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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Mesoscale modelling of dynamic porosity in cement hydrate gel during a water sorption cycle: A lattice Boltzmann study

We describe a lattice Boltzmann modelling framework for fluid sorption coupled to a dynamic model of cement hydrate microstructure upon which it is possible to explore ideas of water sorption in cement emergent from NMR and other recent experimental studies. The results of the first simulations using the model are presented. We show that it is possible to extract transport and microstructural relaxation parameters from the simulations that are in good qualitative agreement with experiment. We discuss limitations of the methodology.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Uptake of aqueous heavy metal ions (Co2+, Cu2+ and Zn2+) by calcium-aluminium-silicate-hydrate gels

Highlights: • C-A-S-H gels containing metal ions (Co{sup 2+}, Cu{sup 2+} or Zn{sup 2+}) were precipitated by a sol-gel technique. • Uptake mechanism and immobilization capacity of divalent metal ions by C-A-S-H are elucidated. • Up to ~55–60 mol% of Zn can be incorporated in defective tobermorite-type C-A-S-H. • Metal uptake by C-A-S-H is controlled mainly by isomorphous substitution for Ca ions. • Crystal-chemical features of C-A-S-H gels and implications for practical application are discussed. Calcium-aluminium-silicate-hydrate (C-A-S-H) gels containing heavy metal ions (Me: Co{sup 2+}, Cu{sup 2+} or Zn{sup 2+}) were precipitated at different Me/Si molar ratios to study the uptake mechanism and immobilization capacity. Aqueous solution chemistry and solid-phase characterization using XRD, FTIR, ESEM-EDX, TEM-HAADF and TG-DSC methods reveal threshold values for ion substitution of ~55–60 mol% for Zn, ~30–40 mol% for Co and ~25–30 mol% for Cu in defective tobermorite-type C-A-S-H with (Ca + Me)/(Si + Al) molar ratios from 0.86 to 1.04. At higher aqueous Me concentrations, Me (chloride) hydroxides start to co-precipitate. The uptake mechanism of Me ions by C-A-S-H is based on (i) isomorphous substitution of Me for Ca in the CaO layer, (ii) ion exchange in the interlayer, (iii) tetrahedral substitution (Zn) within the dreierketten chains and (iv) surface adsorption onto the C-A-S-H gel structure. Systematics in crystal-chemistry of Me-bearing C-A-S-H and implications for application and performance in natural and man-made settings are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Simulation of axial tensile well deformation during reservoir compaction in offshore unconsolidated methane hydrate-bearing formation

Sand production encountered in the 2013 offshore field gas production tests at the Nankai Trough, Japan, could be attributed to well failure during reservoir compaction. In this study, well integrity under various reservoir compaction patterns for the Nankai Trough case is examined using a well-formation finite element model. Here, the modelling details include the inclusion of a cement sheath as well as the modelling of construction processes (such as cement shrinkage). Well elongation in the overburden layer becomes significant when the reservoir subsidence is localized near the wellbore under large depressurization. Results show that the maximum plastic deviatoric strain level in the cement could reach 0.7% when the maximum reservoir subsidence reaches 0.85 m and cement shrinkage is limited. When cement shrinkage rises to 0.75%, the maximum plastic deviatoric strain increases to 2.4% as the cement accumulates additional plastic strain during shrinkage due to its deformation being constrained by the casing. In order to prevent the cement from failure, it might be effective to hold the pressure drawdown at a low level (e.g., several MPa) until the hydrate dissociation front advances to a certain radius from the well (e.g., a couple of tens of metres).

