystallization of molten salts is of importance to a wide range of technological applications. Recent work [Fan et al., Proc. Natl. Acad. Sci. USA 122, e2425702122 (2025)] revealed that crystal nucleation in molten LiF salt is a multistage process according to the molecular-dynamics (MD) simulations based on an atomic cluster expansion (ACE) machine-learning interatomic potential (MLIP). In order to understand the influence of increasing cation size on nucleation pathways and nucleation rates of molten fluoride salts, here we develop two new ACE MLIPs for NaF and KF. The two ACE MLIPs feature DFT-SCAN-level accuracy for liquid and multiple solid polymorphs over a wide temperature (0–2000 K) and pressure (0–100 GPa) range, and also reproduce well a number of experimental data for solid and liquid equilibrium properties. The efficiency of the two ACE MLIPs enable million-atom-scale or microsecond-scale MD simulations. The two general-purpose ACE MLIPs are expected to be useful for atomistic simulations for different purposes, in addition to studying crystallization of molten NaF and KF salts.
Linear regression analysis of water pressure and critical temperature in plagioclase-silicate liquid equilibrium
Geothermometer based on plagioclase-magmatic liquid equilibrium
Some problems associated with the automatic control of liquid metal and plasma systems under conditions of weightlessness are examined, with particular reference to the problem of stability of liquid equilibrium configurations. The theoretical fundamentals of automatic control of processes in electrically conducting continuous media are outlined, and means of using electromagnetic fields for simulating technological processes in a space environment are discussed.
This paper describes the steps of a two-step zone purification procedure for completed minicells filled with ultrahigh-purity succinonitrile (SCN) in which the CNS is under its own vapor pressure. The solid-liquid equilibrium, as determined by melting and freezing point measurements, is therefore considered to be a realization of the triple-point. The freezing-point plateaus measured at a variety of bath temperatures demonstrated both the fundamental reproducibility of the measurement for a given sample and the lack of dependence of that measurement on the bath temperature which controls the freezing rate. The measurement reproducibility and the sample consistency indicate that the method described is indeed suitable for the preparation of pure material which can be used for the purposes of thermistor and thermometer calibration at 58.0796 + or - 0.0015 C.
Eleven splits from the mafic-mineral-rich part of anorthosite 60025 were studied in order to establish the exact nature and causes of compositional variations in the minerals of lunar ferroan anorthosites. All splits were analyzed by INAA, and five were studied intensively by petrologic techniques. All splits were found to have similar cataclastic textures and show textural evidence of at least two episodes of deformation. The whole-rock split contains mafic minerals having a wide range of compositions and is probably polymict. It is suggested that the rare-earth patterns for all splits can be duplicated safactorily, assuming that the equilibrium liquids had flat, or nearly flat, chondrite-normalized rare-earth patterns. The plagioclases in all splits were found to be identical. Data obtained indicate that in ferroan anorthosites An content in plagioclase and mg' of associated mafic minerals are not strongly correlated.