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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 559 records · Page 31
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Modeling of particle agglomeration in nanofluids

Agglomeration strongly influences the stability or shelf life of nanofluid. The present computational and experimental study investigates the rate of agglomeration quantitatively. Agglomeration in nanofluids is attributed to the net effect of various inter-particle interaction forces. For the nanofluid considered here, a net inter-particle force depends on the particle size, volume fraction, pH, and electrolyte concentration. A solution of the discretized and coupled population balance equations can yield particle sizes as a function of time. Nanofluid prepared here consists of alumina nanoparticles with the average particle size of 150 nm dispersed in de-ionized water. As the pH of the colloid was moved towards the isoelectric point of alumina nanofluids, the rate of increase of average particle size increased with time due to lower net positive charge on particles. The rate at which the average particle size is increased is predicted and measured for different electrolyte concentration and volume fraction. The higher rate of agglomeration is attributed to the decrease in the electrostatic double layer repulsion forces. The rate of agglomeration decreases due to increase in the size of nano-particle clusters thus approaching zero rate of agglomeration when all the clusters are nearly uniform in size. Predicted rates of agglomeration agree adequate enough with the measured values; validating the mathematical model and numerical approach is employed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

Heterogeneous Activation, Local Structure, and Softness in Supercooled Colloidal Liquids

We experimentally characterize heterogeneous nonexponential relaxation in bidisperse supercooled colloidal liquids utilizing a recent concept called “softness”. Particle trajectory and structure data enable classification of particles into subgroups with different local environments and propensities to hop. We determine residence times t R between particle hops and show that t R derived from particles in the same softness subgroup are exponentially distributed. Using the mean residence time t¯ R for each softness subgroup, and a Kramers’ reaction rate model, we estimate the activation energy barriers E b for particle hops, and show that both t¯ R and E b are monotonic functions of softness. Lastly, we derive information about the combinations of large and small particle neighbors that determine particle softness, and we explicitly show that multiple exponential relaxation channels in the supercooled liquid give rise to its nonexponential behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2019

In Operando Monitoring of Dynamic Recovery in 3D-Printed Thermoset Nanocomposites by XPCS

Extrusion-based additive manufacturing methods, such as direct-write of carbon fiber-reinforced epoxy inks, have become an attractive route toward development of structural composites in recent years, because of emerging techniques such as big area additive manufacturing. The development of improved materials for these methods has been a major focus area; however, an understanding of the effects of the printing process on the structural and dynamic recovery in printed materials remains largely unexplored. Here, our goal is to capture multiscale and temporal morphology and dynamics within thermosetting composite inks to determine the parameters during the printing process that influence the recovery of the printed material. Herein, we use X-ray photon correlation spectroscopy in small-angle scattering geometry to reveal both morphology and recovery dynamics of a nanoparticle (layered-silicate Cloisite 30B) in a thermoset epoxy resin (EPON 826) during the printing process in real time. Our results show that the dynamics of the layered silicate particles during recovery are anisotropic and slow down to behavior which is characteristic of aging in colloidal clay suspensions around tage ≈ 12 s. The dynamics and alignment of the particles during recovery were tempo-spatially mapped, and the recovery post printing was shown to be strongly influenced by the deposition onto the build plate in addition to the extrusion through the print head. Finally, our in operando results provide insight into the parameters that must be considered when optimizing materials and methods for precisely tailored local properties during 3D printing.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Nanophotonic force microscopy: Characterizing particle–surface interactions using near-field photonics

Direct measurements of particle–surface interactions are important for characterizing the stability and behavior of colloidal and nanoparticle suspensions. Current techniques are limited in their ability to measure pico-Newton scale interaction forces on submicrometer particles due to signal detection limits and thermal noise. In this paper, we present a new technique for making measurements in this regime, which we refer to as nanophotonic force microscopy. Using a photonic crystal resonator, we generate a strongly localized region of exponentially decaying, near-field light that allows us to confine small particles close to a surface. From the statistical distribution of the light intensity scattered by the particle we are able to map out the potential well of the trap and directly quantify the repulsive force between the nanoparticle and the surface. Finally, as shown in this Letter, our technique is not limited by thermal noise, and therefore, we are able to resolve interaction forces smaller than 1 pN on dielectric particles as small as 100 nm in diameter.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Shape-driven, emergent behavior in active particle mixtures