58 GEOSCIENCES↗
DOE OSTI2021

Interfacial and Confinement-Mediated Organization of Gas Hydrates, Water, Organic Fluids, and Nanoparticles for the Utilization of Subsurface Energy and Geological Resources

Harnessing the subsurface geologic environments in an efficient and environmentally sustainable manner is challenged by uncertainties associated with predicting the fate of fluids and sustaining porosity and permeability in subsurface geologic environments. Some of these uncertainties arise from confined and interfacially induced structures of fluids in subsurface geologic environments. The formation of gas hydrates, phase transitions of confined fluids, assembly and deposition of heavy hydrocarbons, and the agglomeration and fate of nanoparticles in confined environments are summarized in this review. Nanoscale confinement contributes to anisotropic structures and dynamics of fluids, which is the basis for anomalous phase transition thermodynamics, reactivity, transport, and geomechanical behavior. In this review, we discuss the structures of confined fluids and deviation in observed properties from bulk fluids. The factors influencing the structures of confined fluids can be generally divided into two groups: (a) pore characteristics including pore size, pore surface chemistry, and pore geometry and (b) confined fluid/solid characteristics such as molecular structure, concentrations, charges, pore filling, and presence of additives. Scientific advancements and knowledge gaps in our understanding of the structures of confined fluids and the associated differences in observed properties compared to bulk fluids are discussed. Here, the phenomena discussed in this review are of particular relevance to our efforts in harnessing the subsurface environments for a low carbon future by increasing the utilization of geothermal energy, using CO 2 as a working fluid, and storing CO 2 in subsurface geologic environments.

42 ENGINEERING↗
DOE OSTI2023

Hydrogen Bond Network Disruption by Hydration Layers in Water Solutions with Salt and Hydrogen-Bonding Polymers (PEO)

A mean field theory model describing the interaction of ion hydration layers with the network of hydrogen bonds of both water and the nonionic polymer poly(ethylene oxide) (PEO) is presented. The predictions of the model for types and statistics of hydrogen bonds, the number of water molecules bound to PEO, or their dependence on temperature are successfully verified from all-atom simulations at different NaCl and PEO concentrations. Furthermore, our simulations show that the binding of cations to PEO increases monotonically with salt concentration, in agreement with recent experimental results, through a mechanism in which the sum of the number of bound water and cations is independent of salt concentration. Here, the model introduced is general and can describe any salt or hydrogen-bond-forming polymer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Mesoporous Crystalline Niobium Oxide with a High Surface Area: A Solid Acid Catalyst for Alkyne Hydration

A mesoporous crystalline niobium oxide with tunable pore sizes was synthesized via the sol–gel-based inverse micelle method. The material shows a surface area of 127 m 2 /g, which is the highest surface area reported so far for crystalline niobium oxide synthesized by soft template methods. The material also has a monomodal pore size distribution with an average pore diameter of 5.6 nm. A comprehensive characterization of niobium oxide was performed using powder X-ray diffraction, Brunauer–Emmett–Teller, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, UV–vis, and X-ray photoelectron spectroscopy. The material acts as an environmentally friendly, solid acid catalyst toward hydration of alkynes under with excellent catalytic activity (99% conversion, 99% selectivity, and 4.39 h –1 TOF). Brønsted acid sites present in the catalyst were found to be responsible for the high catalytic activity. Lastly, the catalyst was reusable up to five cycles without a significant loss of the activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

PDADMAC/PSS Oligoelectrolyte Multilayers: Internal Structure and Hydration Properties at Early Growth Stages from Atomistic Simulations

We analyze the internal structure and hydration properties of poly(diallyl dimethyl ammonium chloride)/poly(styrene sulfonate sodium salt) oligoelectrolyte multilayers at early stages of their layer-by-layer growth process. Our study is based on large-scale molecular dynamics simulations with atomistic resolution that we presented recently [Sánchez et al., Soft Matter 2019, 15, 9437], in which we produced the first four deposition cycles of a multilayer obtained by alternate exposure of a flat silica substrate to aqueous electrolyte solutions of such polymers at 0.1M of NaCl. In contrast to any previous work, here we perform a local structural analysis that allows us to determine the dependence of the multilayer properties on the distance to the substrate. We prove that the large accumulation of water and ions next to the substrate observed in previous overall measurements actually decreases the degree of intrinsic charge compensation, but this remains as the main mechanism within the interface region. We show that the range of influence of the substrate reaches approximately 3 nm, whereas the structure of the outer region is rather independent from the position. This detailed characterization is essential for the development of accurate mesoscale models able to reach length and time scales of technological interest.

