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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 253 records · Page 14

Additively Manufactured Carbon Fiber-Reinforced Siliconized Silicon Carbide Composites Using Carbon Fiber-Reinforced Poly-Ether-Ether-Ketone (PEEK) as a Precursor

Herein, we report a method to additively manufacture carbon fiber-reinforced siliconized silicon carbide composites. The process involves the pyrolysis of a 3D-printed carbon fiber-reinforced poly-ether-ether-ketone (PEEK) composite to produce a porous carbon fiber-reinforced carbon matrix composite preform, which is subsequently infiltrated with molten silicon to obtain a carbon fiber-reinforced siliconized silicon carbide composite. A key aspect of the method is limiting polymer melt flow during pyrolysis of PEEK, which is achieved by thermally annealing the 3D-printed carbon fiber-reinforced PEEK preform in air at a temperature below PEEK’s melting temperature. Rheological and differential scanning calorimetry (DSC) measurements demonstrate that the thermal annealing treatment altered the melting behavior of PEEK, while NMR and FTIR measurements provided a mechanistic explanation for the structural changes responsible for the behavior. It was also found that dimensional changes during pyrolysis were anisotropic with greater shrinkage in the stacking direction of the material.

Yoon, Bola [ORNL] (ORCID:0000000260875373)↗

Design issues for propulsion systems using metallized propellants

Metallized propellants are liquid propellants that contain metal particles. These particles are suspended in a gelled fuel or oxidizer. Aluminum is used as the metal additive. The addition of metal to conventional propellants can increase their specific impulse and their density over conventional propellants, and consequently, the payload delivered on Mars and lunar transportation vehicles, Earth-to-Orbit vehicles and upper stages for robotic planetary missions. Gelled fuels also provide increased safety during accidental propellant leakage or spills. To take full advantage of these potential performance increases, there are changes that must be made to the vehicle design. The differences are discussed between metallized propellant and traditional liquid propellants and their effect on the propulsion system design. These differences include the propellant density, mixture ratio, engine performance, and propellant rheology. Missions related to the Space Exploration Initiative are considered as design examples to illustrate these issues.

Palaszewski, Bryan↗

Design issues for propulsion systems using metallized propellants

Metallized propellants are liquid propellants that contain metal particles. These particles are suspended in a gelled fuel or oxidizer. Aluminum is used as the metal additive. The addition of metal to conventional propellants can increase their specific impulse and their density over conventional propellants, and consequently, the payload delivered on Mars and lunar transportation vehicles, Earth-to-Orbit vehicles and upper stages for robotic planetary missions. Gelled fuels also provide increased safety during accidental propellant leakage or spills. To take full advantage of these potential performance increases, there are changes that must be made to the vehicle design. The differences are discussed between metallized propellant and traditional liquid propellants and their effect on the propulsion system design. These differences include the propellant density, mixture ratio, engine performance, and propellant rheology. Missions related to the Space Exploration Initiative are considered as design examples to illustrate these issues.

Palaszewski, Bryan↗

Localized and Collective Dynamics in Liquid-like Polyethylenimine-Based Nanoparticle Organic Hybrid Materials

In this work, broadband dielectric spectroscopy, rheology, and nuclear magnetic resonance spectroscopy are employed to study molecular dynamics in a nanoparticle organic hybrid materials(NOHMs)system comprising 20 wt% silica nanoparticles ionically-bonded to a polyethylenimine canopy. By comparing the neat polymer (used as a canopy) to the derivative NOHMs, we find that timescales characterizing segmental dynamics in the NOHM are identical to those for the neat polymer. Detailed analysis of the carbon-spin lattice relaxation times yields mechanistic insights into localized and collective dynamics, in quantitative agreement with dielectric results. Interestingly, the NOHMs retain liquid-like characteristics unlike conventional polymer nanocomposites but exhibit higher viscosity due to additional contributions from tethered polymer chains, and mesoscopic structuring. These findings demonstrate the potential of achieving unique and desired material properties via NOHMs by an informed choice of the canopy material.

