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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 127 records · Page 7

Ionic Tunability of Conjugated Polyelectrolyte Solutions

Conjugated polyelectrolytes (CPEs), which combine a π-conjugated polymer backbone with pendant ionic functionalities, offer an opportunity for electrostatic control of materials properties. In this work, the mesoscale morphology and physical properties of a high-mobility conjugated polyelectrolyte are tuned by the addition of salt, variation of the charge-compensating counterion, and complexation with an oppositely charged polyelectrolyte containing the same π-conjugated backbone. In systems with a single polyelectrolyte species, added ions screen the electrostatic repulsions stabilizing the gel-phase, resulting in the dissolution of ionic cross-links and hydrophobic collapse. Further, exchanging the charge compensating counterion is found to enable finer structural control of the solution behavior and modulation of the self-doping behavior. Finally, novel CPE–CPE complexes resulting in dense solutions and gels of semiconductive material are produced by combination of oppositely charged polyelectrolytes. Such concentrated CPE formulations should be useful materials for mixed electronic–ionic conduction and pseudocapacitative energy storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Visualizing pectin polymer-polymer entanglement produced by interfacial water movement

In this report, we investigated the physical conditions for creating pectin polymer-polymer (homopolymer) entanglement. The potential role of water movement in creating pectin entanglement was investigated by placing water droplets-equivalent to the water content of two gel phase films-between two glass phase films and compressing the films at variable probe velocities. Slow probe velocity (0.5 mm/sec) demonstrated no significant debonding. Furthermore, corresponding videomicroscopy demonstrated an occasional water bridge, but no evidence of stranding or polymer entanglement. In contrast, fast probe velocity (5 mm/sec) resulted in 1) an increase in peak adhesion strength, 2) a progressive debonding curve, and 3) increased work of cohesion (p < .001). Corresponding videomicroscopy demonstrated pectin stranding and delamination between pectin films. Scanning electron microscopy images obtained during pectin debonding provided additional evidence of both stranding and delamination. We conclude that water movement can supply the motive force for the rapid chain entanglement between pectin films.

59 BASIC BIOLOGICAL SCIENCES↗

Belite cements and their activation

Belite cements, BCs, containing mainly belite, alite and calcium aluminates, are currently used as low heat cements. These binders produce high amounts of C–S–H gel and have very good durability properties which are reviewed. Additional advantages include: (i) lower limestone demand, with lower associated CO{sub 2} emissions; (ii) lower energy demand; (iii) lower kiln operating temperature, which means lowering CO{sub 2} and NO{sub x} emissions from fuel burning; and (iv) lower temperature increase at early hydration age. However, early-age strength developments are not competitive with those of Portland cements. Hence, to improve their early-age strength developments is a research priority known as activation. This enhancement can be attained by three compatible approaches: (i) chemical, (ii) physical; and (iii) admixture activations. The current research status for BCs activation is reviewed including: cost-effective element substitutions to stabilize high-temperature forms; fast cooling, milling and mild temperature hydration as physical activation; and the use of C–S–H seeds as admixture activation. After discussion of the resulting microstructures, a research outlook is exercised.

36 MATERIALS SCIENCE↗

Nanoporous Silica Thermal Insulation for Space Shuttle Cryogenic Tanks: A Case Study

Nanoporous silica (with typical 10-50 nm porous radii) has been benchmarked for thermal insulators capable of maintaining a 150 K/cm temperature gradient. For cryogenic use in aerospace applications, the combined features for low-density, high thermal insulation factors, and low temperature compatibility are demonstrated in a prototype sandwich structure between two propulsion tanks. Theoretical modelling based on a nanoscale fractal structure suggest that the thermal conductivity scales proportionally (exponent, 1.7) with the material density-lower density increases the thermal insulation rating. Computer simulations, however, support the optimization tradeoff between material strength (Young moduli, proportional to density with exponent, 3.7), the characteristic (colloidal silica, less than 5 nm) particle size, and the thermal rating. The results of these simulations indicate that as nanosized particles are incorporated into the silica backbone, the resulting physical properties will be tailored by the smallest characteristic length and their fractal interconnections (dimension and fractal size). The application specifies a prototype panel which takes advantage of the processing flexibility inherent in sol-gel chemistry.