Abstract Active particle systems can vary greatly from one-component systems of spheres to mixtures of particle shapes at different composition ratios. We investigate computationally the combined effect of anisotropy and stoichiometry on the collective behavior of two-dimensional active colloidal mixtures of polygons. We uncover three emergent phenomena not yet reported in active Brownian particle systems. First, we find that mixtures containing hexagons exhibit micro-phase separation with large grains of hexagonal symmetry. We quantify a measurable, implicit ‘steric attraction’ between the active particles as a result of shape anisotropy and activity. This calculation provides further evidence that implicit interactions in active systems, even without explicit attraction, can lead to an effective preferential attraction between particles. Next, we report stable fluid clusters in mixtures containing one triangle or square component. We attribute the fluidization of the dense cluster to the interplay of cluster destabilizing particles, which introduce grain boundaries and slip planes into the system, causing solid-like clusters to break up into fluid clusters. Third, we show that fluid clusters can coexist with solid clusters within a sparse gas of particles in a steady state of three coexisting phases. Our results highlight the potential for a wide variety of behavior to be accessible to active matter systems and establish a route to control active colloidal systems through simple parameter designs.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

High Temperature, Isothermal Growth Promotes Close Packing and Thermal Stability in DNA-Engineered Colloidal Crystals

Here, we report a strategy to accelerate the synthesis and increase the crystallinity of colloidal crystals engineered with DNA. Specifically, by holding the DNA-modified Au particle building blocks above the T m of the individual nanoparticle building blocks, but slightly below the T m of the anticipated colloidal crystal during the assembly process, crystallinity is increased, and enthalpically-favored phases with high degrees of facet registration are observed. We studied the utility of this approach with systems for which the commonly adopted slow-cooling approach yielded primarily amorphous aggregates. In particular, we used it to synthesize high-volume fraction colloidal crystals from large (80 nm) anisotropic nanoparticles (cubes and rhombic dodecahedra) with short (<14 nm) DNA designed to restrict the degrees of freedom for the DNA bonds and maintain the anisotropy of the particle building block. Small-angle X-ray scattering and electron microscopy studies show that the crystalline phases synthesized via this method are more thermally stable than their corresponding aggregate phases, likely due to an increased number of DNA-DNA bonds between particles. Crystal size tunability (between 0.5 and 15 µm edge lengths) and epitaxial growth were demonstrated using this strategy by modulating the NaCl concentration in tandem with previously synthesized colloidal crystal nuclei. Taken together, this isothermal strategy provides a route to deliberately crystallize a wide variety of anisotropic colloidal materials and expands the phase space accessible to nanoparticles modified with DNA.

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

Non-Reciprocity, Metastability, and Dynamic Reconfiguration in Co-Assembly of Active and Passive Particles

Living organisms often exhibit non-reciprocal interactions where the forces acting on the objects are not equal in magnitude or opposite in direction. The combination of reciprocal and non-reciprocal interactions between synthetic building blocks remains largely unexplored. Here, out-of-equilibrium assemblies of non-motile isotropic passive and metal-patched motile active particles are formed by overlapping bulk interactions with directed self-propulsion. An external alternating current (AC) electric field generates concurrent dipolar and induced-charge electrophoretic forces between the particles which are evaluated using microscopy. The interaction force measurements allow to determine the degree of reciprocity in interactions, which is tunable by designing the active particle and its trajectory. While linearly-propelled active particles evade assembly with passive particles, helically propelled active particles form active-passive clusters with dynamic reconfiguration and long-lived metastability. Large clusters display programmable fluctuations and reconfigurability by controlling the fraction of active particles. The study establishes principles of integrating reciprocal and non-reciprocal interactions in guided colloidal assembly of reconfigurable metastable structures.

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

Microstructure and nonlinear signatures of yielding in a heterogeneous colloidal gel under large amplitude oscillatory shear

We investigate yielding in a colloidal gel that forms a heterogeneous structure, consisting of a two-phase bicontinuous network of colloid-rich domains of fractal clusters and colloid-poor domains. Combining large amplitude oscillatory shear measurements with simultaneous small and ultra-small angle neutron scattering (rheo-SANS/USANS), we characterize both the nonlinear mechanical processes and strain amplitude-dependent microstructure underlying yielding. We observe a broad, three-stage yielding process that evolves over an order of magnitude in strain amplitude between the onset of nonlinearity and flow. Analyzing the intracycle response as a sequence of physical processes reveals a transition from elastic straining to elastoplastic thinning (which dominates in region I) and eventually yielding (which evolves through region II) and flow (which saturates in region III), and allows quantification of instantaneous nonlinear parameters associated with yielding. These measures exhibit significant strain rate amplitude dependence above a characteristic frequency, which we argue is governed by poroelastic effects. Correlating these results with time-averaged rheo-USANS measurements reveals that the material passes through a cascade of structural breakdown from large to progressively smaller length scales. In region I, compression of the fractal domains leads to the formation of large voids. In regions II and III, cluster-cluster correlations become increasingly homogeneous, suggesting breakage and eventually depercolation of intercluster bonds at the yield point. All significant structural changes occur on the micron-scale, suggesting that large-scale rearrangements of hundreds or thousands of particles, rather than the homogeneous rearrangement of particle-particle bonds, dominate the initial yielding of heterogeneous colloidal gels.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Zeta potential measurements of SiO 2 and TiO 2 particles in anionic and cationic surfactant solutions