36 MATERIALS SCIENCE↗

Oxidation of Glycolate in the Defense Waste Processing Facility (DWPF) Recycle Collection Tank - 20305

The Savannah River Site's Defense Waste Processing Facility (DWPF) operations are being upgraded with the introduction of the Nitric-Glycolic Flowsheet. Glycolic acid has been shown superior to formic acid as the reducing acid used during chemical processing. The new flowsheet improves or maintains necessary parameters such as 1) reduction of mercury, 2) adjustment of feed rheology and 3) adjustment of melter oxidation/reduction potential. Further, the potential for catalytic hydrogen generation in DWPF processing is virtually eliminated. DWPF process condensates are collected and returned to the SRS Concentration, Storage and Transfer Facilities (CSTF). The Recycle Collection Tank (RCT) collects off-gas condensate during chemical processing, vitrification, and other unit operations performed in DWPF and is the singular return vessel delivering recycle effluent back to CSTF. Each batch of recycle may contain a small amount of glycolate from chemical processing and melter off-gas condensates. To avoid potential flammability issues due to thermolysis of glycolate in the CSTF, chemical oxidation within the RCT has been investigated as an option for mitigating the transfer of glycolate. Sodium permanganate has been down-selected as the best option for oxidation of glycolate. Testing was performed using both 2-L and 22-L reactors (16,800:1 and 1,530:1 scale by volume) with non-radioactive waste simulants to approximate the expected RCT compositions. RCT simulants were evaluated at various process pH and temperature conditions. Also, RCT operations, namely the sequence of addition of corrosion inhibitors (NaOH and NaNO{sub 2}) versus a permanganate strike, were evaluated. Glycolate was introduced via a sludge simulant to mimic both expected entrainment and abnormal process foam-over conditions - the range being between 68 and 5100 mg/kg glycolate. Glycolate destruction was monitored by ion chromatography (IC). The corresponding manganese behavior was monitored in real-time using in situ ultraviolet-visible (UV-Vis) spectroscopy. RCT glycolate content can be reduced to below the IC detection limit within 90 minutes for all concentrations investigated. Ion Chromatography analysis revealed that under alkaline conditions, glycolate is primarily oxidized to oxalate with no significant formation of CO{sub 2} or carbonate, and nitrite is not oxidized to nitrate. Initially, complete oxidation of organics species and nitrite was assumed. Determination of the mechanistic chemical reaction has allowed the required amount of permanganate to be more accurately predicted and the total addition to be significantly reduced. UV-Vis measurements reveal that permanganate (Mn{sup 7+}) is reduced to manganate (Mn{sup 6+}) in the RCT. The oxidant stoichiometry is defined by using the initial permanganate to glycolate (P/G) molar ratio. At low initial glycolate concentration (68 and 140 mg/kg), the minimum required initial permanganate to glycolate (P/G) molar ratio was found to be 5-6. With high initial glycolate concentrations (5100 mg/kg) a lower (P/G) molar ratio of ∼2.5 was needed. The final portion of this effort supporting the nitric/glycolic flowsheet will be to test actual (fully radioactive) RCT samples as per the above simulant tests. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Modular Approach for the Synthesis of Bottlebrush Diblock Copolymers from Poly(Glycidyl Methacrylate)-block-Poly(Vinyldimethylazlactone) Backbones

A strategy that enables the facile synthesis of bottlebrush block copolymers with flexible backbones was developed. A demonstration of the strategy’s utility was carried out by grafting end-functionalized polymethylmethacrylate (PMMA) and polystyrene (PS) to the dually reactive block copolymer, poly(glycidyl methacrylate)-block-poly(vinyldimethylazlactone) (PGMA-b-PVDMA). Five different bottlebrush diblock copolymers were investigated by size-exclusion chromatography (SEC), 1H NMR, Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC), X-ray scattering methods, atomic force microscopy (AFM), rheology and computational simulations using molecular dynamics (MD), and self-consistent field theory (SCFT). A relationship between the glass transition temperature and the fraction of chain ends was demonstrated by DSC and highlights the potential of this synthetic method to tailor polymer properties. All five samples were found to be in a disordered phase exhibiting multiscale structures revealed by two broad peaks in small-angle X-ray scattering (SAXS) that can be attributed to graft-to-graft and backbone-to-backbone density correlations using MD simulations. The SCFT-based simulations justify the observation of a disordered phase due to its stabilization by the grafts. Additionally, this modular approach can be easily extended to other grafts, including responsive, conducting, and charged polymers with the prerequisite end groups. The versatility and ease of assembling these functional bottlebrushes constitute a powerful “toolbox” method for the rapid and scalable synthesis of novel bottlebrush block copolymers with desired properties.

