Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “structured liquids”

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 253 records · Page 14

Path integral Monte Carlo approach to the structural properties and collective excitations of liquid $$^3{\text {He}}$$ without fixed nodes

Abstract Due to its nature as a strongly correlated quantum liquid, ultracold helium is characterized by the nontrivial interplay of different physical effects. Bosonic $$^4{\text {He}}$$ 4 He exhibits superfluidity and Bose-Einstein condensation. Its physical properties have been accurately determined on the basis of ab initio path integral Monte Carlo (PIMC) simulations. In contrast, the corresponding theoretical description of fermionic $$^3{\text {He}}$$ 3 He is severely hampered by the notorious fermion sign problem, and previous PIMC results have been derived by introducing the uncontrolled fixed-node approximation. In this work, we present extensive new PIMC simulations of normal liquid $$^3{\text {He}}$$ 3 He without any nodal constraints. This allows us to to unambiguously quantify the impact of Fermi statistics and to study the effects of temperature on different physical properties like the static structure factor $$S({\mathbf {q}})$$ S ( q ) , the momentum distribution $$n({\mathbf {q}})$$ n ( q ) , and the static density response function $$\chi ({\mathbf {q}})$$ χ ( q ) . In addition, the dynamic structure factor $$S({\mathbf {q}},\omega )$$ S ( q , ω ) is rigorously reconstructed from imaginary-time PIMC data. From simulations of $$^3{\text {He}}$$ 3 He , we derived the familiar phonon–maxon–roton dispersion function that is well-known for $$^4{\text {He}}$$ 4 He and has been reported previously for two-dimensional $$^3{\text {He}}$$ 3 He films (Nature 483:576–579 (2012)). The comparison of our new results for both $$S({\mathbf {q}})$$ S ( q ) and $$S({\mathbf {q}},\omega )$$ S ( q , ω ) with neutron scattering measurements reveals an excellent agreement between theory and experiment.

97 MATHEMATICS AND COMPUTING↗

Double-Helical Tiled Chain Structure of the Twist-Bend Liquid Crystal Phase in CB7CB

The twist-bend nematic liquid crystal phase is a three-dimensional fluid in which achiral bent molecules spontaneously form an orientationally ordered, macroscopically chiral, heliconical winding of a ten nanometer-scale pitch in the absence of positional ordering. Here, the structure of the twist-bend phase of the bent dimer CB7CB and its mixtures with 5CB is characterized, revealing a hidden invariance of the self-assembly of the twist-bend structure of CB7CB, such that over a wide range of concentrations and temperatures, the helix pitch and cone angle change as if the ground state for a pitch of the TB helix is an inextensible heliconical ribbon along the contour formed by following the local molecular long axis (the director). Remarkably, the distance along the length for a single turn of this helix is given by 2πR mol , where R mol is the radius of bend curvature of a single all-trans CB7CB molecule. This relationship emerges from frustrated steric packing due to the bent molecular shape: space in the fluid that is hard to fill attracts the most flexible molecular subcomponents, a theme of nanosegregation that generates self-assembled, oligomer-like correlations of interlocking bent molecules in the form of a brickwork-like tiling of pairs of molecular strands into duplex double-helical chains. At higher temperatures in the twist-bend phase, the cone angle is small, the director contour is nearly along the helix axis z, and the duplex chains are sequences of biaxial elements formed by overlapping half-molecule pairs, with an approximately 45° rotation of the biaxis between each such element along the chain.

36 MATERIALS SCIENCE↗

Theory of Ion-Mediated Segmental Localization, Activated Structural Relaxation, and the Glass Transition in Polymerized Ionic Liquids