Zeta potential measurements can provide valuable insights into colloidal stability and may reflect changes in the electrochemical double layer that influence electrocatalysis. In this study, we used zeta potential measurements to monitor and investigate the adsorption behavior of anionic sodium dodecyl sulfate (SDS), cationic dodecyl trimethyl ammonium bromide (DTAB), and cationic cetyl trimethyl ammonium bromide (CTAB) surfactants on SiO 2 and TiO 2 particles in DI water. The zeta potentials of SiO 2 and TiO 2 particles were measured as a function of particle concentration in 1.0 mM, 5.0 mM, and 10.0 mM surfactant solutions. Results indicate that there is no significant adsorption of DS - ions on SiO 2 particles across all SDS concentrations investigated in this study. The zeta potential of TiO 2 particles shifts from negative to positive as particle concentration increases at 1.0 mM SDS, indicating a decrease in DS - ions adsorption per TiO 2 particle. Adsorption plateaus at 5.0 mM SDS for all TiO 2 concentrations studied. In contrast, DTA + and CTA + ions showed clear adsorption on SiO 2 particles, but DTA + exhibited no apparent adsorption on TiO 2 particles. Interestingly, CTA + adsorption on TiO 2 was only evident at higher surfactant concentrations. This study presents a systematic investigation of zeta potential behavior as a function of particle and surfactant concentration, highlighting adsorption saturation and electrostatic reversal. Unlike prior work that was limited to single particle concentration measurements, our approach reveals how surfactant adsorption per particle decreases with increasing surface area. Despite the structural similarity between DTAB and CTAB, this study captured the different adsorption behaviors of both surfactants on SiO 2 and TiO 2 , emphasizing the role of the overall structure of the surfactant on surfactant adsorption behavior. These insights refine the interpretation of zeta potential data and advance understanding of surfactant adsorption on oxide particles. The insight provided in this study about surfactant adsorption on SiO 2 and TiO 2 particles could have important implications for the design of more effective colloidal and catalytic systems.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
NASA NTRS1984

The role of water in slip casting

Slips and casting are considered in terms of physical and colloidal chemistry. Casting slips are polydisperse suspensions of lyophobic particles in water, whose degree of coagulation is controlled by interaction of flocculating and deflocculating agents. Slip casting rate and viscosity are functions of temperature. Slip rheology and response to deflocculating agents varies significantly as the kinds and amounts of colloid modifiers change. Water is considered as a raw material. Various concepts of water/clay interactions and structures are discussed. Casting is a de-watering operation in which water moves from slip to cast to mold in response to a potential energy termed moisture stress. Drying is an evaporative process from a free water surface.