36 MATERIALS SCIENCE↗

Dynamic Mechanical Properties of N-Phenylnadimide Modified PMR Polyimide Composites

The rheological behavior of newly developd Celion 6000/N-phenylnadimide modified PMR polyimide and PMR-15 composites was investigated. The dynamic mechanical properties were correlated with the structure of N-phenylnadimide modified PMR polyimides. The storage modulus (G'), loss modulus (G''), and loss tangent (tan delta) of four composite systems were measured over a temperature range from -150 to 400 C. Three well defined peaks were seen in the regions of 360, 100, and -120 C, corresponding to the alpha, beta, and gamma relaxations, respectively, of the matrix resins. The activation energies of the alpha, beta, and gamma relaxations were estimated to be 232, 60, and 14 kcal/mole, respectively, for PMR-15. Addition of N-phenylnadimide to the PMR-15 composition lowered the glass transition temperature and the activation energies of PMR-15 polyimide. The dynamic mechanical data appear to be consistent with the formation of a copolymer from N-phenylnadimide and a PMR-15 prepolymer.

Pater, R. H.↗

Block Polyelectrolyte Additives That Modulate the Viscoelasticity and Enhance the Printability of Gelatin Inks at Physiological Temperatures

We demonstrate the utility of block polyelectrolyte (bPE) additives to enhance viscosity and resolve challenges with the three-dimensional (3D) printability of extrusion-based biopolymer inks. The addition of oppositely charged bPEs to solutions of photocurable gelatin methacryloyl (GelMA) results in complexation-driven self-assembly of the bPEs, leading to GelMA/bPE inks that are printable at physiological temperatures, representing stark improvements over GelMA inks that suffer from low viscosity at 37 °C, leading to low printability and poor structural stability. The hierarchical microstructure of the self-assemblies (either jammed micelles or 3D networks) formed by the oppositely charged bPEs, confirmed by small-angle X-ray scattering, is attributed to the enhancements in the shear strength and printability of the GelMA/bPE inks. Varying bPE concentration in the inks is shown to enable tunability of the rheological properties to meet the criteria of pre- and postextrusion flow characteristics for 3D printing, including prominent yielding behavior, strong shear thinning, and rapid recovery upon flow cessation. Moreover, the bPE self-assemblies also contribute to the robustness of the photo-cross-linked hydrogels; photo-cross-linked GelMA/bPE hydrogels are shown to exhibit higher shear strength than photo-cross-linked GelMA hydrogels. Last, the assessment of the printability of GelMA/bPE inks indicates excellent printing performance, including minimal swelling postextrusion, satisfactory retention of the filament shape upon deposition, and satisfactory shape fidelity of the various printed constructs. We envision this study to serve as a practical guide for the printing of bespoke extrusion inks where bPEs are used as scaffolds and viscosity enhancers that can be emulated in a range of photocurable precursors.

36 MATERIALS SCIENCE↗

A Bayesian Approach for In-Situ Stress Prediction and Uncertainty Quantification for Subsurface Engineering

Many subsurface engineering applications require accurate knowledge of the in-situ state of stress for their safe design and operation. Existing methods to meet this need primarily include field measurements for estimating one or more of the principal stresses from a borehole, or optimization methods for constructing a 3D geomechanical model in terms of geophysical measurements. These methods, however, often contain considerable uncertainty in estimating the state of stress. Here, in this paper, we build on a Bayesian approach to quantify uncertainty in stress estimations for subsurface engineering applications. This approach can provide an estimate of the 3D distribution of stress throughout the volume of interest and provide an estimate of the uncertainty arising from the stress measurement, the rheology parameters, and a paucity of measurements. The value of this approach is demonstrated using stress measurements from the In Salah carbon storage site, which was one of the world’s first industrial carbon capture and storage projects. This demonstration shows the application of this Bayesian approach for estimating the initial state of stress for In Salah and quantifying the uncertainty in the estimated stress. Also, an assessment of a maximum injection pressure to prevent geomechanical risks from CO 2 injection pressures is provided in terms of the probability distribution of the minimum principal stress quantified by the approach. With the In Salah case study, this paper demonstrates that using the Bayesian approach can provide additional insights for site explorations and/or project operations to make informed-site decisions for subsurface engineering applications.