Here we combine polymer integral equation theory for structural correlations with a force-level theory for activated segmental relaxation to construct a microscopic theory for how ions modify the onset of segmental localization, the polymer alpha relaxation time, and glass transition temperature, T g , in dry polymerized ionic liquids (PolyILs). Our most important findings concerning the behavior of T g are (i) a weak dependence on anion–cation Coulomb attraction strength due to strong decoupling of ion and segmental dynamics, (ii) strong reduction with increasing mobile ion size due to both plasticization effects and weakening of ion-modified monomer caging, and (iii) increase with backbone rigidity and intrachain dynamic cooperativity. We quantitatively estimate T g variations as ion size and polymer static and dynamic rigidity are widely varied. The experimental data of 19 PolyILs are organized into a specific pattern consistent with the theoretical predictions with glass transition temperatures varying over a very wide range (~250 K) as observed experimentally. Based on the theoretical results, suggestions are made concerning the search for high conductivity Li- or Na-based PolyILs based on further lowering of T g via new polymer synthesis. Calculations of the alpha time as a function of packing fraction reveal the dynamic fragility increases for larger mobile ions, a more flexible backbone, and/or a smaller degree of intrachain dynamic cooperativity, as a consequence of the increasing importance of collective elasticity in determining the activation barrier. An analysis of transient segmental localization and a crossover to activated dynamics reveals similar, but not identical, trends as predicted at the laboratory vitrification timescale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In-situ/operando study of Cu-based nanocatalysts for CO 2 electroreduction using electrochemical liquid cell TEM

The structure of a nanocatalyst during electrocatalytic reactions often deviates from its pristine structure due to intrinsic properties, or physical and chemical adsorption at the catalytic surfaces. Taking Cu-based catalysts for CO 2 electroreduction reactions (CO 2 RR) as an example, they often experience segregation, leaching, and alloying during reactions. With the recent breakthrough development of high-resolution polymer electrochemical liquid cells, in-situ electrochemical liquid cell transmission electron microscopy (EC-TEM) alongside other advanced microscopy techniques, has become a powerful platform for revealing electrocatalysts restructuring at the atomic level. Considering the complex reactions involving electrified solid-liquid interfaces and catalyst structural evolution with intermediates, systematic studies with multimodal approaches are crucial. In this article, we demonstrate a research protocol for the study of electrocatalysts structural evolution during reactions using the in-situ EC-TEM platform. Using Cu and CuAg nanowire catalysts for CO 2 RR as model systems, we describe the experimental procedures and findings. We highlight the platform’s crucial role in elucidating atomic-scale pathways of nanocatalyst restructuring and identifying catalytic active sites, as well as avoiding potential artifacts to ensure unbiased conclusions. Using the multimodal characterization toolbox, we provide the opportunity to correlate the structure of a working catalyst with its performance. Finally, we discuss advancements as well as the remaining gap in elucidating the structural-performance relationship of working catalysts. We expect this article will assist in establishing guidelines for future investigations of complex electrochemical reactions, such as CO 2 RR and other catalytic processes, using the in-situ EC-TEM platform.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Origin of short- and medium-range order in supercooled liquid Ge 3 Sb 2 Te 6 from ab initio molecular dynamics simulations

Phase-change materials such as Ge–Sb–Te compounds have attracted much attention due to their potential value in electrical data storage. In contrast to the amorphous and crystalline phases, supercooled liquids are far from being deeply understood despite their inevitable role in both amorphization and crystallization processes. To this end, we have studied the dynamics properties and structural characteristics of liquid and supercooled liquid Ge 3 Sb 2 Te 6 during the fast cooling process. As the temperature decreases, chemical bonds become more homogeneous, but coordination numbers of Ge, Sb and Te atoms change very little. Meanwhile, the structural order of short-range configuration is obviously enhanced. Further studies suggest that Ge-centered, Sb-centered and Te-centered configurations change to the more ordered defective octahedrons mainly by adjusting the bond-angle relationship and bond length, rather than just by changing the coordination environment. It is the more ordered octahedrons that promote the formation of medium-range order. Our findings provide a deep insight into the origin of local structural order in supercooled liquid Ge 3 Sb 2 Te 6 , which is of great importance for the comprehensive understanding of amorphization and crystallization processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and Stability of the Ionic Liquid Clusters [EMIM]n[BF4]n+1- (n = 1 – 9): Implications for Electrochemical Separations

