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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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At least 91 records · Page 5

Multicomponent and Multiphase Lipid Nanotubes Formed by Gliding Microtubule-Kinesin Motility and Phase-Separated Giant Unilamellar Vesicles

Cytoskeletal filaments and motor proteins are critical components in the transport and reorganization of membrane-based organelles in eukaryotic cells. Previous studies have recapitulated the microtubule-kinesin transport system in vitro to dynamically assemble large-scale nanotube networks from multilamellar liposomes and polymersomes. Moving toward more biologically relevant systems, this work examines whether lipid nanotube (LNT) networks can be generated from giant unilamellar vesicles (GUVs) and subsequently characterizes how the lipid composition may be tuned to alter the dynamics, structure, and fluidity of networks. Here, we describe a two-step process in which microtubule motility (i) drives the transport and aggregation of GUVs to form structures with a decreased energy barrier for LNT formation and (ii) extrudes LNTs without destroying parent GUVs, allowing for the formation of large LNT networks. We further show that the lipid composition of the GUV influences formation and morphology of the extruded LNTs and associated networks. For example, LNTs formed from phase-separated GUVs (e.g., liquid–solid phase-separated and coexisting liquid-ordered and liquid-disordered phase-separated) display morphologies related to the specific phase behavior reflective of the parent GUVs. Overall, the ability to form nanotubes from compositionally complex vesicles opens the door to generating lipid networks that more closely mimic the structure and function of those found in cellular systems.

59 BASIC BIOLOGICAL SCIENCES↗

Phase Separation, Capillarity, and Odd-Surface Flows in Chiral Active Matter

Active phase separations evade canonical thermodynamic descriptions and have thus challenged our understanding of coexistence and interfacial phenomena. Considerable progress has been made towards a nonequilibrium theoretical description of these traditionally thermodynamic concepts. Spatial parity symmetry is conspicuously assumed in much of this progress, despite the ubiquity of chirality in experimentally realized systems. Here, in this Letter, we derive a theory for the phase coexistence and interfacial fluctuations of a system that microscopically violates spatial parity. We find suppression of the phase separation as chirality is increased as well as the development of steady-state currents tangential to the interface dividing the phases. These odd flows are irrelevant to stationary interfacial properties, with stability, capillary fluctuations, and surface area minimization determined entirely by the capillary surface tension. Using large-scale Brownian dynamics simulations, we find excellent agreement with our theoretical scaling predictions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Dynamical Self-Assembly: Constrained phase separation and mesoscale dynamics in lipid membranes (Final Report)

This final technical report summarizes scientific and technical achievements derived through the the award, DE-FG02-04ER46173 [2013-2016, 2016-2017, and 2017-2018(NCE)], for the grant proposal titled, “Dynamical Self-Assembly: Constrained phase separation and mesoscale dynamics in lipid membranes.” The effort was organized into three major scientific aims: (1) characterize the mechanism of inter-layer coupling of laterally phase-separated domains in stacked lipid bilayers; (2) characterize curvature-dependent dynamic reorganization in membrane milieu; and (3) characterize real-time effects of mechanochemical perturbations on lateral phase separation membrane bilayers. The cumulative weight of the activities, including experimental research and collaborative modeling, disseminated through the publications listed above and presentations, has addressed two over-arching objectives: (a) to abstract a physical science based understanding of fundamental rules that determine dynamic self-assembly processes in lipid bilayer membranes - a versatile class of biologically inspired interfacial complex fluids and (b) to translate these physical principles into quantitative design rules for the development of new classes of membrane-based complex materials that exhibit complex, co-operative, and adaptive behavior.

36 MATERIALS SCIENCE↗

Low gravity phase separator

An apparatus is described for phase separating a gas-liquid mixture as might exist in a subcritical cryogenic helium vessel for cooling a superconducting magnet at low gravity such as in planetary orbit, permitting conservation of the liquid and extended service life of the superconducting magnet.