58 GEOSCIENCES↗

Variable domain mutational analysis to probe the molecular mechanisms of high viscosity of an IgG 1 antibody

Subcutaneous injection is the preferred route of administration for many antibody therapeutics for reasons that include its speed and convenience. However, the small volume limit (typically ≤2 mL) for subcutaneous delivery often necessitates antibody formulations at high concentrations (commonly ≥100 mg/mL), which may lead to physicochemical problems. For example, antibodies with large hydrophobic or charged patches can be prone to self-interaction giving rise to high viscosity. Here, we combined X-ray crystallography with computational modeling to predict regions of an anti-glucagon receptor (GCGR) IgG 1 antibody prone to self-interaction. An extensive mutational analysis was undertaken of the complementarity-determining region residues residing in hydrophobic surface patches predicted by spatial aggregation propensity, in conjunction with residue-level solvent accessibility, averaged over conformational ensembles from molecular dynamics simulations. Dynamic light scattering (DLS) was used as a medium throughput screen for self-interaction of ~200 anti-GCGR IgG 1 variants. A negative correlation was found between the viscosity determined at high concentration (180 mg/mL) and the DLS interaction parameter measured at low concentration (2–10 mg/mL). Additionally, anti-GCGR variants were readily identified with reduced viscosity and antigen-binding affinity within a few fold of the parent antibody, with no identified impact on overall developability. The methods described here may be useful in the optimization of other antibodies to facilitate their therapeutic administration at high concentration.

59 BASIC BIOLOGICAL SCIENCES↗

Glacio-Seismotectonics: Ice Sheets, Crustal Deformation and Seismicity

The last decade has witnessed a significant growth in our understanding of the past and continuing effects of ice sheets and glaciers on contemporary crustal deformation and seismicity. This growth has been driven largely by the emergence of postglacial rebound models (PGM) constrained by new field observations that incorporate increasingly realistic rheological, mechanical, and glacial parameters. In this paper, we highlight some of these recent field-based investigations and new PGMs, and examine their implications for understanding crustal deformation and seismicity during glaciation and following deglaciation. The emerging glacial rebound models outlined in the paper support the view that both tectonic stresses and glacial rebound stresses are needed to explain the distribution and style of contemporary earthquake activity in former glaciated shields of eastern Canada and Fennoscandia. However, many of these models neglect important parameters, such as topography, lateral variations in lithospheric strength and tectonic strain built up during glaciation. In glaciated mountainous terrains, glacial erosion may directly modulate tectonic deformation by resetting the orogenic topography and thereby providing an additional compensatory uplift mechanism. Such effects are likely to be important both in tectonically active orogens and in the mountainous regions of glaciated shields.

Sauber, Jeanne↗

Flexure and the role of inplane force around coronae on Venus

Large coronae on Venus, such as Artemis and Latona, are rimmed by conspicuous trenches and associated outer rises. Sandwell and Schubert have observed that these systems resemble terrestrial subduction zones in planform and have succeeded in fitting an elastic plate bending equation to the inferred flexural topography. However, the first zero crossing bending moments required are -2.5 x 10(exp 17) N for Artemis and -5.0 x 10(exp 16) N for Latona. Since these moments are similar in magnitude to those of subducting slabs on Earth, a rollback subduction mechanism was proposed to explain the flexure around the largest coronae, although a differential thermal subsidence model is sufficient to account for the topography around some coronae. The purpose is to investigate the effect of inplane force as a possible alternative to large applied moments in producing flexure at Artemis and Latona. The close correlation of gravity to topography on Venus implies the absence of a low viscosity zone and the strong coupling of the lithosphere to mantle convection. If coronae are the surface manifestations of mantle plumes, they may be the sites of active convective stress coupling. As the upwelling reaches the lithosphere, it spreads radially outward, inducing shear tractions on the base of the plate. In addition, the hot, expanding corona may load the surrounding plate horizonally. Both the basal shear stresses and radial loading can be treated as an equivalent compressive inplane force in the mechanical lithosphere, which contributes to the bending of the outlying plate. Using a model that relates inplane force to the measured gravity anomalies, a rough value of the inplane force at Artemis was calculated. Recent Pioneer Venus spherical harmonic gravity models indicate a geoid anomaly of about 75 m over Artemis, which corresponds to an estimated inplane force on the order of -1x10(exp 13) N/m. The gravity model is unable to resolve Latona, but an inplane force of similar dimensions is assumed. The maximum possible inplane force based on the expected rheology can be constrained by using the approximate 5 K/km thermal gradient inferred from the best fit 30 km elastic plate at Artemis and Latona. For a dry olivine flow law in the upper mantle, the compressional load limit of the 60 km thick mechanical lithosphere is -4 x 10(exp 13) N/m. This value is equivalent to a load of -8 x 10(exp 13) N/m on a 30 km thick elastic plate.