Noever, David A.↗

Production and diffusion of H 2 O 2 during the interaction of a direct current pulsed atmospheric pressure plasma jet on a hydrogel

The interaction of cold atmospheric pressure plasma jets with hydrogels has been used as a model system to study the interaction of plasmas with tissues. In this study, we analyze the diffusion of reactive oxygen species (in particular H 2 O 2 ) and quantify the amount of plasma-produced H 2 O 2 species that penetrates into a gelatin hydrogel. We show that the diffusion constant of H 2 O 2 in 10% gelatin hydrogel is similar to its diffusion constant in water and that the production of H 2 O 2 in the hydrogel is significantly less than the production of H 2 O 2 in distilled water for the same plasma operation conditions suggesting that the scavenging of OH radicals at the plasma-gel interface significantly reduces the H 2 O 2 production.

60 APPLIED LIFE SCIENCES↗

Microscopic theory of onset of decaging and bond-breaking activated dynamics in ultradense fluids with strong short-range attractions

We theoretically study thermally activated “in cage” elementary dynamical processes that precede full structural relaxation in ultra-dense particle liquids interacting via strong short range attractive forces. The analysis is based on a microscopic theory formulated at the particle trajectory level built on the dynamic free energy concept and an explicit treatment of how attractive forces control the formation and lifetime of physical bonds. Mean time scales for bond breaking, the early stage of cage escape, and non-Fickian displacement by a fixed amount are analyzed in the repulsive glass, bonded repulsive (attractive) glass, fluid, and dense gel regimes. The theory predicts a strong length-scale-dependent growth of these time scales with attractive force strength at fixed packing fraction, a much weaker slowing down with density at fixed attraction strength, and a strong decoupling of the shorter bond breaking time with the other two time scales that are controlled mainly by perturbed steric caging. All results are in good accord with simulations, and additional testable predictions are made. In conclusion, the classic statistical mechanical projection approximation of replacing all bare attractive and repulsive forces with a single effective force determined by pair structure incurs major errors for describing processes associated with thermally activated escape from transiently localized states.

36 MATERIALS SCIENCE↗

Single step conversion of ethanol to butadiene

A process for producing 1,3-butadiene (BD) from ethanol in a single step by s7passing a mixture containing ethanol in a gas phase over a multifunctional catalyst having a transition metal dispersion of at least 30% on a silica metal oxide support. In some examples the multifunctional catalyst comprises a silica metal oxide having a surface area of at least 200 m{circumflex over ( )}2/g. The multifunctional catalyst can include a transition metal oxide, a silica metal oxide made from a high purity silica gel, mesoporous silica and fumed silica, such as high purity SBA16, SBA15, or Davisil grade 646.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Colloidal Behavior of Plutonium Oxide in Concentrated Electrolyte Solutions