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

Hydration of divalent lanthanides, Sm 2+ and Eu 2+ : A molecular dynamics study with polarizable AMOEBA force field

The chemistry of divalent lanthanides, Ln 2+ , is a growing sub-field of heavy element chemistry owing to new synthetic approaches. However, some theoretical aspects of these unusual cations are currently underdeveloped, especially as they relate to their dynamic properties in solution. In this study, we address the hydration of two of the classical Ln 2+ cations, Sm 2+ and Eu 2+ , using atomic multipole optimized energetic for biomolecular applications (AMOEBA) force fields. These cations have not been parameterized to date with AMOEBA, and few studies are available because of their instability with respect to oxidation in aqueous media. Coordination numbers (CN's) of 8.2 and 8.1 respectively for Sm 2+ and Eu 2+ , and 8.8 for both Sm 3+ and Eu 3+ have been obtained and are in good agreement with the few available AIMD and X-ray absorption fine structures studies. The decreased CN of Ln 2+ compared with Ln 3+ arises from progressive water exchange events that indicates the gradual stabilization of 8-coordinate structures with respect to 9-coordinate geometries. Moreover, the effects of the chloride counter anions on the coordination of Ln 2+ cations have been studied at different chloride concentrations in this work. Lastly, water exchange times of Ln 2+ cations have been calculated to provide a comprehensive understanding of the behavior of Eu 2+ and Sm 2+ in aqueous chloride media.

AMOEBA force field parameterization↗
DOE OSTI2025

Giant Dipole Moments: Remarkable Effects Mono‐, Di‐, and Tri‐ Hydrated 5,6‐Diaminobenzene‐1,2,3,4‐Tetracarbonnitrile

The molecule 5,6-diaminobenzene-1,2,3,4-tetracarbonnitrile (MOI) was first synthesized by Müllen and coworkers in 2016 and boasts an ultrastrong dipole moment of $14.1\pm 0.7$ Debye in THF. Gas phase DFT computations do not fully reflect this ultrastrong dipole moment, demonstrating the role of solvent in increasing this dipole moment. Here, we investigate the effect of solvent molecule position on the dipole moment of this species, computationally examining systems with giant dipole moments. These systems are optimized in the gas phase with the B3LYP functional, employing the aug-cc-pVTZ and def2-TZVP basis sets, as well as the B3LYP-D3BJ/aug-cc-pVTZ functional in Orca. Single point DLPNO-CCSD/aug-cc-pVDZ results were obtained from Orca and Psi4, as well as DLPNO-CCSD(T)/CBS information from Psi4. Additionally, these are compared to the dipole moments of di- and tri-hydrated systems, and the SMD models for THF and water at the B3LYP/aug-cc-pVTZ level of theory. The dissociation energies, HOMO-LUMO energy gaps, and dipole moments are presented. These metrics show the nh1nh1′ THF system boasts the largest dissociation energy and dipole moment of the singly solvated systems, due to its strong hydrogen bonding. The importance of solvent placement is highlighted and may guide the synthesis of macromolecules or organic frameworks incorporating the MOI or MOI-like subunits. Remarkably, a single solvent molecule provides a good model for the difference between the gas phase and solvated species. The predicted gas phase dipole moments computed with B3LYP/aug-cc-pVTZ for the MOI, its monohydrated complex, dihydrated complex, and its trihydrated complex are 9.6, 14.2, 16.0, and 16.8 Debye, respectively.

dipole↗
DOE OSTI2025

Speciation and diffusive dynamics in hydrated grain boundaries of complex oxide Gd2Ti2O7