Brown, C. David↗

Lost Circulation Materials in Geothermal Drilling: Thermal Degradation, Viscosity, Compression, and Flow Loop Tests

This dataset provides a set of experimental data on the performance of lost circulation materials (LCMs) used in geothermal drilling operations. It includes results from four distinct tests: thermal degradation, viscosity measurements, compression tests, and high-temperature flow loop experiments. The materials tested, such as cedar fiber, cotton seed hulls, magma fiber, microcellulose, and sawdust, were analyzed under a range of conditions to assess their effectiveness in mitigating fluid losses in geothermal wells. Data on thermal degradation explores mass loss, water loss, and gas release for each material when subjected to temperatures between 90C and 250C. Viscosity measurements capture the behavior of LCM mixtures under different temperatures, while compression tests investigate the structural integrity of both undegraded and thermally degraded materials. The high-temperature flow loop experiments simulate geothermal well conditions, analyzing how different materials and mixtures affect fluid flow and sealing performance in a fractured reservoir environment. In addition to the experimental data, the dataset includes photos documenting the materials, schematics of test setups, and several published manuscripts that provide detailed insights into the experimental methods and findings.

15 GEOTHERMAL ENERGY↗

Index tests for geosynthetic clay liners containing bentonite–polymer composites

The hydraulic conductivity of geosynthetic clay liners (GCLs) containing bentonite–polymer composites (BPCs) is controlled by a pore clogging mechanism related to the swelling of sodium bentonite (NaB) granules and formation of polymer gel in the pore space. Three index testing procedures that are influenced by bentonite swelling and rheology of the polymer gel were evaluated in this study for screening BPC GCLs for hydraulic conductivity: viscosity, liquid limit by fall-cone penetration and active water content. Experiments were conducted using polyacrylamide (PAM) polymer, dry-blended mixtures of PAM and NaB and a BPC from a commercially available GCL. These materials were contacted with inorganic solutions representing leachates from a range of waste containment scenarios. For the BPC that was evaluated, hydraulic conductivities less than 10 -10 m/s were obtained when the viscosity exceeded 220 mPa s and the active water content exceeded 300%. Hydraulic conductivities less than 10 -11 m/s were achieved for viscosity exceeding 350 mPa s, fall-cone liquid limit exceeding 190 and active water content exceeding 300%. Additional testing is needed to assess the generality of these index tests and the identified thresholds when applied to other BPC GCLs and other permeant liquids.

Engineering↗

Summary of JAYGO mixing and FSM-1 application of castable inhibitor and liner

Two JAYGO planetary mixers (12 and 42 gallon) are being qualified to mix STW5-3224 liner and STW5-3223 castable inhibitor. These mixers are an integral part of a mix process which allows for safe addition of the asbestos component. An essential part of the engineering evaluation (ETP-0347) of these mixers is the generation of static test fire data. Ultimately, these results will help confirm the adequacy of these mixers for production mixing of liner and inhibitor. (These data are not required for qualification of the Certification Test Plan CTP-0125). The details on the mixing, inhibiting, and sling-lining of JAYGO-mixed castable inhibitor and liner which were applied to the FSM-1 segments are presented. The objectives are the following: (1) to document processing events surrounding the JAYO mixing of castable inhibitor and liner, and the subsequent inhibiting and sling lining onto the FSM-1 segments; and (2) to substantiate the measured properties of these JAYGO-mixed materials (rheological and mechanical) and compare these properties to existing production database.

