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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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XPCS Microrheology and Rheology of Sterically Stabilized Nanoparticle Dispersions in Aprotic Solvents

In this study, X-ray photon correlation spectroscopy (XPCS) microrheology and conventional bulk rheology were performed on silica nanoparticle dispersions associated with battery electrolyte applications to probe the properties of these specific complex materials and to explore the utility of XPCS microrheology in characterizing nanoparticle dispersions. Sterically stabilized shear-thickening electrolytes were synthesized by grafting poly(methyl methacrylate) chains onto silica nanoparticles. Coated silica dispersions containing 5–30 wt % nanoparticles dispersed in propylene carbonate were studied. In general, both XPCS microrheology and conventional rheology showed that coated silica dispersions were more viscous at higher concentrations, as expected. The complex viscosity of coated silica dispersions showed shear-thinning behavior over the frequency range probed by XPCS measurements. However, measurements using conventional mechanical rheometry yielded a shear viscosity with weak shear-thickening behavior for dispersions with the highest concentration of 30% particles. Our results indicate that there is a critical concentration needed for shear-thickening behavior, as well as appropriate particle size and surface polymer chain length, for this class of nanoparticle-based electrolytes. The results of this study can provide insights for comparing XPCS microrheology and bulk rheology for related complex fluids and whether XPCS microrheology can capture expected macroscopic rheological properties by probing small-scale particle dynamics.

36 MATERIALS SCIENCE↗

Techniques to characterize dynamics in biomaterials microenvironments: XPCS and microrheology of alginate/PEO–PPO–PEO hydrogels

Many recent studies have highlighted the timescale for stress relaxation of biomaterials on the microscale as an important factor in regulating a number of cell-material interactions, including cell spreading, proliferation, and differentiation. Relevant timescales on the order of 0.1–100 s have been suggested by several studies. While such timescales are accessible through conventional mechanical rheology, several biomaterials have heterogeneous structures, and stress relaxation mechanisms of the bulk material may not correspond to that experienced in the cellular microenvironment. Here we employ X-ray photon correlation spectroscopy (XPCS) to explore the temperature-dependent dynamics, relaxation time, and microrheology of multicomponent hydrogels comprising of commercial poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) triblock copolymer F127 and alginate. Previous studies on this system have shown thermoreversible behavior in the bulk oscillatory shear rheology. At physiological temperatures, bulk rheology of these samples shows behavior characteristic of a soft solid, with G' > G" and no crossover between G' and G" over the measurable frequency range, indicating a relaxation time >125 s. By contrast, XPCS-based microrheology shows viscoelastic behavior at low frequencies, and XPCS-derived correlation functions show relaxation times ranging from 10–45 s on smaller length scales. Finally, we are able to use XPCS to effectively probe the viscoelasticity and relaxation behavior within the material microenvironments.

36 MATERIALS SCIENCE↗

Microrheological modeling of lithium ion battery anode slurry

The rheological properties of electrode slurries used in the manufacturing of lithium-ion batteries affect the manufacturing processes as well as the battery quality, such as electrochemical and durability performance. There is thus an urgent need to develop a physics-based model to describe the rheological properties of these electrode slurries to enable further optimization of battery electrode production. Here in this paper, we present a microrheological model for estimating the viscosity of electrode slurries that incorporates colloidal forces such as van der Waals and polymeric steric repulsion forces. Finally, the model shows good agreement with the experimentally determined viscosities of a graphite-based anode slurry and should be extendable to describe the rheological properties of cathode slurries.

25 ENERGY STORAGE↗

Active microrheology and dynamic phases for pattern-forming systems with competing interactions

We consider the driven dynamics of a probe particle moving through an assembly of particles with competing long-range repulsive and short-range attractive interactions, which form crystal, stripe, labyrinth, and bubble states as the ratio of attraction to repulsion is varied. We show that the probe particle exhibits a depinning-like threshold from an elastic regime, where the probe particle is trapped by interactions with the other particles, to a plastic flow regime, where the probe particle can break bonds in the surrounding medium. For a fixed particle density, the depinning threshold and sliding velocity of the probe particle vary nonmonotonically as the attraction term is increased. A velocity minimum appears near the crystal to stripe crossover, and there is a significant increase in the depinning threshold in the bubble regime when the probe particle is strongly confined inside the bubbles. For fixed attractive interaction but increasing particle density, the behavior is also nonmonotonic, and there are jumps and drops in the velocity and depinning threshold corresponding to points at which the system transitions between different structures. There are also several distinct flow states that can be characterized by the amount of plastic deformation induced by the probe particle in the surrounding medium. Each flow state generates a different amount of effective drag on the probe particle, and there can be jumps in the velocity-force curve at transitions between the states. In conclusion, we also find that when oriented stripes are present, the probe particle can move along the stripe in an edge transport state that has a finite Hall angle.