Smoot, G. F.↗

Zero-g experiments with a He II active phase separator for space application

An active phase separator (APS) for temperature control of He II space cooling systems was tested in a zero-g environment during a series of parabolic flights on a NASA KC 135 aircraft. The APS provides for liquid-gas separation and features an annular gap, a downstream heat exchanger and an upstream ball closure. The apparatus was operated during acceleration and floating and in two different heat load situations. The tests confirmed that adequate mass flow rates could be maintained using a vacuum pump to simulate space vacuum and that residual liquid could be evaporated from the heat exchanger after closing a ball valve to seal off flows.

Denner, H. D.↗

ATRP Enhances Structural Correlations In Polymerization–Induced Phase Separation**

Synthetic methods to control the structure of materials at sub–micron scales are typically based on the self–assembly of structural building blocks with precise size and morphology. On the other hand, many living systems can generate structure across a broad range of length scales in one step directly from macromolecules, using phase separation. Here, we introduce and control structure at the nano– and microscales through polymerization in the solid state, which has the unusual capability of both triggering and arresting phase separation. In particular, we show that atom transfer radical polymerization (ATRP) enables control of nucleation, growth, and stabilization of phase–separated poly–methylmethacrylate (PMMA) domains in a solid polystyrene (PS) matrix. ATRP yields durable nanostructures with low size dispersity and high degrees of structural correlations. Furthermore, we demonstrate that the length scale of these materials is controlled by the synthesis parameters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward Lithium Recovery Using Modular (and Membraneless) Phase Separation and Extraction (MPSE) Technology with Ionic Liquid (IL) Solvents: Effect of Coatings

In this work, a single-channel slope-plate Modular and Membrane-less Phase Separation and Extraction (MPSE) device was fabricated using 3D printing. The slope-plate was designed with an insertable glass slide to enable surface modification with coatings. Self-assembled monolayers (SAMs) and perfluoropolyether (Zdol) coatings were applied to tailor surface wettability and enhance phase separation. Using a model biphasic system of water and hexadecane, both coatings significantly improved the separation efficiency compared to the uncoated device by promoting selective wetting. Building on these results, lithium extraction from a simulated saline solution was investigated using 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf₂]) as the ionic liquid (IL) extractant. The IL effectively extracted Li⁺ from the aqueous phase in bulk extraction, demonstrating its potential for lithium recovery. However, the low interfacial tension between the IL and aqueous phases posed challenges for phase separation. The application of SAM and Zdol coatings effectively mitigated this issue. Overall, integrating tailored surface chemistry with the slope-plate MPSE design shows great promise as an efficient and scalable platform for studying liquid–liquid separation and optimizing ionic liquid–based extraction processes for lithium recovery from saline sources.

3D printing↗

Size-Dependent Liquid–Liquid Phase Separation in Atmospherically Relevant Complex Systems

Physical properties of aerosol particles, such as liquid-liquid phase separation (LLPS), have the potential to impact the climate system. Model systems have been shown to have size-dependent LLPS in the submicron regime, yet, these systems are an extreme simplification of ambient aerosol, which can include myriad organic compounds. In our research, we expand the studies of LLPS in particles consisting of ammonium sulfate and more complex organic mixtures from multiple organic compounds to α-pinene secondary organic matter (SOM). All systems display a size-dependent morphology, with small particles remaining homogeneous while large particles phase separate. Surprisingly, three-phase particles were also observed in some of the systems in addition to a new phase state that we have termed channel morphology, which can arise upon efflorescence. The existence of size-dependent LLPS in complex organic mixtures and SOM provides evidence that this is a relevant phenomenon for ambient aerosol and should be considered when modeling atmospheric aerosol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modulating the Mixing Gibbs Free Energy to Enhance Solid–Liquid Phase Separation for High–Performance Organic Solar Cells

