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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Solvent-Dependent Dynamics of Cellulose Nanocrystals in Process-Relevant Flow Fields

Flow-assisted alignment of anisotropic nanoparticles is a promising route for the bottom-up assembly of advanced materials with tunable properties. While aligning processes could be optimized by controlling factors such as solvent viscosity, flow deformation, and the structure of the particles themselves, it is necessary to understand the relationship between these factors and their effect on the final orientation. In this study, we investigated the flow of surface-charged cellulose nanocrystals (CNCs) with the shape of a rigid rod dispersed in water and propylene glycol (PG) in an isotropic tactoid state. In situ scanning small-angle X-ray scattering (SAXS) and rheo-optical flow-stop experiments were used to quantify the dynamics, orientation, and structure of the assigned system at the nanometer scale. The effects of both shear and extensional flow fields were revealed in a single experiment by using a flow-focusing channel geometry, which was used as a model flow for nanomaterial assembly. Due to the higher solvent viscosity, CNCs in PG showed much slower Brownian dynamics than CNCs in water and thus could be aligned at lower deformation rates. Moreover, CNCs in PG also formed a characteristic tactoid structure but with less ordering than CNCs in water owing to weaker electrostatic interactions. The results indicate that CNCs in water stay assembled in the mesoscale structure at moderate deformation rates but are broken up at higher flow rates, enhancing rotary diffusion and leading to lower overall alignment. Albeit being a study of cellulose nanoparticles, the fundamental interplay between imposed flow fields, Brownian motion, and electrostatic interactions likely apply to many other anisotropic colloidal systems.

36 MATERIALS SCIENCE↗
NASA NTRS2012

Combustion, Complex Fluids, and Fluid Physics Experiments on the ISS

From the very early days of human spaceflight, NASA has been conducting experiments in space to understand the effect of weightlessness on physical and chemically reacting systems. NASA Glenn Research Center (GRC) in Cleveland, Ohio has been at the forefront of this research looking at both fundamental studies in microgravity as well as experiments targeted at reducing the risks to long duration human missions to the moon, Mars, and beyond. In the current International Space Station (ISS) era, we now have an orbiting laboratory that provides the highly desired condition of long-duration microgravity. This allows continuous and interactive research similar to Earth-based laboratories. Because of these capabilities, the ISS is an indispensible laboratory for low gravity research. NASA GRC has been actively involved in developing and operating facilities and experiments on the ISS since the beginning of a permanent human presence on November 2, 2000. As the lead Center for combustion, complex fluids, and fluid physics; GRC has led the successful implementation of the Combustion Integrated Rack (CIR) and the Fluids Integrated Rack (FIR) as well as the continued use of other facilities on the ISS. These facilities have supported combustion experiments in fundamental droplet combustion; fire detection; fire extinguishment; soot phenomena; flame liftoff and stability; and material flammability. The fluids experiments have studied capillary flow; magneto-rheological fluids; colloidal systems; extensional rheology; pool and nucleate boiling phenomena. In this paper, we provide an overview of the experiments conducted on the ISS over the past 12 years.

Motil, Brian↗
DOE OSTI2021

Transport and Assembly of Magnetic Surface Rotors**

This minireview focuses on recent advances with surface magnetic rotors, namely field-responsive spherical or anisotropic microparticles that translate close to, or are embedded in a confining surface. The application of external magnetic modulations allows these microscopic wheels to be remotely spun and steered while also tuning their interactions and inducing assembly from a collection of disordered, moving units. With optical microscopy one can observe and characterize the complex collective phenomena that emerge in dissipative colloidal systems driven far from equilibrium by external fields. From a technological point of view, magnetic surface rotors envisage implementation into microfluidic devices, and can be used for drug delivery, mixing as well as a model system for biological active matter.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Effect of ethoxylation and lauryl alcohol on the self-assembly of sodium laurylsulfate: Significant structural and rheological transformation

