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At least 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Grain boundary segregation beyond the dilute limit: Separating the two contributions of site spectrality and solute interactions

Solute segregation at grain boundaries (GBs) is known to have a profound impact on material properties, and as such is becoming routinely used as an element in alloy design. Beyond the dilute limit, the extent of solute GB segregation is known to be concentration dependent. Using hybrid Monte Carlo/Molecular Statics simulations of Mg segregation in Al, in this work we decouple the two contributions to this composition dependence: (i) spectrality of atomic environments at the boundary and (ii) solute-solute interactions. Although only contribution (ii) is typically considered in the literature, we argue that both contributions are equally important to understand concentration dependence and correctly quantify GB solute segregation in a binary alloy. Finally, a thermodynamic segregation isotherm is outlined that accounts for both the spectrality of grain boundary sites and solute-solute interactions. Unlike classical isotherms like those of McLean or Fowler-Guggenheim, which can be successfully fitted to GB segregation data only over a limited range of composition and temperature, our proposed model is shown to be accurate across the composition-temperature space.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A simple method to measure the isosteric energy of adsorption

The effect of temperature on water vapour desorption isotherms can be described simply using the Clausius-Clapeyron equation and the isosteric energy of adsorption, the latter conventionally estimated using two (or more) isotherms obtained at different temperatures. This approach has some disadvantages, however, and this article puts forward a simple alternative methodology for characterising this isosteric energy experimentally. Our method is based on monitoring the relative humidity of a cementitious material heated under sealed conditions. The evolution of the relative humidity as a function of temperature makes it possible to directly evaluate the isosteric energy. In practice, the tests are performed using a cell of the type that is used for self-desiccation studies.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Macroscopic and microscopic behaviors of Mn(II) (ad)sorption to goethite with the effects of dissolved carbonates under anoxic conditions

Manganese and its compounds have been extensively researched because of their far-reaching roles in a wide range of biogeochemical processes in natural systems. The (ad)sorption behavior of Mn(II), however, is poorly understood despite its important role as the primary reaction step for surface-catalyzed Mn(II) oxidation that is the principal abiotic process forming various Mn (oxyhydr)oxides in nature. Here, we systematically examined Mn(II) (ad)sorption to one of the most common natural sorbents, goethite, in oxygen- and carbonate-free systems. Traditional sorption edge and isotherm experiments were conducted by varying sorbate-to-sorbent ratio (0.027–15 μmol∙m -2 ) and solution pH (pH 5.0–9.0). The effects of dissolved carbonates on Mn(II) sorption were also assessed in a range of naturally prevalent concentrations (0.5–10 mM NaHCO 3 ). The Mn(II) uptake on goethite followed a typical Langmuir isotherm in the absence of dissolved carbonates, with increasing maximum adsorption capacities (Γ max ) from 0.19 at pH 6.5 to 3.4 μmol∙m -2 at pH 9.0. The presence of dissolved carbonates raised the extent of Mn(II) adsorption, which appeared to be directly correspondent to that of the adsorption of dissolved carbonates. Extended X-ray absorption fine structure (EXAFS) analysis indicated that Mn(II) predominantly formed inner-sphere binuclear bidentate surface complexes. Mn(II) uptake became deviated from the Langmuir model and showed a clear indication of surface precipitation when the Mn(II) sorption density (Γ) exceeded a threshold value in a given solution composition. This secondary Mn(II) phase was identified as rhodochrosite using X-ray diffraction (XRD) and transmission electron microscope (TEM). Furthermore, it would be plausible that a minor fraction of adsorbed Mn(II) coexisted with the secondary rhodochrosite according to a linear combination fitting (LCF) of the X-ray absorption near edge structure (XANES) spectra of Mn reference and samples. These systematic investigations of the macroscopic and microscopic behaviors of Mn(II) (ad)sorption to goethite provide a critical avenue for disentangling surface-catalytic Mn(II) oxidation processes, which ultimately lead to the formation of diverse Mn (oxyhydr)oxides in the environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