Organic solar cells (OSC) feature a hierarchical structure with the electron donor/acceptor layer sandwiched by anode and cathode, which raises the importance of controlling the molecular crystal orientation, domain size, and vertical distribution to facilitate the charge collection at electrodes. However, the similar conjugated backbone of donor/acceptor material and fast film–formation kinetics have led to spinodal–decomposition–orientated phase separation that result in the film presenting an intimately mixed morphology and random molecular orientation. To solve the issue, the mixing Gibbs free energy–triggered solid–liquid phase separation during the film formation process is enhanced by solidifying one component and solvating the other based on a liquid additive. Following the liquid evaporation process, a favorable vertical distribution is obtained. Meanwhile, the prolonged solvation process enlarges the domain size and assists the molecules to diffuse and orient properly, enabling better exciton/charge dynamics during the power conversion processes. As a result, the fabricated devices exhibit a fill factor over 80% and an efficiency of 18.72%, which is one of the top efficiencies for binary OSCs. In conclusion, insights and a methodology is provided here to manipulate the organic donor/acceptor phase separation in terms of mixing Gibbs free energy.

14 SOLAR ENERGY↗

Suppression of phase separation in AlGaInAs compositionally graded buffers for 1550 nm photovoltaic converters on GaAs

We investigate strategies to suppress phase separation and reduce threading dislocation density (TDD) in AlGaInAs compositionally graded buffers (CGBs) that span the lattice constant range from GaAs to InP. Combining the results from high resolution x-ray diffraction, cathodoluminescence, transmission electron microscopy, and photovoltaic device measurements, we correlate the choices of epitaxial growth conditions with the defect structure of the CGBs and subsequent device performance. Both the use of substrates with high misorientation off (100) toward the (111)A plane and Zn doping instead of Si doping are shown to suppress phase separation and reduce TDD. We demonstrate a 0.74 eV GaInAs device grown on a GaAs substrate offcut 19.5° toward (111)A using a Zn-doped AlGaInAs CGB with TDD = 3.5 ± 0.2 × 10 6 cm -2 that has a bandgap-open circuit voltage offset of only 0.434 V measured under the AM1.5G solar spectrum. We characterized this device under high-intensity irradiance from a 1570 nm laser and measured a 31.9% peak laser power conversion efficiency at 3.6 W/cm 2 irradiance. These results provide a roadmap to the manufacture of laser- and thermal-power conversion devices with the performance and cost-effectiveness needed to drive adoption of these technologies at scale.

14 SOLAR ENERGY↗

Examining phase separation and crystallization in glasses with X-ray nano-computed tomography

X-ray nano-computed tomography (nano-CT) is a powerful technique to characterize and visualize 3 dimensional (3D) phenomena in complex glasses at the nanoscale. This technique can offer a unique opportunity to explore the intricate morphology of multicomponent glass and glass-ceramic samples, due to its low X-ray energy and high spatial resolution (down to 50 nm). In the current demonstration paper, nano-CT provided insight into crystallization and phase separation, as well as a variety of other phenomena, including corrosion, fracture, and porosity. At scales ranging from 100 to 20 μm, the microstructures of phase separation in borosilicate, complex silicate, and chalcogenide glass compositions were examined. In addition, crystallites present in simulant nuclear waste glasses, volcanic glasses, and other related samples were explored. Nano-CT analysis can add to the understanding of (1) the formation processes, (2) distributions, interactions, and compositions of phases, and (3) the mechanisms, structures, and growth of crystallization and phase separation. Nano-CT offers wide potential in the field of glass science, especially when (1) common characterization methods are insufficient, (2) simple sample preparation is required, (3) 3D rendering is needed, or (4) compelling images of small, complex features are desired.

36 MATERIALS SCIENCE↗

Gas-Liquid Flows and Phase Separation

Common issues for space system designers include:Ability to Verify Performance in Normal Gravity prior to Deployment; System Stability; Phase Accumulation & Shedding; Phase Separation; Flow Distribution through Tees & Manifolds Boiling Crisis; Heat Transfer Coefficient; and Pressure Drop.The report concludes:Guidance similar to "A design that operates in a single phase is less complex than a design that has two-phase flow" is not always true considering the amount of effort spent on pressurizing, subcooling and phase separators to ensure single phase operation. While there is still much to learn about two-phase flow in reduced gravity, we have a good start. Focus now needs to be directed more towards system level problems .

