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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

Micropatterning tractional forces in living cells

Here we describe a method for quantifying traction in cells that are physically constrained within micron-sized adhesive islands of defined shape and size on the surface of flexible polyacrylamide gels that contain fluorescent microbeads (0.2-microm diameter). Smooth muscle cells were plated onto square (50 x 50 microm) or circular (25- or 50-microm diameter) adhesive islands that were created on the surface of the gels by applying a collagen coating through microengineered holes in an elastomeric membrane that was later removed. Adherent cells spread to take on the size and shape of the islands and cell tractions were quantitated by mapping displacement fields of the fluorescent microbeads within the gel. Cells on round islands did not exhibit any preferential direction of force application, but they exerted their strongest traction at sites where they formed protrusions. When cells were confined to squares, traction was highest in the corners both in the absence and presence of the contractile agonist, histamine, and cell protrusions were also observed in these regions. Quantitation of the mean traction exerted by cells cultured on the different islands revealed that cell tension increased as cell spreading was promoted. These results provide a mechanical basis for past studies that demonstrated a similar correlation between spreading and growth within various anchorage-dependent cells. This new approach for analyzing the spatial distribution of mechanical forces beneath individual cells that are experimentally constrained to defined sizes and shapes may provide additional insight into the biophysical basis of cell regulation. Copyright 2002 Wiley-Liss, Inc.

NASA Discipline Cell Biology↗

Silicon wafer fracture stress for tracking sensors in particle physics experiments

For the construction of the ATLAS Inner Tracker strip detector, silicon strip sensor modules are glued directly onto carbon fibre support structures using a soft silicone gel. During tests at temperatures below -35°C, several of the sensors were found to crack due to a mismatch in coefficients of thermal expansion between polyimide circuit boards with copper metal layers (glued onto the sensor) and the silicon sensor itself. While module assembly procedures were developed to minimise variations between modules, cold tests showed a wide range of temperatures at which supposedly comparable modules failed. The observed variance (fracture temperatures between -35°C and -70°C) for supposedly comparable modules suggests an undetected variation between modules suspected to be intrinsic to the silicon wafer itself. Therefore, a test programme was developed to investigate the fracture stress of representative sensor wafer cutoffs. This paper presents results for the fracture stress of silicon sensors used in detector modules.

Detector design and construction technologies and ↗

Characterization of aluminum/RP-1 gel propellant properties

Research efforts are being conducted by the NASA Lewis Research Center to formulate and characterize the properties of Al/RP-1 and RP-1 gelled propellants for rocket propulsion systems. Twenty four different compositions of gelled fuels were formulated with 5 and 16 micron, atomized aluminum powder in RP-1. The total solids concentration in the propellant varied from 5 to 60 wt percent. Tests were conducted to evaluate the stability and rheological characteristics of the fuels. Physical separation of the solids occurred in fuels with less than 50 wt percent solids concentration. The rheological characteristics of the Al/RP-1 fuels varied with solids concentration. Both thixotropic and rheopectic gel behavior were observed. The unmetallized RP-1 gels, which were formulated by a different technique than the Al/RP-1 gels, were highly viscoelastic. A history of research efforts which were conducted to formulate and characterize the properties of metallized propellants for various applications is also given.

Rapp, Douglas C.↗

Characterization of aluminum/RP-1 gel propellant properties

Research efforts are being conducted by the NASA Lewis Research Center to formulate and characterize the properties of Al/RP-1 and RP-1 gelled propellants for rocket propulsion systems. Twenty four different compositions of gelled fuels were formualted with 5 and 16 micron, atomized aluminum powder in RP-1. The total solids concentration in the propellant varied from 5 to 60 wt percent. Tests were conducted to evaluate the stability and rheological characteristics of the fuels. Physical separation of the solids occurred in fuels with less than 50 wt percent solids concentration. The rheological characteristics of the Al/RP-1 fuels varied with solids concentration. Both thixotropic and rheopectic gel behavior were observed. The unmetallized RP-1 gels, which were formulated by a different technique than the Al/RP-1 gels, were highly viscoelastic. A history of research efforts which were conducted to formulate and characterize the properties of metallized propellants for various applications is also given.