Precise functionalization of electrodes with size-selected ionic liquid (IL) clusters may improve the application of ILs in electrochemical separations. Herein, we report our combined experimental and theoretical investigation of the IL clusters [EMIM]????[BF4]????+1- (n = 1 – 9) and demonstrate their selectivity and efficiency towards targeted adsorption of molecules from solution. The structures and energies of the IL clusters, predicted with global optimization, agree with and help interpret the ion abundances and stabilities measured by high mass resolution electrospray ionization mass spectrometry and collision induced dissociation experiments. The [EMIM][BF4]2- cluster, which was identified as the most stable IL cluster, was selectively soft landed onto a working electrode. Electrochemical impedance spectroscopy revealed a lower charge transfer resistance on the soft-landed electrode containing [EMIM] [BF_4 ]_2^- compared to an electrode prepared by drop casting of IL solution, which contains the full range of IL clusters. Our findings indicate that specific IL clusters may be used to increase the efficiency of electrochemical separations by lowering the overpotentials involved.

Zhang, Jun↗

Anion-dependent phase behavior of methylimidazolium-based ionic liquids mixed with water: Correlation between local molecular structure and mesoscale behaviors

The mesoscopic phase behavior of decylmethylimidazolium (C 10 mim) ionic liquids (ILs) bearing three monovalent anions—thiocyanate (SCN − ), nitrate (NO 3 − ), and chloride (Cl − )—mixed with water at relatively high IL contents (50–95 wt%) was investigated. Small-angle and wide-angle X-ray scattering (SAXS/WAXS) were employed to follow the evolution of both local and mesoscale structures across this composition range. In the absence of water, C 10 mimSCN and C 10 mimCl behaved as disordered liquids, whereas C 10 mimNO 3 spontaneously formed a hexagonally ordered cylindrical mesophase and displayed a sticky-solid macroscopic appearance. Upon addition of water, C 10 mimSCN remained a viscous liquid and only weakly ordered lamellar domains were observed. This limited ordering is attributed to the lack of hydrogen bonding and weak interaction energy between SCN − anions and C 10 mim + cations. In contrast, the trigonal-planar NO 3 − and point-like Cl − anions promoted the formation of well-defined hexagonal mesophases up to 35–45 wt% water. The formation of hydrogen bonding of the two anions with imidazolium ring protons likely enabled the creation of compact ion clusters that effectively exclude water molecules from the immediate vicinity of the IL aggregates. These findings demonstrate that the interaction energy between ion pairs dictate IL-water interactions and therefore control the transition from disordered liquids to ordered mesophases in IL/water mixtures with high IL contents. In conclusion, the combined SAXS/WAXS analysis reveals a correlation between local intermolecular structure and the emergence of mesoscopic order, providing a systematic framework for tailoring mesoscale structures in alkylimidazolium-based IL/water systems.

36 MATERIALS SCIENCE↗

Conceptual design of HFIR irradiation experiment for material compatibility study on liquid Sn divertor

Liquid Sn is one of the promising coolants for liquid surface divertor concept of fusion reactors. However, the compatibility between liquid Sn and structural materials is an important issue that has to be addressed, because liquid Sn is extremely corrosive to steels at high temperatures. The corrosion may be mitigated when a protective Al2O 3 layer is formed on the surface of alumina forming steels. However, the effect of neutron irradiation on the integrity of protective layer is not made clear so far. Japan and US joint research project “FRONTIER” started in 2019 to investigate the material compatibility under neutron irradiation. The purpose of the present study is to develop the conceptual design of the irradiation test capsule which enables material compatibility tests for the alumina forming steels - liquid metal systems under neutron irradiation in the High Flux Isotope Reactor at Oak Ridge National Laboratory, TN, USA. The three dimensional drawing of capsule structure was then developed. The validity of the material selections for the capsule design was investigated by means of corrosion tests of SiC, Si3N4, Ti, and Mo in liquid Sn at 773 K for 262 hr.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Nature of the bonded-to-atomic transition in liquid silica to TPa pressures

First-principles calculations and analysis of the thermodynamic, structural, and electronic properties of liquid SiO 2 characterize the bonded-to-atomic transition at 0.1–1.6 TPa and 10 4 –10 5 K (1–9 eV), the high-energy-density regime relevant to understanding planetary interiors. We find strong ionic bonds that become short-lived due to high kinetics during the transition, with sensitivity of the transition temperature to pressure, and our calculated Hugoniots agree with past experimental data. Furthermore, these results reconcile previous experimental and theoretical findings by clarifying the nature of the bond dissociation process in early Earth and “rocky” (oxide) constituents of large planets.