Mccauley, R. A.↗
DOE OSTI2021

Aqueous TiO 2 Nanoparticles React by Proton-Coupled Electron Transfer

Redox reactions of aqueous colloidal TiO 2 4 nm nanoparticles (NPs) have been examined, including both citratecapped and uncapped NPs (c-TiO 2 and uc-TiO 2 ). Photoreduction gave stable blue colloidal c-TiO 2 R NPs with 10–60 electrons per particle. Equilibration of these reduced NPs with soluble redox reagents such as methylviologen (MV 2+ ) provided measurements of the colloid reduction potential as a function of pH. The potentials of c-TiO 2 from pH 2–9 varied linearly with pH, with a slope of –60 ± 5 mV/pH. Estimates of the potential at pH 12 were consistent with extrapolating that line to high pH. The reduction potentials did not correlate with the zeta potentials (ζ) or the surface charge of the NPs across this pH range. Similar reduction potentials were observed for c- and uc-TiO 2 at low pH even though they have quite different ζ potentials. These results show that the common surface-charging explanation of the pH dependence is not tenable in these systems. Oxidation of reduced c-TiO 2 R with the electron-transfer oxidant potassium triiodide (KI 3 ) occurred with a significant drop in pH, showing that protons were released when the electrons were removed from the NPs. Smaller pH drops were observed for the proton-coupled electron transfer (PCET) reagents O 2 (air) and 4-MeO-TEMPO (4-methoxy-2,2,6,6-tetramethylpiperine-1-oxy radical). The difference in the number of protons released with KI 3 vs O 2 and 4-MeO-TEMPO was roughly one proton per electron removed. Thus, the thermodynamically preferred reactivity of these colloidal TiO 2 NPs is PCET over the pH 2–13 range studied. The measured redox potentials refer to the chemical process TiO 2 + H + + e – → TiO 2 ·e – ,H + ; and therefore they do not correspond with an electronic energy such as a conduction band edge or flat band potential. The 1e – /1H + stoichiometry means that the TiO 2 reduction potentials correspond to a TiO 2 –H bond dissociation free energy (BDFE), determined to be 49 ± 2 kcal mol –1 . The PCET description is consistent with the pH dependence of E(TiO 2 /TiO 2 ·e – ,H + ), the release of protons upon oxidation, the lack of correlation with ζ potentials, the similarity of capped and uncapped NPs, and the small change in the potential and BDFE from the first to the last electron/proton pair (H atom) removed. Furthermore, this behavior is suggested to be the norm for redox-active oxide/water interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Strain heterogeneity in sheared colloids revealed by neutron scattering

Recent computational and theoretical studies have shown that the deformation of colloidal suspensions under a steady shear is highly heterogeneous at the particle level and demonstrate a critical influence on the macroscopic deformation behavior. Despite its relevance to a wide variety of industrial applications of colloidal suspensions, scattering studies focusing on addressing the heterogeneity of the non-equilibrium colloidal structure are scarce thus far. Here in this paper, we report the first experimental result using small-angle neutron scattering. From the evolution of strain heterogeneity, we conclude that the shear-induced deformation transforms from nearly affine behavior at low shear rates, to plastic rearrangements when the shear rate is high.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Molecular dynamics and neutron scattering study of the dependence of polyelectrolyte dendrimer conformation on counterion behavior

Atomistic molecular dynamics (MD) simulations and contrast variation small angle neutron scattering (SANS) technique have been used to investigate the generation-5 (G5) polyelectrolyte polyamidoamine (PAMAM) starburst dendrimer with respect to its conformational dependence on counterion behavior at different levels of molecular charge. Satisfactory agreement is seen between the simulated results, such as the excess intra-dendrimer scattering length density (SLD) distribution and hydration level, and their experimental counterparts. The conformational evolution of charged dendrimer appears to be highly dependent on the association behavior of counterion. We explore the nature of the distribution of counterions around charged amines and qualitatively account for its sensitivity to the counterion valency on the difference of excess free energy. Moreover, via extending the concept of electrical double layer for compact charged colloids, we define an effective radius of charged dendrimer based on the spatial distribution of counterions in its vicinity. Within the same framework, the correlation between the strength of intra-dendrimer electrostatic repulsion and counterion valency and dynamics is also addressed.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Simultaneous Insight into Dissolution and Aggregation of Metal Sulfide Nanoparticles through Single-Particle Inductively Coupled Plasma Mass Spectrometry

Nanoparticles (NPs) and their colloidal aggregates are ubiquitous and play important roles in the transport and release of metals. Knowledge of their dissolution rates and aggregation behavior in solution are crucial for better prediction of their fate in biogeochemical cycling, ecotoxicity, and environmental remediation. There are however significant technical challenges to accurately obtain such information as a result of the heterogeneity and highly dynamic transformation exhibited by NPs, particularly at relatively low particle concentrations in aqueous systems. Here, we quantitatively examine the simultaneous dissolution and aggregation behavior of metal sulfide NPs using single-particle inductively coupled plasma mass spectrometry (spICP–MS). We focus on nickel sulfide (NiS), with additional data presented for copper sulfide (CuS) and cobalt sulfide (CoS). The kinetics of metal release (dissolution and disaggregation) of NiS was fastest under strongly oxidizing conditions (from 0.04 to >3 min –1 with H 2 O 2 ) and were slower under near-neutral (HEPES buffer/H 2 O) and acidic (1 mM HNO 3 ) conditions (≤0.006 min –1 ). Metal release kinetics in HNO 3 was not faster than in H 2 O or HEPES, suggesting that the solution pH has an influence over both the dissolution kinetics of individual particles and the NP aggregation states, which in combination affect metal release rates over time. Between different metal sulfides, the measured metal release rates were largely consistent with predictions based on the crystallinity, solubility products, and specific surface areas of the NPs, following an order of CoS > NiS > CuS. Here, the spICP–MS approach described here can be easily applied to the characterization of metal release and aggregation of other NPs at low concentrations (~10 5 particles/mL) typically found in natural environments.