Rapp, Douglas C.↗

Mercury Speciation via Diffusive Gradients Thin-Films Technology

Objectives: Develop and test various diffusive gradient in thin films (DGT) samplers for mercury - SRNL is developing reactive DGTS (rDGTs). Test chemistry to differentiate methylmercury from total and/or inorganic mercury in environmental samples. Fabricate and test rDGT samplers for deployment. Deploy the rDGTs in variable settings. Mercury is a persistent-bioaccumulative-toxic environmental pollutant. Mercury exists in different species such as elemental, inorganic, and methyl. Mercury speciation determine mercury behavior and toxicity. For example, methylmercury strongly accumulates in biota such as fish resulting in potential human health impacts. DGTs are innovative samplers to measure water concentration by diffusion and capture. Types of Hg DGTs used: Total Hg, Inorganic Hg, and Methyl Hg. Deployment Sites: Upper Three Runs, Lower Three Runs, Steele Creek, East Fork Poplar Creek (SRNL Sites), Horizons Creek, NOA Creek, Bruners Creek (ORNL Sites). DGT concentration estimates closely matched alternative measurements for soluble mercury at each Oak Ridge site - DGTs did not respond to particulate mercury. DGTs provide a representative measure for biota uptake since they are left out longer which allows for an average exposure concentration. DMA-80 provided an efficient and quick analysis. Variability in site location made a difference in Hg species. DGT preparations and sampling wasn't as quick and simple as microcolumn technology. Copper reagent degraded agarose gel - more work and cleaner data are needed to assess speciation in rDGTs. Future Work: Use cross-linked polyacrylamide for the collection layer for a stronger plastic. Make a copper diffusion layer without agarose. Test copper separation in lab using realistic stream conditions such as high organic carbon.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Visible-Light-Initiated Free-Radical Polymerization by Homomolecular Triplet-Triplet Annihilation

Polymerization reactions initiated by ultraviolet light are ubiquitous in scores of industrial applications but would markedly benefit from visible-light activation to overcome stability, energy consumption, light penetration, and sample geometry limitations. The current work leverages visible-light-driven homomolecular triplet-triplet annihilation (TTA) in zinc(II) meso-tetraphenylporphyrin (ZnTPP) to initiate facile free-radical polymerization in trimethylolpropane triacrylate (TMPTA) and methyl acrylate (MA) monomers through ultrafast electron transfer quenching. Selective Q-band (S 1 ) excitation of ZnTPP in the green or yellow sensitizes TTA occurring between two 3 ZnTPP* energized chromophores, ultimately generating the highly reducing S 2 excited state on one ZnTPP molecule (E red = –2.13 V versus saturated calomel electrode, SCE). Subsequently, this S 2 state engages in electron transfer with TMPTA or MA, thereby initiating the radical polymerization process. Bimolecular electron transfer was confirmed through optically gated fluorescence upconversion. In conclusion, FT-IR and EPR spin-trapping experiments verified visible-light-initiated polymerization leading to the formation of well-defined macro- and microscopic objects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Automatic multiple-sample applicator and electrophoresis apparatus

An apparatus for performing electrophoresis and a multiple-sample applicator is described. Electrophoresis is a physical process in which electrically charged molecules and colloidal particles, upon the application of a dc current, migrate along a gel or a membrane that is wetted with an electrolyte. A multiple-sample applicator is provided which coacts with a novel tank cover to permit an operator either to depress a single button, thus causing multiple samples to be deposited on the gel or on the membrane simultaneously, or to depress one or more sample applicators separately by means of a separate button for each applicator.