36 MATERIALS SCIENCE↗

Microscale dynamics in thermoreversible hydrogels: Impact of probe size and concentration

Passive microrheology techniques using dynamic light scattering (DLS) and X-ray photon correlation spectroscopy (XPCS) have emerged as important techniques for characterizing the dynamics and viscoelastic properties of soft polymeric biomaterials. However, the impact of probe particle type, size, and concentration are important considerations in interpretation of results and comparison to properties obtained from bulk rheology measurements. In this work, we investigate a model thermoreversible polymeric hydrogel and compare results from DLS-microrheology with different size and concentrations of polystyrene probe particles and XPCS-microrheology with inorganic nanoparticles. We obtained trends that aligned most closely with the macroscopic rheology with probe particles that are slightly larger than the characteristic length scale of the gel structure, but within the same order of magnitude. By contrast, larger probe particles yielded microrheology data that are more dominated by elastic behavior than what we might expect from bulk rheology experiments, while use of small inorganic nanoparticles in XPCS-microrheology resulted in a more a more viscous response than would be expected based on the bulk rheology. Finally, this study demonstrates the utility of passive DLS- and XPCS-based microrheology in characterizing the rheological properties of complex polymeric biomaterials, while also highlighting important considerations in experimental design and choice of type, size, and concentration of probe particles used.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Examining the role of glycoside hydrolases in local rheology of Pseudomonas aeruginosa biofilms

Current research strategies in the treatment of biofilm infections have focused on dispersal, in which bacteria are made to vacate the extracellular polymeric substance (EPS) surrounding them and return to a planktonic state where antimicrobial treatments are more effective. Glycoside hydrolases (GHs), which cleave bonds in EPS polysaccharides, have been shown to promote dispersal in Pseudomonas aeruginosa biofilms. The dispersal mechanism is possibly due to GHs’ ability to directly release bacteria from the EPS, disrupt EPS’ ability to regulate the environment, or reduce overall mechanical stability. In this work, passive microrheology is used to examine the relevance of the last mechanism by exploring the effects of three GHs (α-amylase, cellulase, and xylanase) known to disperse P. aeruginosa on local biofilm viscoelasticity. Compared to control studies in wild-type strains, it is found that treatment with all three GHs results in statistically relatively less elastic and stiffer biofilms, indicating that changes to mechanical stability may be a factor in effective dispersal. Both cellulase and xylanase were observed to have the greatest impact in creating a less stiff and elastic biofilm; these GHs have been observed to be effective at dispersal in the published results. Each GH was further tested on biofilms grown with strains that produced EPS missing specific polysaccharide components. Cellulase specifically targeted Psl, which forms the major structural and mechanical backbone of the EPS, explaining its efficacy in dispersal. However, xylanase did not appear to exhibit any affinity to any polysaccharide within the EPS based on the microrheology results. Overall, these results suggest that the local microrheology of the biofilms is impacted by GHs and that may be one of the factors that is causing the ability of these therapeutics to enhance dispersal.

59 BASIC BIOLOGICAL SCIENCES↗

Interference Provides Clarity: Direct Observation of 2D Materials at Fluid–Fluid Interfaces

Monolayer particles of two-dimensional (2D) materials represent a scientifically and technologically interesting class of anisotropic particles with colloidal-scale lateral sizes but sub-nanometer thicknesses. This atomic-scale thickness leads to interesting phenomena that can be exploited in next-generation thin-film technologies, and fluid-fluid interfaces provide a potentially scalable platform to confine, assemble, and deposit functional thin films of 2D materials. However, directly observing how these materials interact and assemble into a given film morphology is experimentally challenging because of their sub-nanometer thicknesses. Here, we demonstrate the ability to directly observe graphene, molybdenum disulfide (MoS2), and hexagonal boron nitride (h-BN) particles at fluid-fluid interfaces using interference reflection microscopy (IRM). Monolayer MoS2 and graphene particles demonstrated >10% optical contrast at an air-water interface, which allowed us to quantitatively analyze in situ images of self-assembled MoS2 particles and to map trajectories of interacting graphene particles. Additionally, the Brownian motion of a graphene particle was tracked and analyzed in the context of passive microrheology theory for 2D particle probes. Our results demonstrate how IRM can be used to obtain quantitative spatiotemporal information regarding the self-assembly and dynamics of 2D materials at fluid-fluid interfaces. It will have a significant impact on our ability to investigate systems of atomically thin particles at fluid-fluid interfaces, an area that has fundamental scientific importance and materials science applications but has suffered from a lack of direct, in situ observation techniques.