The Hanford Site in Washington State manages legacy high-level radioactive waste streams that display major chemistry and engineering challenges, including the high salt levels and pH values that correspond to conditions under which many classical concepts describing chemical reactivity cannot be applied. One particular challenge that needs to be tackled at Hanford is that Pu concentrations, [Pu], in the soluble phases of the tank wastes are higher than expected based on the solubility of crystalline PuO2, which is widely accepted to be caused by the formation of PuO2 colloid, consisting of nano- to submicron-sized particles (PuO2 NPs). Fundamental research underpinning the behavior of PuO2 NPs under conditions not only relevant to the Hanford tank waste but at high ionic strength in general is needed to reliably predict the chemical reactivity of PuO2 NPs and develop engineering solutions to safely and efficiently process high-level radioactive waste into forms suitable for long-term storage. In this work, we study the behavior of PuO2 NPs (particle size ~100 nm) under high ionic strength conditions by reacting it with highly concentrated (up to 5 M) salt solutions. We explore different electrolyte compositions to elucidate the impact of different anions (NO3-, Cl-, ClO4-, SO42-, C2O42-, CO32-) on the stability of PuO2 NP in the acidic and alkaline pH regime. PuO2 NP aggregation and precipitation as function electrolyte concentration is tracked by a combination of liquid scintillation counting, dynamic light scattering for determination of particle size distributions, and zeta potentials as a proxy for particle charge. At acidic pH, electrolytes containing non-coordinating anions, such as NaNO3, NaCl, and NaClO4 mostly stabilize PuO2 NPs over a large electrolyte concentration range, showing only subtle differences in their reactivity. Other electrolyte anions show a more pronounced effect on the PuO2 NP stability: SO42-, binds directly to the particles’ surface, reverses the particle charge, and precipitates the PuO2 NPs efficiently even at intermediate sulfate concentrations (>0.1 M). In contrast, C2O42- is found to lead to high [Pu] in solution, in the milli-molar range, even at mildly acidic pH (~4). Thermodynamic modeling of the dissolved Pu concentrations using PHREEQC is unable to predict the observed [Pu] in the acidic pH regime, supporting the influence of colloids in maintaining elevated [Pu]. It is noteworthy that the current thermodynamic databases do not include constants for colloidal Pu phases and cannot accurately predict many of the high ionic strength solutions relevant to this work. The mechanisms and models responsible for these observations will need further investigation in the future. At high pH values (~12), PuO2 NPs exhibits classical sol-gel chemistry, meaning that upon destabilization of the colloidal sol, for example by addition of concentrated NaOH, highly porous and viscid PuO2 coagulates are formed that consist of a three-dimensional network likely held together by physical interactions. The PuO2 NP coagulate shows no significant reversibility of the aggregation when contacted with concentrated brines; however, PuO2 NPs can be efficiently resuspended in solution by addition of diluted electrolytes, alkaline solutions containing high amounts of carbonate, or simple addition of water. Especially carbonate is shown to stabilize PuO2 NPs in solution at high pH, characterized by stable colloidal suspensions that are resistant against sedimentation during centrifugation. Thermodynamic modeling of the carbonate system was able to predict an increasing dissolved Pu concentration with increasing carbonate concentration. However, the model was profoundly sensitive to the fixed redox potential and does not include any thermodynamic constants for colloidal Pu species.

Neumann, Julia↗

Quantifying the anomalous water absorption behavior of cement mortar in view of its physical sensitivity to water

The one-dimensional water absorption into cement-based materials, possibly the simplest case of unsaturated water flow playing a fundamental role in predicting mass transport and durability, is still far from being completely understood due to several puzzling anomalies. Considering the water sensitivity of C-S-H gels (swell upon wetting and contract upon drying), a modified Richards equation (MRE) is proposed to quantify the anomalous water absorption into cement-based materials of changing porosity. Consistent experimental tests on a cement mortar and calculations indicate that the MRE with time-decaying water permeability can quantitatively capture the long-term absorption with two linear stages and a nonlinear transition stage between them. The water sensitivity is validated to be responsible for the anomalous deviation of water absorption from the classical square root of time law. It also partially contributes to the anomalous dependence of sorptivity on the temperature-dependent surface tension and viscosity of water and many organic liquids.

36 MATERIALS SCIENCE↗

Lithium Iron Aluminum Nickelate, LiNi x Fe y Al z O 2 —New Sustainable Cathodes for Next–Generation Cobalt–Free Li–Ion Batteries

In recent years, cobalt has become a critical constraint on the supply chain of the Li-ion battery industry. Here, with the ever-increasing projections for electric vehicles, the dependency of current Li-ion batteries on the ever-fluctuating cobalt prices poses serious environmental and sustainability issues. To address these challenges, a new class of cobalt-free materials with general formula of LiNi x Fe y Al z O 2 ( x + y + z = 1), termed as the lithium iron aluminum nickelate (NFA) class of cathodes, is introduced. These cobalt-free materials are synthesized using the sol–gel process to explore their compositional landscape by varying aluminum and iron. These NFA variants are characterized using electron microscopy, neutron and X-ray diffraction, and Mössbauer and X-ray photoelectron spectroscopy to investigate their morphological, physical, and crystal-structure properties. Operando experiments by X-ray diffraction, Mössbauer spectroscopy, and galvanostatic intermittent titration have been also used to study the crystallographic transitions, electrochemical activity, and Li-ion diffusivity upon lithium removal and uptake in the NFA cathodes. NFA compositions yield specific capacities of ≈200 mAh g -1 , demonstrating reasonable rate capability and cycling stability with ≈80% capacity retention after 100 charge/discharge cycles. While this is an early stage of research, the potential that these cathodes could have as viable candidates in next-generation cobalt-free lithium-ion batteries is highlighted here.