Fatty alcohols are added to the surfactant solutions to modify foaming and lubrication properties, while the degree of ethoxylation is increased to improve mildness to the skin. However, it is envisioned that both parameters are capable of manipulating rheological and morphological properties. Therefore, an efficient control over the carbon chain length, amount of fatty alcohol and degree of ethoxylation could modify the surfactant self-assembly in an unprecedented way. The present work is focused on understanding the structural transformation, intermolecular interactions and rheological properties of the colloidal systems containing various amounts of lauryl alcohol (LA), and surfactant with varying degrees of ethoxylation. Additionally, combined small-angle neutron scattering (SANS), nuclear magnetic resonance (NMR) spectroscopy, rheological and morphological studies were performed to elucidate these properties. The results reveal that an increase in LA content increases the system viscosity ultimately forming a gel, and drives the assembly pattern of the surfactant from ellipsoidal micellar to lamellar via a vesicular and vesicular/lamellar mixed intermediates. Conversely, higher degrees of ethoxylation delay the onset of morphological transformation and gel formation. The interplay between hydrophobic and polar interactions coupled with hydrogen bonding interactions drive the overall rheological and morphological transformations. Therefore, fine-tuning residual chemicals can offer a novel tool for optimization of the product formulation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Reentrant glass transition leading to ultrastable metallic glass

Polyamorphs are often observed in amorphous matters, and a representative example is the reentrant glass transition in colloid systems. For metallic amorphous alloys, however, the cases reported so far are limited to metallic glasses (MGs) that undergo electronic transitions under gigapascal applied pressure, or the presence of two liquids at the same composition. In this paper, we report the first observation of a reentrant glass transition in MGs. This unusual reentrant glass transition transforms an MG from its as-quenched state (Glass I) to an ultrastable state (Glass II), mediated by the supercooled liquid of Glass I. Specifically, upon heating to above its glass transition temperature under ambient pressure, Glass I first transitions into its supercooled liquid, which then transforms into a new Glass II, accompanied by an exothermic peak in calorimetric scan, together with a precipitous drop in volume, electrical resistance and specific heat, as well as clear evidence of local structural ordering on the short-to-medium-range scale revealed via in-situ synchrotron X-ray scattering. Atomistic simulations indicate enhanced ordering of locally favored motifs to establish correlations in the medium range that resemble those in equilibrium crystalline compounds. The resulting lower-energy Glass II has its own glass transition temperature higher than that of Glass I by as much as 50 degrees. This route thus delivers a thermodynamically and kinetically ultrastable MG that can be easily retained to ambient conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Crystal Nucleation Kinetics and Mechanism: Influence of Interaction Potential

Modulating liquid-to-solid transitions and the resulting crystalline structure for tailored properties is much desired. Colloidal systems are exemplary to this end, but the fundamental knowledge gaps in relating the influence of intermolecular interactions to crystallization behavior continue to hinder progress. In this study, we address this knowledge gap by studying nucleation and growth in systems with modified Lennard-Jones potential. Specifically, we study the commonly used 12-6 potential and a softer 7-6 potential. The thermodynamic state point for the study is chosen such that both systems are investigated at the same level of supercooling and pressure. Under these conditions, we find that the nucleation rate for both systems is comparable. Interestingly, the nucleation pathways and resulting crystal structures are different. In the 12-6 system, nucleation and growth occur predominantly through the FCC structure. Softening the potential alters the critical nucleus composition and introduces two distinct nucleation pathways. One pathway predominantly leads to the nucleus with a body-centered cubic (BCC) structure, while the other favors the face-centered cubic (FCC) arrangement. Our study illustrates that polymorph selection can be achieved through modifications to intermolecular interactions without impacting nucleation kinetics. The results have significant implications in designing approaches for polymorph selection and modulating self-assembly mechanisms.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Reversible Binding Interfaces Made of Microstructured Polymer Brushes