On the Thermodynamic Condition for Adsorption Azeotropes

Adsorption azeotropy is a common phenomenon in mixed-gas adsorption equilibria. Since the first literature report of binary adsorption azeotropes in 1933, numerous studies investigated the thermodynamic conditions for adsorption azeotropes but failed to reach definitive conclusions. Based on the generalized Langmuir isotherm model for multicomponent adsorption equilibria which takes into account the vacant site as part of the adsorbed phase, this study presents the thermodynamic condition for adsorption azeotropes as derived from the generalized Langmuir isotherm to be the equality of the ratios of adsorbed phase activity coefficient γi and adsorption equilibrium constant $K$$^{o}_{i}$ for the two adsorbates in the binary 1–2 adsorption system, i.e., γ 1 /$K$$^{o}_{1}$ = γ 2 /$K$$^{o}_{2}$. This adsorption azeotropic condition is analogous to the vapor–liquid equilibrium azeotropic condition, i.e., the equality of the products of liquid phase activity coefficient and saturation vapor pressure Pisat for the two components, i.e., γ 1 $P$$^{sat}_{1}$ = γ 2 $P$$^{sat}_{2}$. We validated the thermodynamic condition for adsorption azeotropes with 14 azeotrope-forming adsorption systems in this study. As a result, we investigated the effects of the pressure, temperature, and adsorbed phase nonideality on azeotrope formation.

42 ENGINEERING↗
DOE OSTI2025

The Temperature Dependence of the Langmuir Adsorption Model for a Single-Site Metal–Organic Framework

The single-site Langmuir adsorption model, also known as the Langmuir isotherm equation, is one of the simplest possible descriptions of adsorption phenomena, and yet finds widespread applicability across a range of disciplines. In its simplest form, it is deployed to treat adsorption equilibria at constant temperature (i.e., along isotherms); however, at the heart of its derivation is a more general class of models that each incorporate an explicit temperature dependence, subject to assumptions about the spatial/translational degrees of freedom of the adsorbed species. In this work, measurements of the temperature dependence of supercritical adsorption of H 2 on a single-site metal-organic framework (MOF) are presented, and fitted using a range of Langmuir models with distinct treatments of degrees of freedom in the adsorbed phase. Surprisingly, all of the models can be used to adequately represent the measured data, despite yielding significantly different values for binding energy and the temperature dependence of the isosteric enthalpy of adsorption (i.e., the isosteric heat, qst). Furthermore, a critical finding is that the mean-temperature isosteric enthalpy of adsorption remains consistent across all models within experimental error, highlighting its reliability for evaluating adsorption thermodynamics.

08 HYDROGEN↗
DOE OSTI2022

Liquid-Phase Effects on Adsorption Processes in Heterogeneous Catalysis

Aqueous solvation free energies of adsorption have recently been measured for phenol adsorption on Pt(111). Endergonic solvent effects of ~1 eV suggest solvents dramatically influence a metal catalyst’s activity with significant implications for the catalyst design. However, measurements are indirect and involve adsorption isotherm models, which potentially reduces the reliability of the extracted energy values. Computational, implicit solvation models predict exergonic solvation effects for phenol adsorption, failing to agree with measurements even qualitatively. In this study, an explicit, hybrid quantum mechanical/molecular mechanical approach for computing solvation free energies of adsorption is developed, solvation free energies of phenol adsorption are computed, and experimental data for solvation free energies of phenol adsorption are reanalyzed using multiple adsorption isotherm models. Explicit solvation calculations predict an endergonic solvation free energy for phenol adsorption that agrees well with measurements to within the experimental and force field uncertainties. Computed adsorption free energies of solvation of carbon monoxide, ethylene glycol, benzene, and phenol over the (111) facet of Pt and Cu suggest that liquid water destabilizes all adsorbed species, with the largest impact on the largest adsorbates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Modeling ethanol/water adsorption in all-silica zeolites using the real adsorbed solution theory

A comprehensive set of single-component and binary isotherms were collected for ethanol/water adsorption into the siliceous forms of 185 known zeolites using grand-canonical Monte Carlo simulations. Using these data, a systematic analysis of ideal/real adsorbed-solution theory (IAST/RAST) was conducted and activity coefficients were derived for ethanol/water mixtures adsorbed in different zeolites based on RAST. It was found that activity coefficients of ethanol are close to unity while activity coefficients of water are larger in most zeolites, indicating a positive excess free energy of the mixture. This observation can be attributed to water/ethanol interactions being less favorable than water/water interactions in the single-component adsorption of water at comparable loadings. The deviation from ideal behavior can be highly structure-dependent but no clear correlation with pore diameters was identified. Furthermore, our analysis also demonstrates the following: (1) accurate unary isotherms in the low-loading regime are critical for obtaining physically sensible activity coefficients; (2) the global regression scheme to solve for activity model parameters performs better than fitting activity models to activity coefficients calculated locally at each binary state point; and (3) including the dependence on adsorption potential offers only a minor benefit for describing binary adsorption at the lowest fugacities. Finally, the Margules activity model was found incapable of capturing the non-ideal adsorption behavior over the entire range of fugacities and compositions in all zeolites, but for conditions typical of solution-phase adsorption, RAST predictions using zeolite-specific or even bulk Margules parameters provide an improved description compared to IAST.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Phosphorus sorption and its environmental predictors across pantropical forest soils sampled over the past decade