Abstract Grain boundaries in polycrystalline materials significantly affect their properties, such as ionic transport, corrosion, and chemical durability. The pyrochlore compound (Gd 2 Ti 2 O 7 ) is employed as a model for complex oxides and is known for its diverse applications, including nuclear waste immobilization. Density functional theory-based first-principles molecular dynamics simulations were performed at different temperatures on the hydrated grain boundary system. The results show extensive transformations within the grain boundaries among hydrous water species (OH − , H 2 O, and H 3 O + ). The temperature dependence of self-diffusion coefficients follows Arrhenius behavior, with an activation energy of 35.9 kJ/mol for hydrogen and 46.3 kJ/mol for oxygen. The lifetime of OH − is about three to four times longer than that of H 2 O at temperatures from 800 to 2100 K, suggesting the greater stability of OH − over H 2 O, a unique characteristic of the grain boundaries. The estimated lifetime of the hydrous species decreases as the temperature increases, with an activation energy of 9.9 kJ/mol for OH − and 13.4 kJ/mol for H 2 O. While Gd 3 + is more mobile than Ti 4+ , both the Gd 3 + and Ti 4+ cations are orders of magnitude less mobile than the water species. The results suggest that water species are much more mobile within grain boundaries than in the bulk crystal and have the potential to penetrate deep into polycrystalline materials through grain boundaries, leading to grain boundary degradation and dissolution. The different mobilities of cations in complex oxides can lead to leaching of certain cations and incongruent dissolution during the chemical weathering of Earth and industrial materials.

B. Ghosh, Dipta↗
DOE OSTI2023

Uniaxial stress increases layer stacking disorder in calcium silicate hydrates with low calcium content

The long-term stress response of concrete is controlled by the intergrain and intragrain interactions of calcium-silicate-hydrates (C-S-H), nanocrystalline forms of tobermorites. To investigate both types of interactions, we examined the deviatoric stress response of 11 Å tobermorite powder with X-ray diffraction, finding that its layer stacking (i.e., sliding) disorder significantly increases. A similar experiment was performed on nanocrystalline C-S-H powders before and after applying a 360 MPa uniaxial stress. Layer stacking disorder (in the form of intragrain deformation) increases when there is low water content and when the basal spacing is large. We also find that grains with a smaller thickness-to-diameter aspect ratio are first to develop preferred orientation (in the form of intergrain sliding), facilitated by gel water. Furthermore, these findings show that intragrain deformations in C-S-H can occur at relatively low stresses and provide insights into the creep mechanism of C-S-H.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Determining the hydration energetics on carbon-supported Ru catalysts: An adsorption calorimetry and density functional theory study

Fundamental knowledge on the energetics at the interface between a water layer and a metal catalyst is essential so as to understand the roles that water can play in the synthesis, activation and regeneration of noble metal-based catalysts. Here, we report the direct measurement of the enthalpy of water adsorption (Δh ads ) on activated carbon (C) and activated C-supported Ru nanoparticles, which are promising catalyst as applied to the hydrogenation/hydrodeoxygenation (HDO) of oxygenates (phenolics, aldehydes, etc.). Specifically, the near-zero coverage enthalpy of water adsorption on a C-supported Ru catalyst is -75.3 ± 0.4 kJ/(mol water), suggesting favorable water–metal binding. This is much more exothermic than that on C, which has an enthalpy of adsorption of -50.3 ± 1.3 kJ/(mol water). Despite the favorable initial binding, the magnitudes of enthalpies of water condensation on C and Ru-C indicate that overall, their surfaces are both hydrophobic. Moreover, the experimentally-measured near-zero coverage water adsorption enthalpy at the Ru sites is in very good agreement with our density functional theory based calculations. At low coverages, we obtain a water binding energy of -61.7 kJ/(mol water), which increases to -78.1 kJ/(mol water) at saturation. Complementary results are also obtained from a thermal analysis, which employed a thermogravimetric analysis–differential scanning calorimetry–mass spectrometry (TG-DSC-MS), a spectroscopic investigation using ex situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and a morphological evaluation with transmission electron microscopy (TEM). We point out that in carbon-supported metal catalysts, such as Ru-C, a strong hydration at near-zero coverage and relative weak water-surface interactions occurs upon saturation. Such heterogeneity is essential and crucial for catalytic hydrogenation/HDO reactions that involve balanced interactions among the water-rich reactant mixture and nonpolar organic products.