The polymer brush architecture of the end-tethered polymer molecules is one of the most widely used efficient methods to regulate interfacial interactions in colloidal systems found in live matter and manufactured materials. Emerging applications of polymer brush structures require solutions to new tasks in the control of interfacial interactions. The rapid development of live cell manufacturing relies on scalable and efficient cell harvesting methods. Stimuli-responsive surfaces made of surface-grafted poly(N-isopropylacrylamide) (PNIPAM) can bind and detach the adherent cell upon changes in temperature and have been used for cell growth and harvesting. The applications are limited by the requirement to satisfy a range of PNIPAM coating characteristics that depend on the dimensions of the integrin complex in the cell membrane and the basal surface. The analysis of the microstructured surfaces, when adhesive and disjoining functions of the microdomains are decoupled, shows that many limitations of PNIPAM one-component coatings can be avoided by using a much broader range of structural characteristics of the microstructured interfaces composed of alternating disjoining PNIPAM domains and adhesive polymeric domains with cell-affinity functional groups. Temperature-controlled reversible adhesion to such microstructured interfaces is studied here experimentally with model systems of solid spherical particles and by employing simulations for solid and soft membranes interacting with the microstructured surfaces to mimic interactions with soft and solid disk-like particles.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Dynamics of a Supercooled Disordered Sphere-Forming Diblock Copolymer as Determined by X-ray Photon Correlation and Dynamic Mechanical Spectroscopies

Here, we report the dynamic behavior of a sphere-forming poly(styrene)-block-poly(1,4-butadiene) (PS–PB) diblock copolymer comprising 20 vol % PB below the order–disorder transition temperature ( T ODT = 153 °C) using dynamic mechanical spectroscopy (DMS) and X-ray photon correlation spectroscopy (XPCS). A time–temperature transformation diagram was constructed by monitoring the elasticity of the sample as a function of time following rapid quenches of the disordered melt to various temperatures T < T ODT . Isothermal frequency spectra acquired prior to nucleation of the ordered BCC phase were time–temperature superposed, and the shift factors were fit using the Williams–Landel–Ferry (WLF) equation. For comparison, XPCS measurements were used to extract relaxation times from the supercooled liquid as a function of the quench temperature. Alignment of the temperature dependence of the XPCS-based relaxation times with that of the WLF shift factors in the range T = 125–140 °C indicates that both techniques probe the fluctuating mesomorphic micelle dynamics mediated by the relaxation modes of individual chains, including interparticle chain exchange. For deeper quench temperatures, T ODT – T ≥ 28 °C, departure of the XPCS time constant from WLF behavior is consistent with a jamming transition, analogous to that encountered in concentrated colloidal systems. We postulate that the dominant relaxation mode in the supercooled disordered liquid transitions from ergodic dynamics governed by chain exchange to a nonergodic regime dominated by local rearrangement of micellar particles at T ≈ T erg , where T erg denotes the ergodicity temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Electrochemically Determined and Structurally Justified Thermochemistry of H atom Transfer on Ti-Oxo Nodes of the Colloidal Metal–Organic Framework Ti-MIL-125

Titanium dioxide (TiO 2 ) has long been employed as (photo)electrodes for reactions relevant to energy storage and renewable energy synthesis. Proton-coupled electron transfer (PCET) reactions with equimolar amounts of protons and electrons at the TiO 2 surface or within the bulk structure lie at the center of these reactions. Because a proton and an electron are thermochemically equivalent to an H-atom, these reactions are essentially H-atom transfer reactions. Thermodynamics of H-atom transfer has a complex dependence on the synthetic protocol and chemical history of the electrode, the reaction medium, and many others; together, these complications preclude the understanding of the H-atom transfer thermochemistry with atomic-level structural knowledge. Herein, we report our success in employing open-circuit potential (E OCP ) measurements to quantitatively determine the H-atom transfer thermochemistry at structurally well-defined Ti-oxo clusters within a colloidally stabilized metal–organic framework (MOFs), Ti-MIL-125. The free energy to transfer H-atom, Ti 3+ O–H bond dissociation free energy (BDFE), was measured to be 68(2) kcal mol -1 . To the best of our understanding, this is the first report on using E OCP measurements to quantify thermochemistry on any MOFs. The proton topology, the structural change upon the redox reaction, and BDFE values were further quantitatively corroborated using computational simulations. Furthermore, comparisons of the E OCP -derived BDFEs of Ti-MIL-125 to similar parameters in the literature suggest that E OCP should be the preferred method for quantitatively accurate BDFE calculations. Here, the reported success in employing E OCP for nanosized Ti- MIL-125 should lay the ground for thermochemical measurements of other colloidal systems, which are otherwise challenging. Implications of these measurements on Ti-MIL-125 as an H-atom acceptor in chemical reactions and comparisons with other MOFs/metal oxides are discussed.