Tropical forest productivity is frequently constrained by soil phosphorus (P) availability, yet global Land Surface Model (LSM), which are used to simulate ecosystem processes, still represent P cycling in tropical regions only in a limited way, largely because of scarce observational data. Phosphorus adsorption and desorption of dissolved inorganic P to and from soil minerals (hereafter termed sorption), is an important process for predicting how much P is available to plants. This dataset was created to improve predictions of soil P sorption in tropical soils by identifying the isotherm equation that best describes pantropical soils. It includes raw measurements of environmental variables, such as soil properties and climate, together with P sorption data collected from 40 forest soil pits from 9 Forest Global Earth Observatory (ForestGEO) sites across 7 tropical countries during 2018-2022. The data are organized by site, country, and continent. Each site may include several soil pits. For each pit, P sorption was measured across a range of soil P concentrations to build sorption isotherm curves, typically with about 6 to 8 measurements per curve. While sorbed P varies across these concentration levels, the other environmental variables remain constant at the plot level.

Aluminum oxide↗
DOE OSTI2024

Transforming an Ionic Conductor into an Electronic Conductor via Crystallization: In Situ Evolution of Transference Numbers and Structure in (La,Sr)(Ga,Fe)O 3–x Perovskite Thin Films

Mixed-conducting perovskites are workhorse electrochemically active materials, but typical high-temperature processing compromises their catalytic activity and chemo-mechanical integrity. Low-temperature pulsed laser deposition of amorphous films plus mild thermal annealing is an emerging route to form homogeneous mixed conductors with exceptional catalytic activity, but little is known about the evolution of the oxide-ion transport and transference numbers during crystallization. Here the coupled evolution of ionic and electronic transport behavior and structure in room-temperature-grown amorphous (La,Sr)(Ga,Fe)O 3-x films as they crystallize is explored. In situ ac-impedance spectroscopy with and without blocking electrodes, simultaneous capturing-synchrotron-grazing-incidence X-ray diffraction, dc polarization, transmission electron microscopy, and molecular dynamics simulations to evaluate isothermal and non-isothermal crystallization effects and the role of grain boundaries on transference numbers is combined. Ionic conductivity increases by ≈2 orders of magnitude during crystallization, with even larger increases in electronic conductivity. Consequently, as crystallinity increases, LSGF transitions from a predominantly ionic conductor to a predominantly electronic conductor. The roles of evolving lattice structural order, microstructure, and defect chemistry are examined. Grain boundaries appear relatively nonblocking electronically but significantly blocking ionically. The results demonstrate that ionic transference numbers can be tailored over a wide range by tuning crystallinity and microstructure without having to change the cation composition.

36 MATERIALS SCIENCE↗
DOE OSTI2022

How Reproducible are Surface Areas Calculated from the BET Equation?

Abstract Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer–Emmett–Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of micro‐ and mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already‐measured raw adsorption isotherms were provided to sixty‐one labs, who were asked to calculate the corresponding BET areas. This round‐robin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called “BET surface identification” (BETSI), expands on the well‐known Rouquerol criteria and makes an unambiguous BET area assignment possible.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Thermal Dynamics and Lithium Plating Detection in High‐Power Li‐Ion Batteries for eVTOL Applications

The rapid electrification of aerial transportation is driving the need for high‐performance Li‐ion batteries that can operate reliably under stringent thermal and safety constraints. The unique mission profile of electric Vertical Take‐off and Landing (eVTOL) aircraft necessitates a focused investigation into the thermal behavior and safety characteristics of these batteries. Here, in this study, operando isothermal microcalorimetry is employed to examine the thermal evolution of Li‐ion batteries under cycling conditions representative of eVTOL operations. These findings reveal that high‐power discharge events—such as those during take‐off and landing—shift the thermal response toward exothermic behavior, in contrast to the typically endothermic response expected under near‐equilibrium cycling conditions. Additionally, the results suggest that advanced electrolyte formulations may help suppress excess heat generation, thereby improving battery safety. Notably, the calorimetric results exhibit a distinct thermal signature associated with lithium plating, offering a potential diagnostic for detecting Li plating during eVTOL operation. Overall, this study demonstrates the utility of isothermal microcalorimetry as a valuable tool for assessing thermal risks in Li‐ion batteries for eVTOL applications, and highlights the importance of targeted design strategies to mitigate safety hazards during high‐power demand scenarios.