Grunbaum, B. W.↗

Biotropic liquid crystal phase transformations in cellulose-producing bacterial communities

Biological functionality is often enabled by a fascinating variety of physical phenomena that emerge from orientational order of building blocks, a defining property of nematic liquid crystals that is also pervasive in nature. Out-of-equilibrium, “living” analogs of these technological materials are found in biological embodiments ranging from myelin sheath of neurons to extracellular matrices of bacterial biofilms and cuticles of beetles. However, physical underpinnings behind manifestations of orientational order in biological systems often remain unexplored. For example, while nematiclike birefringent domains of biofilms are found in many bacterial systems, the physics behind their formation is rarely known. Here, using cellulose-synthesizing Acetobacter xylinum bacteria, we reveal how biological activity leads to orientational ordering in fluid and gel analogs of these soft matter systems, both in water and on solid agar, with a topological defect found between the domains. Furthermore, the nutrient feeding direction plays a role like that of rubbing of confining surfaces in conventional liquid crystals, turning polydomain organization within the biofilms into a birefringent monocrystal-like order of both the extracellular matrix and the rod-like bacteria within it. We probe evolution of scalar orientational order parameters of cellulose nanofibers and bacteria associated with fluid-gel and isotropic-nematic transformations, showing how highly ordered active nematic fluids and gels evolve with time during biological-activity-driven, disorder-order transformation. In conclusion, with fluid and soft-gel nematics observed in a certain range of biological activity, this mesophase-exhibiting system is dubbed “biotropic,” analogously to thermotropic nematics that exhibit solely orientational order within a temperature range, promising technological and fundamental-science applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Porous and Amorphous Mn x Mo 3 S 13 Chalcogel Electrode for High-Capacity Conversion-Based Lithium-Ion Batteries

While Li-ion batteries (LIBs) are a leading energy storage technology, their energy densities are limited by the low capacity of conventional intercalation cathodes, driving interest in high energy-density Li–S batteries that make use of conversion chemistry. Achieving high capacity, reversibility, and cycle stability, and controlling volume changes in conversion batteries during the charge–discharge process, however, remains challenging. Here, in this study, we present a porous, amorphous, sulfide-based Mn x Mo 3 S 13 chalcogel, which concurrently offers high capacity and cycle stability. The solution-processable room temperature synthesized Mn x Mo 3 S 13 (x = 0.25) chalcogel exhibits a local structure that resembles the Mo 3 S 13 cluster with Mn 2+ distributed across the Mo 3 S 13 matrix, as determined by synchrotron X-ray pair distribution function (PDF) and extended X-ray absorption fine structure (EXAFS). Ab initio molecular dynamics (AIMD) simulations reveal that Mn 2+ incorporation shortens the polysulfide chain in the gel matrix compared to the Mo 3 S 13 chalcogel, while forming a coordination environment with disulfide groups, analogous to the experimental findings. A Li/Mn 0.25 Mo 3 S 13 half-cell delivers 897 mAh g –1 capacity during the first discharge and retains 571 mAh g –1 capacity after 100 cycles at a C/3 rate. Distribution of relaxation time (DRT) unveils a stable solid–electrolyte interphase (SEI) formation upon cycling that enables charge–discharge reversibility. Here, the enhanced capacity retention and cycle stability compared to those of the Li/Mo 3 S 13 cell are attributed to the reduced dissolution of active mass into the electrolyte, facilitated by the formation of shorter polysulfide chains within the Mn 0.25 Mo 3 S 13 structure and the strong affinity of Lewis-acidic Mn 2+ for polysulfide anions generated during the charge–discharge process of the Li/Mn 0.25 Mo 3 S 13 cell. Thus, this work illustrates a design principle of material for high-capacity and cycle-stable Li-metal sulfide batteries.

25 ENERGY STORAGE↗

Layered supramolecular hydrogels from thioglycosides

Low molecular weight hydrogels are made of small molecules that aggregate via noncovalent interactions. Here, comprehensive characterization of the physical and chemical properties of hydrogels made from thioglycolipids of the disaccharides lactose and cellobiose with simple alkyl chains is reported. While thiolactoside hydrogels are robust, thiocellobioside gels are metastable, precipitating over time into fibrous crystals that can be entangled to create pseudo-hydrogels. Rheology confirms the viscoelastic solid nature of these hydrogels with storage moduli ranging from 10–600 kPa. Additionally, thiolactoside hydrogels are thixotropic which is a desirable property for many potential applications. Freeze-fracture electron microscopy of xerogels shows layers of stacked sheets that are entangled into networks. These structures are unique compared to the fibers or ribbons typically reported for hydrogels. Differential scanning calorimetry provides gel-to-liquid phase transition temperatures ranging from 30 to 80 °C. Prodan fluorescence spectroscopy allows assignment of phase transitions in the gels and other lyotropic phases of high concentration samples. Phase diagrams are estimated for all hydrogels at 1–10 wt% from 5 to ≥ 80 °C. In conclusion, these hydrogels represent a series of interesting materials with unique properties that make them attractive for numerous potential applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring polyvinyl alcohol-sodium alginate (PVA-SA) hydrogel beads by controlling crosslinking pH and time