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

Observation of ordered organic capping ligands on semiconducting quantum dots via powder X-ray diffraction

Abstract Powder X-ray diffraction is one of the key techniques used to characterize the inorganic structure of colloidal nanocrystals. The comparatively low scattering factor of nuclei of the organic capping ligands and their propensity to be disordered has led investigators to typically consider them effectively invisible to this technique. In this report, we demonstrate that a commonly observed powder X-ray diffraction peak around $$q=1.4{\AA}^{-1}$$ q = 1.4 Å − 1 observed in many small, colloidal quantum dots can be assigned to well-ordered aliphatic ligands bound to and capping the nanocrystals. This conclusion differs from a variety of explanations ascribed by previous sources, the majority of which propose an excess of organic material. Additionally, we demonstrate that the observed ligand peak is a sensitive probe of ligand shell ordering. Changes as a function of ligand length, geometry, and temperature can all be readily observed by X-ray diffraction and manipulated to achieve desired outcomes for the final colloidal system.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Many-Body Potential for Simulating Self-Assembly of Polymer-Grafted Nanoparticles in a Polymer Matrix

Many-body interactions between polymer-grafted nanoparticles (NPs) play a key role in promoting their assembly into low-dimensional structures within polymer melts, even when the particles are spherical and isotropically grafted. However, capturing such interactions in simulations of NP assembly is very challenging because explicit modeling of the polymer grafts and melt chains is highly computationally expensive, even using coarse-grained models. Here, we develop a many-body potential for describing the effective interactions between spherical polymer-grafted NPs in a polymer matrix through a machine-learning approach. The approach involves using permutationally invariant polynomials to fit two- and three-body interactions derived from the potential of mean force calculations. The potential developed here reduces the computational cost by several orders of magnitude, thereby, allowing us to explore assembly behavior over large length and time scales. We show that the potential not only reproduces previously known assembled phases such as 1D strings and 2D hexagonal sheets, which generally cannot be achieved using isotropic two-body potentials, but can also help discover interesting phases such as networks, clusters, and gels. We demonstrate how each of these assembly morphologies intrinsically arises from a competition between two- and three-body interactions. Our approach for deriving many-body effective potentials can be readily extended to other colloidal systems, enabling researchers to make accurate predictions of their behavior and dissect the role of individual interaction energy terms of the overall potential in the observed behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Towards predictive control of reversible nanoparticle assembly with solid-binding proteins

Although a broad range of ligand-functionalized nanoparticles and physico-chemical triggers have been exploited to create stimuli-responsive colloidal systems, little attention has been paid to the reversible assembly of unmodified nanoparticles with non-covalently bound proteins. Previously, we reported that a derivative of green fluorescent protein engineered with oppositely located silica-binding peptides mediates the repeated assembly and disassembly of 10-nm silica nanoparticles when pH is toggled between 7.5 and 8.5. We captured the subtle interplay between interparticle electrostatic repulsion and their protein-mediated short-range attraction with a multiscale model energetically benchmarked to collective system behavior captured by scattering experiments. Here, in this work, we show that both solution conditions (pH and ionic strength) and protein engineering (sequence and position of engineered silica-binding peptides) provide pathways for reversible control over growth and fragmentation, leading to clusters ranging in size from 25 nm protein-coated particles to micrometer-size aggregate. We further find that the higher electrolyte environment associated with successive cycles of base addition eventually eliminates reversibility. Our model accurately predicts these multiple length scales phenomena. The underpinning concepts provide design principles for the dynamic control of other protein- and particle-based nanocomposites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Self-organized internal architectures of chiral micro-particles

The internal architecture of polymeric self-assembled chiral micro-particles is studied by exploring the effect of the chirality, of the particle sizes, and of the interface/surface properties in the ordering of the helicoidal planes. The experimental investigations, performed by means of different microscopy techniques, show that the polymeric beads, resulting from light induced polymerization of cholesteric liquid crystal droplets, preserve both the spherical shape and the internal self-organized structures. The method used to create the micro-particles with controlled internal chiral architectures presents great flexibility providing several advantages connected to the acquired optical and photonics capabilities and allowing to envisage novel strategies for the development of chiral colloidal systems and materials.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Coupled electrostatic and material surface stresses yield anomalous particle interactions and deformation