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

Longitudinal eigenvibration of multilayer colloidal crystals and the effect of nanoscale contact bridges

Longitudinal contact-based vibrations of colloidal crystals with a controlled layer thickness are studied. These crystals consist of 390 nm diameter polystyrene spheres arranged into close packed, ordered lattices with a thickness of one to twelve layers. Using laser ultrasonics, eigenmodes of the crystals that have out-of-plane motion are excited. The particle–substrate and effective interlayer contact stiffnesses in the colloidal crystals are extracted using a discrete, coupled oscillator model. Extracted stiffnesses are correlated with scanning electron microscope images of the contacts and atomic force microscope characterization of the substrate surface topography after removal of the spheres. Solid bridges of nanometric thickness are found to drastically alter the stiffness of the contacts, and their presence is found to be dependent on the self-assembly process. Measurements of the eigenmode quality factors suggest that energy leakage into the substrate plays a role for low frequency modes but is overcome by disorder- or material-induced losses at higher frequencies. These findings help further the understanding of the contact mechanics, and the effects of disorder in three-dimensional micro- and nano-particulate systems, and open new avenues to engineer new types of micro- and nanostructured materials with wave tailoring functionalities via control of the adhesive contact properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
NASA NTRS2000

Studies of Particle Sedimentation by Novel Scattering Techniques

The four-year grant began May 1, 1996 (5-1-96 to 4-30-00, $100,000/year). We have finished 4 major research projects and published 10 papers during this grant period. An important aspect of this research has been the education of students at graduate and undergraduate levels. They have been fully involved in the research described below: 1. Polymer-induced depletion interaction in colloid-polymer mixtures. 2. Colloidal sedimentation in polymer solutions. 3. Velocity fluctuations in particle sedimentation. New laser light scattering techniques for velocity difference measurements.

Tong, Penger↗
DOE OSTI2011

Gel formation and aging in weakly attractive nanocolloid suspensions at intermediate concentrations

We report x-ray photon correlation spectroscopy (XPCS) and rheometry experiments to study the temporal evolution of gel formation and aging in suspensions of silica nanocolloids possessing a tunable short-range attraction. The colloid volume fractions, {phi} = 0.20 and 0.43, are below the glass regime at high concentration and above the fractal regime at low concentration. Following a sudden initiation of the interparticle attraction, the suspensions display a protracted latency period in which they remain fluid before acquiring a measurable elastic shear modulus. The duration of the latency period and the subsequent rate of increase of the modulus vary strongly with the strength of the attraction. The XPCS results indicate dynamic heterogeneity among the colloids during this gel formation in which a growing fraction of the particles become localized. The temporal evolution of this localization correlates with that of the rheology. In particular, the time scale over which the fraction of localized particles increases tracks the duration of the latency period. Also, at {phi} = 0.20 the localization length characterizing the motion of the localized fraction scales onto the shear modulus with no free parameters as predicted by a self-consistent theory based on mode coupling [K. S. Schweizer and G. Yatsenko, J. Chem. Phys. 127, 164505 (2007)10.1063/1.2780861], while deviations from the predicted scaling at {phi} = 0.43 are observed near the gel point. The XPCS results also reveal slow, hyperdiffusive motion of the colloids in the newly formed gels that is attributed to strain from the relaxation of internal stress. While some features of this motion correlate with the evolving rheology, others appear decoupled from the macroscopic mechanical behavior.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2018

Silver Nanoparticles Formed in a Colloidal System and a Polymer Matrix

The growth kinetics and particle-size distribution of Ag particles in a polyvinyl alcohol (PVA) composite, PVA film, and aqueous sol were studied using UV and visible spectroscopy, atomic force microscopy, and dynamic light scattering. A hypsochromic shift (55 nm) of the Ag nanoparticle (NP) surface plasmon absorption maximum was measured on going from the PVA composite to the film. The kinetics of Ag NP formation and their sizes were shown to depend considerably on UV irradiation, ultrasound action, and PVA concentration. It was established that UV irradiation accelerated Ag NP formation in the presence of reductants and destroyed the resulting NPs with a deficit of reductant. Partial destruction of the Ag NPs occurred under the influence of ultrasound whereas ultrasound action after UV irradiation reduced Ag{sup +} on the clusters.

77 NANOSCIENCE AND NANOTECHNOLOGY↗