Abstract Hydrogel-encapsulated catalysts are an attractive tool for low-cost intensification of (bio)-processes. Polyvinyl alcohol-sodium alginate hydrogels crosslinked with boric acid and post-cured with sulfate (PVA-SA-BS) have been applied in bioproduction and water treatment processes, but the low pH required for crosslinking may negatively affect biocatalyst functionality. Here, we investigate how crosslinking pH (3, 4, and 5) and time (1, 2, and 8 h) affect the physicochemical, elastic, and process properties of PVA-SA-BS beads. Overall, bead properties were most affected by crosslinking pH. Beads produced at pH 3 and 4 were smaller and contained larger internal cavities, while optical coherence tomography suggested polymer cross-linking density was higher. Optical coherence elastography revealed PVA-SA-BS beads produced at pH 3 and 4 were stiffer than pH 5 beads. Dextran Blue release showed that pH 3-produced beads enabled higher diffusion rates and were more porous. Last, over a 28-day incubation, pH 3 and 4 beads lost more microspheres (as cell proxies) than beads produced at pH 5, while the latter released more polymer material. Overall, this study provides a path forward to tailor PVA-SA-BS hydrogel bead properties towards a broad range of applications, such as chemical, enzymatic, and microbially catalyzed (bio)-processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural and optical properties of nanoparticles formed by laser ablation of porous silicon in liquids: Perspectives in biophotonics

The paper discusses the possibility of manufacturing silicon nanoparticles, which are suitable for contrasting biological tissues imaged by optical coherence tomography, by femtosecond laser ablation of porous silicon in various liquids. The manufactured nanoparticles are characterised by average sizes of 87, 112, and 102 nm for cases of ablation in water, ethanol, and liquid nitrogen, respectively, as well as a relatively narrow size distribution, which provides additional advantages for subsequent delivery into biological tissues. Electrochemical etching, which results in the formation of layers of porous silicon, allows the yield of ablation products to be increased several-fold by lowering the ablation threshold, thereby increasing the light scattering efficiency of the prepared suspensions compared with the case of using crystalline silicon as targets. The possibility of obtaining high-contrast images of a biotissue phantom based on an agar gel with embedded nanoparticles is shown. The magnitude of the contrast depends on the liquid used for ablation and correlates with the values of the reduced scattering coefficient of the studied suspensions. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Modular Iron–Bipyridine-Based Conjugated Aerogels as Catalysts for Oxygen Reduction Reaction

Aerogels have a large surface area and a porous structure, which make them an attractive catalyst support materials for fuel cells. Modifying the aerogels’ building blocks and introducing catalytic sites into their backbones allow them to function as both catalysts and supports, thereby increasing the density and distribution of catalyst active sites. In this work, we studied conjugated aerogels containing iron–bipyridine catalytic sites for the oxygen reduction reaction. To demonstrate the variation in physical and electrochemical properties of these aerogels, a series of aerogels were synthesized by a Glaser coupling reaction. Iron salt was added to the three-dimensional gel to produce iron–bipyridine complexes and obtain atomically dispersed catalytic sites. The electrocatalytic activity and electrical conductivity of the aerogels were increased after their heat treatment to yield Fe-doped carbon aerogels. The control of metal loadings was accomplished by changing the bipyridine content during the aerogel synthesis, resulting in 0.9–4.1 wt % Fe. In conclusion, the results show a correlation between Fe loading, aerogel structure, and catalytic activity, achieving high performance for the oxygen reduction reaction in both acidic and alkaline media.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rheology and dynamics of a solvent segregation driven gel (SeedGel)