Like-charges repel, and opposite charges attract. This fundamental tenet is a result of Coulomb's law. However, the electrostatic interactions between dielectric particles remain topical due to observations of like-charged particle attraction and the self-assembly of colloidal systems. Here, we show, using both an approximate description and an exact solution of Maxwell's equations, that nonlinear charged particle forces result even for linear material systems and can be responsible for anomalous electrostatic interactions such as like-charged particle attraction and oppositely charged particle repulsion. Furthermore, these electrostatic interactions and the deformation of such particles have fundamental implications for our understanding of macroscopic electrodynamics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Temperature Quenching and Fluorescence Depolarization of Carbon Nanodots Obtained via Paraffin Pyrolysis

A temperature effect on fluorescence intensity and polarization of a colloidal system of carbon nanodots in glycerol under linearly polarized pumping conditions is studied. Nanodots are obtained via pyrolysis of paraffin in nanopores of a mesoporous silica. An increase in temperature leads to quenching of nanodots fluorescence, and activation energy of the quenching process is assessed. An experimental relationship between the linear fluorescence polarization and temperature is described by the Levshin–Perrin equation, which takes into account the rotational diffusion of luminescent particles (fluorophores) in a liquid matrix. The size of fluorophores is noticeably smaller than that of carbon nanodots according to the Levshin–Perrin model. A difference between the dimensions of the fluorophore and the nanodot indicates that the small atomic groups responsible for luminescence of the nanodot possess high segmental mobility.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Ordered and disordered skyrmion states on a square substrate

We examine the ordering of skyrmions interacting with a square substrate created from a modulation of anisotropy using atomistic simulations. We consider fillings of ƒ = 1.5, 2.0, 2.5, 3.0, and 3.5 skyrmions per potential minimum as a function of magnetic field and sample size. For a filling of ƒ = 2.0, we find various dimer orderings, such as tilted dimer states, as well as antiferromagnetic ordering that is similar to the colloidal dimer ordering seen on square substrates. Furthermore, the ability of the skyrmions to change shape or annihilate produces additional states that do not occur in the colloidal systems. For certain parameters at ƒ = 2.0, half of the skyrmions can annihilate to form a square lattice, or a superlattice of trimers and monomers containing skyrmions of different sizes can form. At lower fields, ordered stretched skyrmion states can appear, and for zero field, there can be ordered stripe states. For ƒ = 3.0, we find ferromagnetic ordered trimers, tilted lattices, columnar lattices, and stretched phases. For fillings of ƒ = 1.5 and 2.5, we find bipartite lattices, different ordered and disordered states, and several extended disordered regions produced by frustration effects.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Mixed-Phase Clouds: Progress and Challenges

Mixed-phase clouds represent a three-phase colloidal system consisting of water vapor, ice particles, and coexisting supercooled liquid droplets. Mixed-phase clouds are ubiquitous in the troposphere, occurring at all latitudes from the polar regions to the tropics. Because of their widespread nature, mixed-phase processes play critical roles in the life cycle of clouds, precipitation formation, cloud electrification, and the radiative energy balance on both regional and global scales.Yet, in spite of many decades of observations and theoretical studies, our knowledge and understanding of mixed-phase cloud processes remains incomplete.Mixed-phase clouds are notoriously difficult to represent in numerical weather prediction and climatemodels, and their description in theoretical cloud physics still presents complicated challenges. In this chapter, the current status of our knowledge on mixed-phase clouds, obtained from theoretical studies and observations, is reviewed. Recent progress, along with a discussion of problems and gaps in understanding the mixed-phase environment is summarized. Specific steps to improve our knowledge of mixed-phase clouds and their role in the climate and weather system are proposed.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1989

An asymptotic description of transient settling and ultrafiltration of colloidal dispersions

The present model for the sedimentation of colloidal systems includes a diffusion term in the governing equation which, in the regions above the sediment, acts as small perturbation to the Kynch (1952) theory. Within the sediment, diffusion is comparable to convection due to the the high solid volume fraction. An application of the method of matched asymptotic expansions to the conservation equation allows a complete description of the settling process to be formulated, with specific attention to volume-fraction evolution in the sediment.

Davis, K. E.↗