Li plating↗
DOE OSTI2020

Sulfonyl PIM–1: A diverse separation membrane with dilation resistance

A sulfone modified variant (soPIM–1) of the first polymer of intrinsic microporosity has been studied through molecular simulations to analyze its applicability for adsorption–based separations of diverse nonpolar, quadrupolar, and dipolar adsorbate species. Single component gas phase adsorption isotherms of each adsorbate are provided. Here, the adsorptive properties of soPIM–1 are reported from the application of two methods: (a) traditional grand canonical Monte Carlo (GCMC) simulations and (b) a combination of Monte Carlo and molecular dynamics (GCMC/MD) techniques, which accounts for sorption–induced polymer dynamics. The calculated isosteric heats of adsorption are compared to those from the parent PIM–1 structure and reveals increased CO2 affinity with relatively no change in hydrocarbon affinity. Moreover, to quantify soPIM–1's resistance to dilation the evolution of the microporous structure across the adsorption isotherm loading pressures has been evaluated. Relatedly, nonequilibrium MD simulations have been utilized to determine that soPIM–1 is approximately twice as stiff as PIM–1.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Porous Covalent Organic Polymers for Efficient Fluorocarbon‐Based Adsorption Cooling

Abstract Adsorption‐based cooling is an energy‐efficient renewable‐energy technology that can be driven using low‐grade industrial waste heat and/or solar heat. Here, we report the first exploration of fluorocarbon adsorption using porous covalent organic polymers (COPs) for this cooling application. High fluorocarbon R134a equilibrium capacities and unique overall linear‐shaped isotherms are revealed for the materials, namely COP‐2 and COP‐3. The key role of mesoporous defects on this unusual adsorption behavior was demonstrated by molecular simulations based on atomistic defect‐containing models built for both porous COPs. Analysis of simulated R134a adsorption isotherms for various defect‐containing atomistic models of the COPs shows a direct correlation between higher fluorocarbon adsorption capacities and increasing pore volumes induced by defects. Combined with their high porosities, excellent reversibility, fast kinetics, and large operating window, these defect‐containing porous COPs are promising for adsorption‐based cooling applications.

Zheng, Jian↗
DOE OSTI2021

Porous Covalent Organic Polymers for efficient Fluorocarbon-based Adsorption Cooling

Adsorption-based cooling is an energy-efficient renewable-energy technology that can be driven using low-grade industrial waste heat and/or solar heat. Here, we report the first exploration of fluorocarbon adsorption using porous covalent organic polymers (COPs) for this cooling application. High fluorocarbon R134a equilibrium capacities and unique overall linear-shaped isotherms are revealed for the materials, namely COP-2 and COP-3. The key role of mesoporous defects on this unusual adsorption behavior was demonstrated by molecular simulations based on atomistic defect-containing models built for both porous COPs. Analysis of simulated R134a adsorption isotherms for various defect-containing atomistic models of the COPs shows a direct correlation between higher fluorocarbon adsorption capacities and increasing pore volumes induced by defects. Combined with their high porosities, excellent reversibility, fast kinetics, and large operating window, these defect-containing porous COPs are promising for adsorption-based cooling applications.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Manipulating Conjugated Polymer Backbone Dynamics through Controlled Thermal Cleavage of Alkyl Side Chains

The morphological stability of an organic photovoltaic (OPV) device is greatly affected by the dynamics of donors and acceptors occurring near the device's operational temperature. These dynamics can be quantified by the glass transition temperature (T g ) of conjugated polymers (CPs). Because flexible side chains possess much faster dynamics, the cleavage of the alkyl side chains will reduce chain dynamics, leading to a higher T g . In this work, the T g s for CPs are systematically studied with controlled side chain cleavage. Isothermal annealing of polythiophenes featuring thermally cleavable side chains at 140 °C, is found to remove more than 95% of alkyl side chains in 24 h, and raise the backbone T g from 23 to 75 °C. Coarse grain molecular dynamics simulations are used to understand the T g dependence on side chain cleavage. X-ray scattering indicates that the relative degree of crystallization remains constantduring isothermal annealing process. The effective conjugation length is not influenced by thermal cleavage; however, the density of chromophore is doubled after the complete removal of alkyl side chains. Here, the combined effect of enhancing T g and conserving crystalline structures during the thermal cleavage process can provide a pathway to improving the stability of optoelectronic properties in future OPV devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Comment on Comment on “Anomalous structural recovery in the near glass transition range in a polymer glass: Data revisited in light of temperature variability in vacuum oven‐based experiments”*