2D material↗

Crossover from positive to negative optical torque in mesoscale optical matter

The photons in circularly polarized light can transfer their quantized spin angular momentum to micro- and nanostructures via absorption and scattering. This normally exerts positive torque on the objects wher the sign (i.e., handedness or angular direction) follows that of the spin angular momentum. Here we show that the sign of the optical torque can be negative in mesoscopic optical matter arrays of metal nanoparticles (NPs) assembled in circularly polarized optical traps. Crossover from positive to negative optical torque, which occurs for arrays with different number, separation and configuration of the constituent particles, is shown to result from many-body interactions as clarified by electrodynamics simulations. Our results establish that both positive and negative optical torque can be readily realized and controlled in optical matter arrays. This property and reconfigurability of the arrays makes possible programmable materials for optomechanical, microrheological and biological applications.

36 MATERIALS SCIENCE↗

How actin crosslinking and bundling proteins cooperate to generate an enhanced cell mechanical response

Actin-crosslinking proteins organize actin filaments into dynamic and complex subcellular scaffolds that orchestrate important mechanical functions, including cell motility and adhesion. Recent mutation studies have shown that individual crosslinking proteins often play seemingly non-essential roles, leading to the hypothesis that they have considerable redundancy in function. We report live-cell, in vitro, and theoretical studies testing the mechanical role of the two ubiquitous actin-crosslinking proteins, alpha-actinin and fascin, which co-localize to stress fibers and the basis of filopodia. Using live-cell particle tracking microrheology, we show that the addition of alpha-actinin and fascin elicits a cell mechanical response that is significantly greater than that originated by alpha-actinin or fascin alone. These live-cell measurements are supported by quantitative rheological measurements with reconstituted actin filament networks containing pure proteins that show that alpha-actinin and fascin can work in concert to generate enhanced cell stiffness. Computational simulations using finite element modeling qualitatively reproduce and explain the functional synergy of alpha-actinin and fascin. These findings highlight the cooperative activity of fascin and alpha-actinin and provide a strong rationale that an evolutionary advantage might be conferred by the cooperative action of multiple actin-crosslinking proteins with overlapping but non-identical biochemical properties. Thus the combination of structural proteins with similar function can provide the cell with unique properties that are required for biologically optimal responses.

Non-NASA Center↗

Recent Advances in Soft Matter Characterization Capabilities Developed at NASA GRC for Lunar Exploration: Differential Dynamic Microscopy to Spectroscopy to Computer Vision

In 1991, famous French scientist Pierre-Gilles de Genes was awarded Nobel prize for his impactful research in soft matter, more specifically polymers. He is defined as the founding father of soft matter. In his Nobel lecture (https://www.nobelprize.org/uploads/2018/06/gennes-lecture.pdf ) he described soft matter aka complex fluids as materials with two primary features – (a) complexity and (b) flexibility. The sub-categories of soft matter (e.g.- granular materials, polymers, foams, colloids etc.) are defined on the basis of Pierre-Gilles de Gennes’ definition. At NASA GRC, we are pushing the boundaries for fundamental study of soft matter on Lunar Surface. With regard to Lunar surface science, we are focusing on developing capabilities pertaining to granular materials and bio-soft/active matter to facilitate future efforts in ISRU and bio-ISRU capabilities. In order to achieve fundamental goals of soft matter research within the limitations of Lunar environment, the scientific capabilities need to be small, flexible, modular, off the shelf and the focus needs to be more on developing an interdisciplinary capability that leverages the recent growth in AI/ML and Computer Vision to augment our understanding of fundamental science. This strategy would allow us to reduce our resource requirement during launch, installation, and occupied real estate footprint on Lunar surface In this talk, we will go over 3 different capabilities that we have developed in house and in close collaboration – (a) Differential Dynamic Microscopy (DDM), (b) Portable In-situ Chemical Spectroscopy (PICS) and (c) Computer Vision Enabled Observation. At very high level, Differential Dynamic Microscopy (DDM) allows us to study the structure-property-process relation (microrheology) of bio-soft/active matter using optical microscope and improved image analysis capabilities. PICS uses AI/ML-based advanced signal deconvolution and analysis technique that can work with existing portable spectroscopy tools to perform materials analysis (e.g.- granular materials and bio-soft/active matter) inspection on the go. Finally, computer vision enabled analysis allows us to use simple camera images for 3D reconstruction of experimental process and tracking of objects of interest in an experiment. We expect that this detailed process will allow us reach a thorough understanding of soft matter in Lunar environment. The capabilities developed by us will help to validate and establish fundamental understanding in Lunar environment. This will, in turn, allow us to guide future space exploration missions and expand the knowledge base of the scientific and engineering communities.