Bicontinuous structures promise applications in a broad range of research fields, such as energy storage, membrane science, and biomaterials. Kinetically arrested spinodal decomposition is found responsible for stabilizing such structures in different types of materials. A recently developed solvent segregation driven gel (SeedGel) is demonstrated to realize bicontinuous channels thermoreversibly with tunable domain sizes by trapping nanoparticles in a particle domain. As the mechanical properties of SeedGel are very important for its future applications, a model system is characterized by temperature-dependent rheology. The storage modulus shows excellent thermo-reproducibility and interesting temperature dependence with the maximum storage modulus observed at an intermediate temperature range (around 28 °C). SANS measurements are conducted at different temperatures to identify the macroscopic solvent phase separation during the gelation transition, and solvent exchange between solvent and particle domains that is responsible for this behavior. Further, the long-time dynamics of the gel is further studied by X-ray Photon Correlation Spectroscopy (XPCS). The results indicate that particles in the particle domain are in a glassy state and their long-time dynamics are strongly correlated with the temperature dependence of the storage modulus.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Static and Dynamic Gradient Based Directional Transportation of Neutral Molecules in Swollen Polymer Films

Abstract Materials which selectively transport molecules offer powerful opportunities for concentrating and separating chemical agents. Here, utilizing static and dynamic chemical gradients, transport of molecules within swollen crosslinked polymers is demonstrated. Using an ≈200 μm static hydroxyl to hexyl gradient, the neutral ambipolar nerve agent surrogate diethyl (cyanomethyl)phosphonate (DECP) is directionally transported and concentrated 60‐fold within 4 hours. To accelerate transport kinetics, a dynamic gradient (a “travelling wave”) is utilized. Here, the non‐polar dye pyrene was transported. The dynamic gradient is generated by an ion exchange process triggered by the localized introduction of an aqueous NaCl solution, which converts the gel from hydrophobic to hydrophilic. As the hydrophilic region expands, associated water enters the gel, and pyrene is pushed ahead of the expansion front. The dynamic gradient provides about 10‐fold faster transport kinetics than the static gradient.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbon molecular sieve hollow fiber membranes derived from dip-coated precursor hollow fibers comprising nanoparticles

We report a novel approach to economically fabricate dual-layer composite nanoparticle-containing carbon molecular sieve (CMS) hollow fiber membranes having excellent gas separation performance. The economically favored process comprises dip coating engineered support layer fibers to form a dense skin layer in a CMS precursor. The coated fibers are then pyrolyzed to form a high-performance CMS hollow fiber membrane. The nano-particle containing composite carbon molecular sieve hollow fiber membranes showed very attractive selectivities and productivities. As a result, this work shows how to produce high performance CMS hollow fiber membrane by coating, which exceeds that achieved with the standard sol-gel support stabilization technique.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interplay of surface energy and rheology in biopolymer soil enhancement

Biopolymers such as xanthan gum (XG) and locust bean gum (LBG) hold great potential as eco-friendly alternative soil binders. In this work, we investigated the impact of XG/LBG mixtures on the unconfined compressive strength (UCS) of sand. The high strength of dry biopolymer/sand arises from the cohesion between solid polymer films and sand particles which supported by work of adhesion calculation and soil mechanics measurement. LBG exhibits much lower sand reinforcement efficacy because polymers unevenly distributed within sand matrix. The formation of a core-shell structure in LBG/sand is an interplay of surface free energy and viscoelastic properties of polymer solutions. This structure is altered when LBG mixed with XG at varying ratios as those physical properties changed due to the complexity of polymer chains association. By probing these factors, we aim to elucidate the role of surface energies and polymer physics in governing the strength of the sand/polymer network, thereby contributing to a more comprehensive understanding polymer-sand interface. The low strength of gels (G’ ∼10Pa) cannot solely account for the increased UCS of wet sand over 10 kPa. Instead, the high strength of biopolymer/sand is more likely derived from the granular particles with biopolymers as solid glue.

36 MATERIALS SCIENCE↗