Abstract Cangialosi, Alegría, and Colmenero have made a comment on a paper of ours [Polym. Eng. Sci. 2022:1–13], in which we discussed the concern that the enthalpy recovery data reported by Cangialosi and co‐workers [Phys. Rev. Lett. 2013;111(9):095701] for polystyrene aged up to 15 K below glass transition temperature was anomalous and contradicted existing experimental results from the literature over a similar range of aging conditions. Their response shifts the focus away from the raised questions about their experimental results and attempts to invalidate the data that we cited in support of our argument. Here we respond to the comment and add additional analysis that suggests the structural recovery response of glassy materials exhibits smooth behavior over the full range of measurements, up to 7 or 8 logarithmic decades. We do this by referring to the work on the intrinsic isotherm down‐jump and memory responses of poly(vinyl acetate) between 40°C and 15°C over six logarithmic decades by Kovacs [Fortsch. Hochpolym. Fo. 1963;3(1/2):394–508], the small‐strain tensile creep of poly(vinyl chloride) quenched from 90°C to 40°C (approximately 40°C below T g ) over seven logarithmic decades from Struik [Polym Eng. Sci., 1977;17:165–173], and the volume recovery behavior for aging times up to 3 months in a temperature range between 95°C and −50°C by Greiner and Schwarzl [Rheol. Acta. 1984;23(4):378–395]. We also add discussion that an isothermal aging procedure using a vacuum oven is highly vulnerable to temperature errors due to the problem of good temperature control when the heat transfer mechanism is primarily radiative.

Jin, Shuang↗
DOE OSTI2021

Precipitate Phase Stability and Mechanical Properties of Alloy 263 and Variants in Wrought or Cast Form

Alloy 263 is a candidate Ni-based superalloy for use in advanced ultra-supercritical (AUSC) power plants that are targeted to operate above 700 °C. Exposure times in this type of environment are considerable with target creep properties specified at 100,000 h making phase stability an important parameter in the alloy selection process. In this investigation, the microstructure of alloy 263 and two modified compositions in both cast and cast/wrought forms were investigated after exposure at 800 °C for various times ranging from 1,000 h to 10,000 h. Tension and creep properties were assessed for all alloys in both forms. Modification to the Ti and Al concentrations successfully slowed down the γ' to η transformation while doubling the γ' fraction. Thin elongated η needles or platelets formed in the wrought products while thicker, plate-like, η precipitates were found in the castings. The effect of the various microstructures on the creep properties were determined using isothermally aged specimens aged at 800 °C for 3,000 h and 10,000 h prior to creep screening. Strong precipitation of the η phase was found to considerably decrease creep life and increase minimum creep rate. By modifying the Ti and Al content, the creep life and ductility of the new formulation tested on specimens isothermally aged for 3,000 and 10,000 h were near that of the nominal alloy in its standard aged condition.

Detrois, Martin↗
DOE OSTI2024

Use of a Lignin-Based Admixture for Tailoring the Rheological Properties of Mortars for 3D Printing: Preprint

Efforts toward decarbonizing construction materials and industrial processes related to cement and concrete can be aided via multifaceted approaches that target alternative admixtures as well as precision control of fabrication. Chemical admixtures for water reduction have played a crucial role in the development of advanced concrete mixtures. Newer biomass processing techniques developed for aviation fuel production from corn stover biomass produce a more reactive lignin byproduct that is suitable for chemical modifications to mimic the properties of polycarboxylate ether admixtures with a smaller carbon footprint. The present study examines the use of lignin-based water-reducing admixture in cement pastes and mortar mixtures for 3D printing. The experimental program explores the use of different dosages of lignin-based admixture to produce 3D-printed samples with appropriate extrudability and buildability. The rheological characterization was performed to determine the flow curve of various mixtures. Finally, the heat of hydration of cement pastes was monitored via isothermal calorimetry to assess the impact of lignin-based admixtures on the hydration process of cement. The results of this study indicate that the use of biomass by-products, such as lignin-based admixtures have great potential to effectively control the fresh-state properties of cement-based materials.

bio-based admixtures↗