Suman Sinha Ray↗

Recent Advances in Soft Matter Characterization Capabilities Developed at NASA GRC for Lunar Exploration: Differential Dynamic Microscopy to Spectroscopy to Computer Vision

In 1991, famous French scientist Pierre-Gilles de Genes was awarded Nobel prize for his impactful research in soft matter, more specifically polymers. He is defined as the founding father of soft matter. In his Nobel lecture (https://www.nobelprize.org/uploads/2018/06/gennes-lecture.pdf ) he described soft matter aka complex fluids as materials with two primary features – (a) complexity and (b) flexibility. The sub-categories of soft matter (e.g.- granular materials, polymers, foams, colloids etc.) are defined on the basis of Pierre-Gilles de Gennes’ definition. At NASA GRC, we are pushing the boundaries for fundamental study of soft matter on Lunar Surface. With regard to Lunar surface science, we are focusing on developing capabilities pertaining to granular materials and bio-soft/active matter to facilitate future efforts in ISRU and bio-ISRU capabilities. In order to achieve fundamental goals of soft matter research within the limitations of Lunar environment, the scientific capabilities need to be small, flexible, modular, off the shelf and the focus needs to be more on developing an interdisciplinary capability that leverages the recent growth in AI/ML and Computer Vision to augment our understanding of fundamental science. This strategy would allow us to reduce our resource requirement during launch, installation, and occupied real estate footprint on Lunar surface. In this talk, we will go over 3 different capabilities that we have developed in house and in close collaboration – (a) Differential Dynamic Microscopy (DDM), (b) Portable In-situ Chemical Spectroscopy (PICS) and (c) Computer Vision Enabled Observation. At very high level, Differential Dynamic Microscopy (DDM) allows us to study the structure-property-process relation (microrheology) of bio-soft/active matter using optical microscope and improved image analysis capabilities. PICS uses AI/ML-based advanced signal deconvolution and analysis technique that can work with existing portable spectroscopy tools to perform materials analysis (e.g.- granular materials and bio-soft/active matter) inspection on the go. Finally, computer vision enabled analysis allows us to use simple camera images for 3D reconstruction of experimental process and tracking of objects of interest in an experiment. We expect that this detailed process will allow us reach a thorough understanding of soft matter in Lunar environment. The capabilities developed by us will help to validate and establish fundamental understanding in Lunar environment. This will, in turn, allow us to guide future space exploration missions and expand the knowledge base of the scientific and engineering communities.

Suman Sinha-Ray↗

Recent Advances in Soft Matter Characterization Capabilities Developed at NASA GRC for Lunar Exploration: Differential Dynamic Microscopy to Spectroscopy to Computer Vision

In 1991, famous French scientist Pierre-Gilles de Genes was awarded Nobel prize for his impactful research in soft matter, more specifically polymers. He is defined as the founding father of soft matter. In his Nobel lecture (https://www.nobelprize.org/uploads/2018/06/gennes-lecture.pdf ) he described soft matter aka complex fluids as materials with two primary features – (a) complexity and (b) flexibility. The sub-categories of soft matter (e.g.- granular materials, polymers, foams, colloids etc.) are defined on the basis of Pierre-Gilles de Gennes’ definition. At NASA GRC, we are pushing the boundaries for fundamental study of soft matter on Lunar Surface. With regard to Lunar surface science, we are focusing on developing capabilities pertaining to granular materials and bio-soft/active matter to facilitate future efforts in ISRU and bio-ISRU capabilities. In order to achieve fundamental goals of soft matter research within the limitations of Lunar environment, the scientific capabilities need to be small, flexible, modular, off the shelf and the focus needs to be more on developing an interdisciplinary capability that leverages the recent growth in AI/ML and Computer Vision to augment our understanding of fundamental science. This strategy would allow us to reduce our resource requirement during launch, installation, and occupied real estate footprint on Lunar surface In this talk, we will go over 3 different capabilities that we have developed in house and in close collaboration – (a) Differential Dynamic Microscopy (DDM), (b) Portable In-situ Chemical Spectroscopy (PICS) and (c) Computer Vision Enabled Observation. At very high level, Differential Dynamic Microscopy (DDM) allows us to study the structure-property-process relation (microrheology) of bio-soft/active matter using optical microscope and improved image analysis capabilities. PICS uses AI/ML-based advanced signal deconvolution and analysis technique that can work with existing portable spectroscopy tools to perform materials analysis (e.g.- granular materials and bio-soft/active matter) inspection on the go. Finally, computer vision enabled analysis allows us to use simple camera images for 3D reconstruction of experimental process and tracking of objects of interest in an experiment. We expect that this detailed process will allow us reach a thorough understanding of soft matter in Lunar environment. The capabilities developed by us will help to validate and establish fundamental understanding in Lunar environment. This will, in turn, allow us to guide future space exploration missions and expand the knowledge base of the scientific and engineering communities.