09 BIOMASS FUELS↗
DOE OSTI2023

Early age hydration behavior of portland cement-based binders incorporating fly ash contaminated with flue gas desulfurization products

Fly ash co-mingled with flue gas desulfurization (FGD) products are currently discarded as off-specification materials based on their high SO3 content. However, previous studies have shown that performance of these fly ashes varies significantly based on FGD product type and as such they may be viable for use in low-CO2 concrete as supplementary cementitious materials (SCMs). In this study, fly ashes with three different types of FGD products including calcium sulfite hemihydrate, calcium sulfate (with some unreacted lime), and sodium sulfate (with some unreacted sodium carbonate) were evaluated. The early age hydration behavior in blended cementitious systems at 20% cement replacement level was studied using Vicat setting time tests, isothermal calorimetry, in-situ quantitative X-ray diffraction, and pore solution analysis. The cause of the setting time retardation and flash setting observed in fly ashes with calcium sulfite hemihydrate and sodium carbonate, respectively, were identified and suitable beneficiation options were suggested for the valorized use of these materials in low-CO 2 concrete.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The first experimental evidence for improved nanomechanical properties of calcium silicate hydrate by polycarboxylate ether and graphene oxide

Graphene oxide (GO) efficiently enhances macroscale mechanical properties of cement-based materials. Yet the nanoscale reinforcing mechanism of GO for calcium silicate hydrate (C-S-H), the key binding phase of concrete, remains poorly understood. Moreover, how polycarboxylate ether (PCE)-based superplasticizers affect the nanomechanical properties of C-S-H remains unclear. The intrinsic mechanical properties of the nanocomposites are measured using high-pressure X-ray diffraction. The influences of GO and PCE on the local Ca and Si environments are probed using X-ray absorption spectroscopy. For the first time, we evidence that PCE-induced well-dispersed GO nanoplatelets strengthen the C-S-H basal planes, whereas poorly water-dispersed GO weakly interacts with basal planes and does not strengthen in plane Casingle bondO bonds. Both PCE and GO only slightly strengthen C-S-H's c-axis. Here, the bulk modulus of C-S-H/PCE/GO nanocomposite is 190% than pure C-S-H. Functional groups of PCE and GO prefer interacting with the Casingle bondO sheets of C-S-Hs instead of silicate tetrahedra.

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

Chemical structure and complex growth modes of magnesium silicate hydrate: Nanoparticle orientation, aggregation, and fusion

The extent of utilization of magnesium silicate hydrate (MSH) in construction is limited partly because of insufficient data ascertaining the kinetics of its precipitation. In this report MSH grown homogeneously or heterogeneously in the range of magnesium to silicon solution molar concentration ratios, [Mg]/[Si] = 0.5-1.5, and temperature = 25-80 °C was analyzed for its chemical structure and morphology. Infrared spectroscopy and geochemical modeling show that increasing the [Mg]/[Si] ratio results in less silicate polymerization in MSH. Atomic force microscopy reveals the presence of nanoparticles that aggregate and fuse to form films. Oriented attachment of nanoparticles and features indicative of enhanced crystallinity were observed at higher temperatures and longer reaction times. These data provide direct evidence for the persistence of hierarchical structures (i.e., nanoparticles forming 3D microparticles and 2D film layers) at the nanoscale to mesoscale. These findings offer insights into the precise chemical synthesis of MSH and its widespread use as a binder for construction purposes.