McQuillen, John↗

Aerosol Optical Tweezers Elucidate the Chemistry, Acidity, Phase Separations, and Morphology of Atmospheric Microdroplets

Aerosol particles represent unique chemical environments because of their high surface area-to-volume ratio that promotes the effects of interfacial chemistry in confined environments. Properties such as viscosity, diffusivity, water content, pH, and morphology—following liquid–liquid phase separation—can strongly alter how a particle interacts with condensable vapors and reactive trace gases, thus modifying its continual evolution and environmental effects. Our understanding of this chemical evolution of atmospheric particulate matter and its environmental impacts is largely limited by our ability to directly observe how these critical particle properties respond to the addition or reactive uptake of new chemical components. Aerosol optical tweezers (AOT) stably trap particles in focused laser beams, providing positional control and the retrieval of many of these critical properties required to understand and predict the chemistry of aerosolized microdroplets. The analytical power of the AOT stems from the retrieval of the cavity-enhanced Raman spectrum induced by the trapping laser. Analysis of the whispering gallery modes (WGMs) that resonate as a standing wave around the droplet’s interface, provide high accuracy measurements of the droplet’s size, refractive index (and thus a measurement of composition), and can distinguish between core–shell, partially engulfed, and homogeneous morphologies. In this study, we have advanced the ability to determine the properties of the core and shell phases in biphasic droplets, including obtaining high-accuracy pH measurements. These capabilities were applied to perform AOT physical chemistry experiments on authentic secondary organic aerosol (SOA) produced directly in the AOT chamber by ozonolysis of terpene vapors. The propensity of the SOA to phase separate as a shell from a wide range of nonpolar to polar core phases was observed, along with the discovery of a stable emulsified state of SOA particles in an aqueous salt droplet. Micron-thick SOA shells did not impede the gain or loss of water or squalane from the core to the surrounding air, indicating no significant diffusional limitations to condensational growth or partitioning even under dry conditions. These experiments formed the foundation of a new framework that predicts how the phase-separated morphology of complex aerosols containing organic carbon evolves during continual atmospheric oxidation processes. Increases in oxidation state will quickly drive conversion from a partially engulfed to core–shell morphology that has dramatically different chemical reactivity since the core phase is completely concealed by the shell. The recent advances in the experimental capabilities of the AOT technique such as presented here enable novel experimental methodologies that provide insights into the chemistry and multidimensional properties of aerosol microdroplets, and how these coevolve and respond to continual chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoscale Phase Separation and Large Refrigerant Capacity in Magnetocaloric Material LaFe 11.5 Si 1.5

Here, ferromagnetic transitions, the magnetocaloric effect, and the atomic-scale microstructure in an annealed bulk material of LaFe 11.5 Si 1.5 were investigated using magnetic measurements, Mössbauer spectroscopy, high-resolution X-ray diffraction analysis, and high-resolution transmission electron microscopy. The results provide evidence of the coexistence of two ferromagnetic phases with different Curie temperatures. The phase with a Curie temperature of 216 K corresponds to a Si-rich phase of a NaZn 13 -type structure with a small lattice volume, whereas the phase with a Curie temperature of 185 K corresponds to a Si-poor phase of a NaZn 13 -type structure with a large lattice volume. This phase coexistence is observed on a nanometer scale and it can account for inverse thermal hysteresis of the ferromagnetic transition in the Si-rich phase during warming. Furthermore, the phase coexistence helps the bulk material achieve a refrigeration capacity of 170 J kg -1 due to a combination of the magnetocaloric effect in each phase. It is determined that the magnetocaloric effect in the Si-rich and the Si-poor phase brings about a maximum of the total entropy change of -3.55 and -6.80 and J kg -1 K -1 at respective Curie temperatures, respectively. Fundamentally, the phase coexistence indicates coloring of Si atoms in the lattice of a NaZn 13 -type structure and can be attributed to nanoscale phase separation of a disordered precursor during annealing of the bulk material. The nanoscale phase separation may occur in other magnetocaloric materials, thus allowing for improvement of their refrigeration capacity.