74 ATOMIC AND MOLECULAR PHYSICS↗

Curing process and pore structure of metakaolin-based geopolymers: Liquid-state 1H NMR investigation

Geopolymers are emerging construction materials with lower carbon dioxide emissions compared to the conventional cementitious materials. The knowledge of the curing process and the related pore structures are important for optimizing the properties of these materials for different applications. The curing process and final pore structure are sensitive to the amount of used water, however the specifics are unclear. The curing process and pore structures of metakaolin-based geopolymers with a narrow water-to-solid (w/s) ratio (0.59–0.66) were monitored by nuclear magnetic resonance (NMR) relaxometry and cryoporometry. The 14-day curing process was investigated by monitoring the change of T{sub 2} and T{sub 1} relaxation times and water signal intensity. After the curing, the pore structures were characterized by 2D T{sub 1}-T{sub 2} correlation and T{sub 2}-T{sub 2} exchange measurements of absorbed water. The pore size distributions (PSDs) were measured with NMR cryoporometry and compared to nitrogen physisorption and mercury intrusion porosimetry (MIP) results. We found that the relaxation times decreased as the pore structure of the geopolymers matured during the curing while the dissolution and the condensation periods of the curing were distinguished by the changes in signal amplitude reflecting the proton density. After the curing, three distinct pore sizes and connectivity between pores were identified from T{sub 1}-T{sub 2} and T{sub 2}-T{sub 2} spectra. Their PSDs were measured, and they were found to correspond to two different pore sizes originating from the arrangement of clusters and defective pores. In the narrow w/s ratio (0.59–0.66), the curing times were the same for all samples when cured at 24 °C while the pore sizes were observed to increase as a function of the w/s ratio.

36 MATERIALS SCIENCE↗

Liquid and Glass Phases of an Alkylguanidinium Sulfonate Hydrogen-Bonded Organic Framework

Glassy phases of framework materials feature unique and tunable properties that are advantageous for gas separation membranes, solid electrolytes, and phase-change memory applications. However, the structural and chemical diversity of porous frameworks that can be liquified and quenched into a glass has been limited by thermal decomposition at-or below-the high temperatures required to induce a melting transition. Utilizing a desymmetrization strategy, in this work we report a new guanidinium organosulfonate hydrogen-bonded organic framework (HOF) that melts and vitrifies below 100 °C. In this low-temperature regime, non-covalent interactions between guest molecules and the porous framework become a dominant contributor to the overall stability of the structure, resulting in unusual phase behavior such as guest dependent melting, glass, and recrystallization transitions. Through molecular dynamics simulations and pair distribution function analysis, we show that the local structure of the amorphous liquid and glass phase resembles that of the parent crystalline framework. Access to molten phases of framework materials at moderate temperatures should permit the use of more thermally sensitive functional groups and enhance the structural control and tunability that can be realized in network-forming glasses.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Tethered from the Head and from the Tail: The Structure of Hydroxyl-Functionalized Ionic Liquids

Ionic liquids with special functionalities are synthesized with the specific purpose of creating new patterns of interaction in the condensed phase. This Letter discusses the case of alcohol-functionalized ILs, the so-called HFILs, which are part of the larger cohort of task-specific ionic liquids. We find that this small chemical modification can cause massive changes in the liquid landscape when the cationic tails are longer. For prototypical ionic liquids, larger alkyl tails act as separators of charge networks, but in the case of HFILs these become physical charge network linkers. The OH functionality adds a large repertoire of interactions and correlations that were mostly unavailable to traditional ILs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

New structural model of a chiral cubic liquid crystalline phase

A new model of a chiral cubic phase is proposed, in which the continuous lattice is embedded on a WP minimal primitive surface and chirality is related to the alternating inclination of molecules in the neighbouring segments of non-flat hexagons.