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

Achieving extraordinary thermal stability of salt hydrate eutectic composites by amending crystallization behaviour with thickener

Commercial thermal energy storage (TES) systems necessitate reliable thermal performance throughout their operational lifetime. Repeated volume changes of the phase change materials (PCMs) during thermal cycling disengages thermal contacts between the conductive fillers like expanded graphite (EG) in TES composites, causing unstable thermal conductivity (k) that fades with cycling. Our in-operando crystallization studies on eutectic PCM made of zinc nitrate hexahydrate (ZNH) and KNO 3 revealed that the thermal stability of PCM composites can be considerably degraded by the formation of large and sharp-cornered PCM crystals during the freezing cycle. While the crystals can push EG particles, disengaging thermal contacts between them, we have newly discovered that carboxymethyl cellulose (CMC) can be used to retain the thermal contacts by forming networks of smaller PCM crystals. Furthermore, the scalable synthesis methodology of EG/ZNH eutectic composites was introduced. Here, in this study, EG particles were strongly connected into a matrix via a stable, corrosion resistant polydimethylsiloxane (PDMS) binder, stabilizing thermal networks and thereby maintaining k up to 1000 melt/freeze cycles. The thermal conductivity of our 25 vol% EG sample (13.3 W m -1 K -1 ) is more than 48% higher than other salt hydrate eutectic composites reported in the literature. We expect this study to provide insights on cooperative interaction between different components of TES systems (PCM, filler, thickener, binder) for exceptionally robust thermal properties.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Dolomites in hydrated fine-grained Antarctic micrometeorites: Effective tools for analyzing secondary processes

We report detailed transmission electron microscope (TEM) observations of carbonates from one hydrated fine-grained Antarctic micrometeorite (H-FgMM). These carbonates show the occurrence of complex chemical variations and microstructures that provide important evidence regarding the formation and evolution of rarely analyzed H-FgMMs. The chemical variations were identified at both micrometer and nanometer scales, indicating that these carbonates formed under localized fluid conditions that suggest a variable chemical microenvironment. Individual carbonates grew from isolated reservoirs of fluid. Moreover, these carbonates contain manganese amounts almost twice as high as those measured in CM chondrites but similar to those identified in CI chondrites. Their particular compositions indicate reducing and progressively evolving conditions in the fluid from which these carbonates precipitated, probably due to water consumption during phyllosilicates formation. In addition to the compositional variability, microstructural features are pervasive in these carbonates, similar to those described in heavily shocked meteorites indicating that these carbonates were probably modified during shock processes after their formation. Since carbonates are highly susceptible to shock metamorphism, we suggest that it is essential to investigate their structure in detail before interpreting the isotopic measurements related to the time of their formation. Additionally, associated with carbonates, ubiquitous phosphates were identified in the micrometeorite analyzed. Future studies of these mineral associations will provide us further insight into the formation and evolution of asteroids, especially since they were both identified in the surface materials of Ryugu and Bennu.

58 GEOSCIENCES↗
DOE OSTI2026

Hydration size-dependent transport of ions across nanoporous graphene membranes

Nanoporous atomically-thin membranes are promising candidates for metal ion separations due to their chemical stability and high permeance and selectivity, but experimental evidence of the mechanisms responsible for ion-ion selectivity is sparse. Here, in this work, we measured the simultaneous diffusion of a dilute mixture of ten different Group I, Group II, and rare earth cations in a salt background across nanoporous graphene (NPG) membranes with sub-nanometer pores. The membranes exhibited ion-ion selectivity, including between similarly-charged ions. Cation transport was governed primarily by the hydrated ion size that was consistent with continuum models of ion diffusion, with additional influence of the ionic charge. Selectivity enhancement was achieved by modifying ion sizes using an ion-selective complexing agent. Our study provides evidence of the importance of size-sieving and electrostatic mechanisms governing ion transport across NPG, and allows for quantitative prediction of transport rates to guide future development of ion-selective atomically-thin membranes.

36 MATERIALS SCIENCE↗