Evans, Kurt B.↗

Lava Flow Dynamics

This grant originally had four major tasks, all of which were addressed to varying extents during the course of the research: (1) Measure the fractal dimensions of lava flows as a function of topography, substrate, and rheology; (2) The nature of lava tube systems and their relation to flow fields; (3) A quantitative assessment of lava flow dynamics in light of the fractal nature of lava flow margins; and (4) Development and application of a new remote sensing tool based on fractal properties. During the course of the research, the project expanded to include the following projects: (1) A comparison of what we can-learn from remote sensing studies of lava flow morphology and from studies of samples of lava flows; (2) Study of a terrestrial analog of the nakhlites, one of the groups of meteorites from Mars; and (3) Study of the textures of Hawaiian basalts as an aid in understanding the dynamics (flow rates, inflation rates, thermal history) of flow interiors. In addition, during the first year an educational task (development and writing of a teacher's guide and activity set to accompany the lunar sample disk when it is sent to schools) was included.

Taylor, G. Jeffrey↗

Surface temperatures and glassy state investigations in tribology, part 1

The research in this report is divided into two categories: (1) lubricant rheological behavior, and (2) thermal behavior of a simulated elastohydrodynamic contact. The studies of the lubricant rheological behavior consists of high pressure, low shear rate viscosity measurements, viscoelastic transition measurements, by volume dilatometry, dielectric transitions at atmospheric pressure and light scattering transitions. Lubricant shear stress-strain behavior in the amorphous glassy state was measured on several fluids. It appears clear from these investigations that many lubricants undergo viscoplastic transitions in typical EHD contacts and that the lubricant has a limiting maximum shear stress it can support which in turn will determine the traction in the contact except in cases of very low slide-roll ratio. Surface temperature measurements were made for a naphthenic mineral oil and a polyphenyl ether. The maximum surface temperature in these experiments was approximately symmetrical about the zero slide-roll ration except for absolute values of slide-roll ratio greater than about 0.9. Additional surface temperature measurements were made in contacts with rough surfaces where the composite surface roughness was approximately equal to the EHD film thickness. A regression analysis was done to obtain a predictive equation for surface temperatures as a function of pressure, sliding speed, and surface roughness. A correction factor for surface roughness effects to the typical flash temperature analysis was found.

Winer, W. O.↗

Structure and stability of hydrous minerals at high pressure

The presence of even small amounts of hydrogen in the Earth's deep interior may have profound effects on mantle melting, rheology, and electrical conductivity. The recent discovery of a large class of high-pressure H-bearing silicates further underscores the potentially important role for hydrous minerals in the Earth's mantle. Hydrogen may also be a significant component of the Earth's core, as has been recently documented by studies of iron hydride at high pressure. In this study, we explore the role of H in crystal structures at high pressure through detailed Raman spectroscopic and x ray diffraction studies of hydrous minerals compressed in diamond anvil cells. Brucite, Mg(OH)2, has a simple structure and serves as an analogue for the more complex hydrous silicates. Over the past five years, this material has been studied at high pressure using shock-compression, powder x ray diffraction, infrared spectroscopy, Raman spectroscopy, and neutron diffraction. In addition, we have recently carried out single-crystal synchrotron x-ray diffraction on Mg(OH)2 and Raman spectroscopy on Mg(OD)2 at elevated pressure. From all these studies, an interesting picture of the crystal chemical behavior of this material at high pressure is beginning to emerge. Some of the primary conclusions are as follows: First, hydrogen bonding is enhanced by the application of pressure. Second, layered minerals which are elastically anisotropic at low pressure may not be so at high pressure. Furthermore, the brucite data place constraints on the effect of hydrogen on seismic velocities and density at very high pressure. Third, the stability of hydrous minerals may be enhanced at high P by subtle structural rearrangements that are difficult to detect using traditional probes and require detailed spectroscopic analyses. Finally, brucite appears to be unique in that it undergoes pressure-induced disordering that is confined solely to the H-containing layers of the structure.

Duffy, T. S.↗