Vaupotič, Nataša↗

Insights on sources and formation mechanisms of liquid-bearing clouds over MOSAiC examined from a Lagrangian framework

Understanding Arctic stratiform liquid-bearing cloud life cycles and properly representing these life cycles in models is crucial for evaluations of cloud feedbacks as well as the faithfulness of climate projections for this rapidly warming region. Examination of cloud life cycles typically requires analyses of cloud evolution and origins on short time scales, on the order of hours to several days. Measurements from the recent Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition provide a unique view of the current state of the central Arctic over an annual cycle. Here, we use the MOSAiC radiosonde measurements to detect liquid-bearing cloud layers over full atmospheric columns and to examine the cloud-generating air masses’ properties. We perform 5-day (120 h) back-trajectory calculations for every detected cloud and cluster them using a unique set of variables extracted from these trajectories informed by ERA5 reanalysis data. This clustering method enables us to separate between the air mass source regions such as ice-covered Arctic and midlatitude open water. We find that moisture intrusions into the central Arctic typically result in multilayer liquid-bearing cloud structures and that more than half of multilayer profiles include overlying liquid-bearing clouds originating in different types of air masses. Finally, we conclude that Arctic cloud formation via prolonged radiative cooling of elevated stable subsaturated air masses circulating over the Arctic can occur frequently (up to 20% of detected clouds in the sounding data set) and may lead to a significant impact of ensuing clouds on the surface energy budget, including net surface warming in some cases.

54 ENVIRONMENTAL SCIENCES↗

Nucleation and growth of blue phase liquid crystals on chemically-patterned surfaces: a surface anchoring assisted blue phase correlation length

In condensed matter, the correlation length is an essential parameter which describes the distance over which a material maintains its structural properties. In liquid crystals, for the orientational order parameter this characteristic length is of the order of nanometers, while in solid crystals it can extend to macroscopic length scales. Here, we report the measurement of the correlation length, or persistence length, of the crystallographic orientation of blue phases (BPs)—chiral liquid crystals with long-range 3D-crystalline structures and submicron-sized lattice-parameters. These materials exhibit phase transformations that have been identified as the liquid analog of crystal-crystal martensitic transformations. In this work, we use liquid epitaxial growth to achieve spontaneous BP-crystal nucleation and subsequent growth. Specifically, we design patterned substrates made of a binary array of regions with different liquid crystal anchoring, which facilitate a uniform nucleation and growth of BP-crystals with (100)-lattice orientation and a simple cubic symmetry. Furthermore, our results indicate that this simple cubic BP, the so-called blue phase II (BPII), forms first on the patterned surface, thereby propagating the growth of domains in directions parallel or perpendicular to the patterned regions. These results are used to understand the emergence of a surface anchoring assisted BPII-correlation length, taken as the distance over which the BP preserves its lattice orientation, as a function of time and pattern characteristics. We found that BPII single crystals can be achieved on patterned regions whose lateral dimensions are equal to or larger than 10 μm, consistent with our measurements of the BPII-correlation length. This newly acquired understanding of the role of surfaces on the formation of BPs is then used to design processes that permit formation of macroscopically large mono-domain, single-crystal BPs by relying on significantly reduced patterned areas (only part of the area is patterned), a feature that could benefit the applications of this intriguing class of materials.

correlation length↗

Impact of Water Extraction on Malonamide Aggregation: A Molecular Dynamics and Graph Theoretic Approach

Solution structure in liquid-liquid extraction affects the efficacy of separation; however, even for simplified organic phases, structural characterization and attribution of aggregation to intermolecular interactions are fundamental challenges. We investigate water uptake into organic phases for two malonamides commonly applied to actinide and lanthanide separations. Extracted water induces reorganization of the amphiphilic extractant molecules, although we find this rearrangement is not strongly manifested in small-angle X-ray scattering making it challenging to probe without methods such as atomistic simulation. Using a graph theoretic approach to define hydrogen bonded water/malonamide aggregates from molecular dynamics simulations, we find evidence of a characteristic aggregate size by water number that results from geometric accommodation of the surrounding malonamide molecules. Furthermore, this implies a degree of size selectivity inherent to these water-in-oil aggregates. Conversely, we find no evidence of a characteristic size of the aggregates with respect to their malonamide number. By defining a separate graphical representation of self-association of the amphiphilic malonamides, we quantify how water affects the local and nonlocal topology of the malonamide network, providing a basis for characterization of the structure and impact of polar solutes in increasingly complex organic phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