Suman Sinha Ray↗

Recent Advances in Soft Matter Characterization Capabilities Developed at NASA GRC

In 1991, famous French scientist Pierre-Gilles de Genes was awarded Nobel prize for his impactful research in soft matter, more specifically polymers. He is defined as the founding father of soft matter. In his Nobel lecture (https://www.nobelprize.org/uploads/2018/06/gennes-lecture.pdf ) he described soft matter aka complex fluids as materials with two primary features – (a) complexity and (b) flexibility. The sub-categories of soft matter (e.g.- granular materials, polymers, foams, colloids etc.) are defined on the basis of Pierre-Gilles de Gennes’ definition. At NASA GRC, we are pushing the boundaries for fundamental study of soft matter on Lunar Surface. With regard to Lunar surface science, we are focusing on developing capabilities pertaining to granular materials and bio-soft/active matter to facilitate future efforts in ISRU and bio-ISRU capabilities. In order to achieve fundamental goals of soft matter research within the limitations of Lunar environment, the scientific capabilities need to be small, flexible, modular, off the shelf and the focus needs to be more on developing an interdisciplinary capability that leverages the recent growth in AI/ML and Computer Vision to augment our understanding of fundamental science. This strategy would allow us to reduce our resource requirement during launch, installation, and occupied real estate footprint on Lunar surface In this talk, we will go over 3 different capabilities that we have developed in house and in close collaboration – (a) Differential Dynamic Microscopy (DDM), (b) Portable In-situ Chemical Spectroscopy (PICS) and (c) Computer Vision Enabled Observation. At very high level, Differential Dynamic Microscopy (DDM) allows us to study the structure-property-process relation (microrheology) of bio-soft/active matter using optical microscope and improved image analysis capabilities. PICS uses AI/ML-based advanced signal deconvolution and analysis technique that can work with existing portable spectroscopy tools to perform materials analysis (e.g.- granular materials and bio-soft/active matter) inspection on the go. Finally, computer vision enabled analysis allows us to use simple camera images for 3D reconstruction of experimental process and tracking of objects of interest in an experiment. We expect that this detailed process will allow us reach a thorough understanding of soft matter in Lunar environment. The capabilities developed by us will help to validate and establish fundamental understanding in Lunar environment. This will, in turn, allow us to guide future space exploration missions and expand the knowledge base of the scientific and engineering communities.

Suman Sinha Ray↗

Driven probe particle dynamics in a bubble and pattern forming system

We numerically examine the dynamics of a probe particle driven at a constant force through an assembly of particles with competing long-range repulsion and short-range attraction that forms a bubble or stripe state. In the bubble regime, we identify several distinct types of motion, including an elastic or pinned regime where the probe particle remains inside a bubble and drags all other bubbles with it. There is also a plastic bubble phase where the bubble in which the probe particle is trapped is able to move past the adjacent bubbles. At larger drives, there is a breakthrough regime where the probe particle jumps from bubble to bubble and, in some cases, can induce correlated rotations or plastic rearrangements of the particles within the bubbles. At the highest drives, the probe particle moves sufficiently rapidly that the background particles undergo only small distortions. The distinctive dynamic flow states and the transitions between them are accompanied by signatures in the effective drag on the driven particle, jumps in the velocity–force curves, and changes in the time-dependent velocity fluctuations. We map the dynamic phase diagram for this system for varied interaction lengths, bubble sizes, and densities.

36 MATERIALS SCIENCE↗

Optical tweezer measurements of asymptotic nonlinearities in complex fluids

This article presents micro-medium-amplitude oscillatory shear (μMAOS), a method to measure the frequency-dependent micromechanical properties of soft materials in the asymptotically nonlinear regime using optical tweezers. For this work, we have developed a theoretical framework to extract these nonlinear mechanical properties of the material from experimental measurements and also proposed a physical interpretation of the third-order nonlinearities measured in single-tone oscillatory tests. We validate the method using a well-characterized surfactant solution of wormlike micelles, and subsequently employ this technique to demonstrate that the cytoplasm of a living cell undergoes strain softening and shear thinning when locally subjected to weakly nonlinear oscillatory deformations.

59 BASIC BIOLOGICAL SCIENCES↗