36 MATERIALS SCIENCE↗

Thermally driven surface phase separation in intermetallic alloys

Intermetallic compounds are widely recognized for their high-temperature phase stability and resistance to composition and structural changes. However, we reveal athermally activated bulk-to-surface mass exchange mechanism that drives surface phase separation, resulting in the formation of surface precipitates with distinct composition andstructure from the bulk matrix. Using the archetypal β-NiAl system, we show that asymmetries in vacancy formation energies between Ni and Al atoms induce preferential Ni segregation to the surface, forming Ni-rich γ'-Ni 3 Al precipitates. By integrating in-situ electron microscopy, synchrotron X-ray absorption spectroscopy and first-principles computational modeling, we establish a direct mechanistic connection between bulk thermal defect dynamics, surface compositional evolution, and phase segregation behavior. This bulk-surface coupling mechanism can be a driver of surface phase separation in multicomponent alloys under thermal stress. In conclusion, these results refine the thermodynamic boundaries of intermetallic stability and provide insights into managingthe performance and durability of intermetallic alloys for demanding high-temperature applications.

36 MATERIALS SCIENCE↗

Magnetic and Optical Properties of Au–Co Solid Solution and Phase-Separated Thin Films and Nanoparticles

The chemical composition and morphology of Au x Co 1–x thin films and nanoparticles are controlled via a combination of cosputtering, pulsed laser-induced dewetting (PLiD), and annealing, leading to tunable magnetic and optical properties. Regardless of chemical composition, the as-deposited thin films and as-PLiD nanoparticles are found to possess a face-centered cubic (FCC) Au x Co 1–x solid-solution crystal structure. Annealing results in large phase-separated grains of Au and Co in both the thin films and nanostructures for all chemical compositions. The magnetic and optical properties are characterized via vibrating sample magnetometry (VSM), ellipsometry, optical transmission spectroscopy, and electron energy loss spectroscopy (EELS). Despite the exceptionally high magnetic anisotropy inherent to Co, the presence of sufficient Au (72 atom %) in the Au x Co 1–x solid solution results in superparamagnetic thin films. Among the as-PLiD nanoparticle samples, an increased Co composition leads to a departure from traditional ferromagnetism in favor of wasp-waisted hysteresis caused by magnetic vortices. Phase separation resulting from annealing leads to ferromagnetism for all compositions in both the thin films and nanoparticles. The optical properties of Au x Co 1–x nanostructures are also largely influenced by the chemical morphology, where the Au x Co 1–x intermixed solid solution has significantly damped plasmonic performance relative to pure Au and comparable to pure Co. Phase separation greatly enhances the quality factor, optical absorption, and electron energy loss spectroscopy (EELS) signatures. The enhancement of the localized surface plasmon resonances (LSPRs) scales with the reduction in Co composition, despite EELS evidence that excitation of the Co portions of a nanoparticle can provide a similar, and in some instances enhanced, LSPR resonance compared to Au. This behavior, however, is seemingly limited to the LSPR dipole mode, while higher-order modes are greatly damped by a Co aloof position. As a result, this observed magneto-plasmonic functionality and tunability could be applicable in biomedicine, namely, cancer therapeutics.

annealing (metallurgy)↗

Vapor-liquid phase separator studies

Porous plugs serve as both entropy rejection devices and phase separation components separating the vapor phase on the downstream side from liquid Helium 2 upstream. The liquid upstream is the cryo-reservoir fluid needed for equipment cooling by means of Helium 2, i.e Helium-4 below its lambda temperature in near-saturated states. The topics outlined are characteristic lengths, transport equations and plug results.

Yuan, S. W. K.↗

A two-dimensional phase separation on the spherical surface of the metallic glass Au55Pb22.5Sb22.5

Recent experiments indicate that a phase separation in a spherical sample of the metallic glass Au55Pb22.5Sb22.5 occurs near the surface of the sphere. This strongly suggests either a contribution of surface-free energy to the decomposition process or a possible influence of near surface impurities absorbed during synthesis of the sphere. The surface phase separation has been studied as a function of cooling rate of the sphere. At high cooling rates (small sphere sizes), the surface separation disappears altogether suggesting that the surface of the parent liquid droplet is initially homogeneous.

Lee, M. C.↗