25 ENERGY STORAGE↗

Biophysical analysis of the plant-specific GIPC sphingolipids reveals multiple modes of membrane regulation

The plant plasma membrane (PM) is an essential barrier between the cell and the external environment, controlling signal perception and transmission. It consists of an asymmetrical lipid bilayer made up of three different lipid classes: sphingolipids, sterols, and phospholipids. The glycosyl inositol phosphoryl ceramides (GIPCs), representing up to 40% of total sphingolipids, are assumed to be almost exclusively in the outer leaflet of the PM. However, their biological role and properties are poorly defined. In this study, we investigated the role of GIPCs in membrane organization. Because GIPCs are not commercially available, we developed a protocol to extract and isolate GIPC-enriched fractions from eudicots (cauliflower and tobacco) and monocots (leek and rice). Lipidomic analysis confirmed the presence of trihydroxylated long chain bases and 2-hydroxylated very long-chain fatty acids up to 26 carbon atoms. The glycan head groups of the GIPCs from monocots and dicots were analyzed by gas chromatograph-mass spectrometry, revealing different sugar moieties. Multiple biophysics tools, namely Langmuir monolayer, ζ-Potential, light scattering, neutron reflectivity, solid state 2H-NMR, and molecular modeling, were used to investigate the physical properties of the GIPCs, as well as their interaction with free and conjugated phytosterols. We showed that GIPCs increase the thickness and electronegativity of model membranes, interact differentially with the different phytosterols species, and regulate the gel-to-fluid phase transition during temperature variations. These results unveil the multiple roles played by GIPCs in the plant PM.

59 BASIC BIOLOGICAL SCIENCES↗

Pectin methylesterase selectively softens the onion epidermal wall yet reduces acid-induced creep

De-esterification of homogalacturonan (HG) is thought to stiffen pectin gels and primary cell walls by increasing calcium cross-linking between HG chains. Contrary to this idea, recent studies found that HG de-esterification correlated with reduced stiffness of living tissues, measured by surface indentation. The physical basis of such apparent wall softening is unclear, but possibly involves complex biological responses to HG modification. To assess the direct physical consequences of HG de-esterification on wall mechanics without such complications, we treated isolated onion (Allium cepa) epidermal walls with pectin methylesterase (PME) and assessed wall biomechanics with indentation and tensile tests. In nanoindentation assays, PME action softened the wall (reduced the indentation modulus). In tensile force/extension assays, PME increased plasticity, but not elasticity. These softening effects are attributed, at least in part, to increased electrostatic repulsion and swelling of the wall after PME treatment. Despite softening and swelling upon HG de-esterification, PME treatment alone failed to induce cell wall creep. Instead, acid-induced creep, mediated by endogenous α-expansin, was reduced. We conclude that HG de-esterification physically softens the onion wall, yet reduces expansin-mediated wall extensibility.

59 BASIC BIOLOGICAL SCIENCES↗

Impact of gel concentration on filter fluxes in microfiltration of Hanford tank wastes and simulants

Abstract Treatment processes have been proposed that will utilize crossflow filtration to concentrate sludge waste streams at the Department of Energy's Hanford Site. Challenges associated with solid–liquid separation of the waste streams drive a necessary evaluation of available Hanford high level waste (HLW) filtration data. Limiting flux conditions during crossflow filtration are elucidated with the formation of a cake layer on the membrane surface. A mass transfer coefficient between the gel and bulk concentrations plays a critical role in determining filter flux. A correlation between the gel concentration and mass transfer coefficient is made to assist in determining filter performance of select HLW streams. As a process alternative to crossflow filtration, gravity settling of waste streams may be deployed as a solid–liquid separation technique. However, this results in a contrasting performance with the centrifuged solids concentration. A method was developed to estimate expected filtration and settling performance based on physical characterization data for Hanford tank waste samples. By assessing the estimated processing performance of HLW, technical support can be provided during flowsheet planning.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of long-term extension of isolated cell walls from growing cucumber hypocotyls

Walls from frozen-thawed cucumber (Cucumis sativus L.) hypocotyls extend for many hours when placed in tension under acidic conditions. This study examined whether such "creep" is a purely physical process dependent on wall viscoelasticity alone or whether enzymatic activities are needed to maintain wall extension. Chemical denaturants inhibited wall creep, some acting reversibly and others irreversibly. Brief (15 s) boiling in water irreversibly inhibited creep, as did pre-incubation with proteases. Creep exhibited a high Q10 (3.8) between 20 degrees and 30 degrees C, with slow inactivation at higher temperatures, whereas the viscous flow of pectin solutions exhibited a much lower Q10 (1.35). On the basis of its temperature sensitivity, involvement of pectic gel-sol transitions was judged to be of little importance in creep. Pre-incubation of walls in neutral pH irreversibly inactivated their ability to creep, with a half-time of about 40 min. At 1 mM, Cu2+, Hg2+ and Al3+ were strongly inhibitory whereas most other cations, including Ca2+, had little effect. Sulfhydryl-reducing agents strongly stimulated creep, apparently by stabilizing wall enzyme(s). The physical effects of these treatments on polymer interactions were examined by Instron and stress-relaxation analyses. Some treatments, such as pH and Cu2+, had significant effects on wall viscoelasticity, but others had little or no apparent effect, thus implicating an enzymatic creep mechanism. The results indicate that creep depends on relatively rugged enzymes that are firmly attached to or entangled in the wall. The sensitivity of creep to SH-reducing agents indicates that thiol reduction of wall enzymes might provide a control mechanism for endogenous cell growth.

NASA Program Space Biology↗

Misfit p-type transparent conductive oxide (TCO) films, methods and applications

A p-type transparent conductive oxide (TCO) mixed metal oxide material layer formed upon a substrate has a formula M1xM2yOz generally, CaxCoyOz more specifically, and Ca3Co4O9 most specifically. Embodiments provide that the p-type TCO mixed metal oxide material may be formed absent an epitaxial crystalline relationship with respect to the substrate while using a sol-gel synthesis method that uses a chelating polymer material and not a block copolymer material.

36 MATERIALS SCIENCE↗

Direct Optical Lithography of Colloidal Metal Oxide Nanomaterials for Diffractive Optical Elements with 2π Phase Control

Spatially patterned dielectric materials are ubiquitous in electronic, photonic, and optoelectronic devices. These patterns are typically made by subtractive or additive approaches utilizing vapor-phase reagents. On the other hand, recent advances in solution-phase synthesis of oxide nanomaterials have unlocked a materials library with greater compositional, microstructural, and interfacial tunability. However, methods to pattern and integrate these nanomaterials in real-world devices are less established. In this work, we directly optically pattern oxide nanoparticles (NPs) by mixing them with photosensitive diazo-2-naphthol-4-sulfonic acid and irradiating with widely available 405 nm light. We demonstrate the direct optical lithography of ZrO 2 , TiO 2 , HfO 2 , and ITO NPs and investigate the chemical and physical changes responsible for this photoinduced decrease in solubility. Micron-thick layers of amorphous ZrO 2 NPs were patterned with micron resolution and shown to allow 2 pi phase control of visible light. We also show multilayer patterning and use it to fabricate features with different thicknesses and distinct structural colors. Upon annealing at 400 degrees C, the deposited ZrO 2 structures have excellent optical transparency across a wide wavelength range (0.3-10 mu m), a high refractive index (n = 1.84 at 633 nm), and are optically smooth. We then fabricate diffractive optical elements, such as binary phase diffraction gratings, that show efficient diffractive behavior and good thermal stability. Different oxide NPs can also be mixed prior to patterning, providing a high level of material tunability. This work demonstrates a general patterning approach that harnesses the processability and diversity of colloidal oxide nanomaterials for use in photonic applications.

2𝜋 phase shift↗