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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
NASA NTRS2014

Synthesis and Properties of Cross-Linked Polyamide Aerogels

We report our ongoing research on polyamide aerogels made by step growth polymerization using a combination of terephthaloyl chloride, isophthaloyl chloride and m-phenylenediamine. Crosslinking of the amine capped polymer chains with 1,3,5-benzenetricarbonyl trichloride causes gelation in as little as two to five minutes. Removing the reaction solvent is accomplished through solvent exchange, followed by drying using supercritical CO2 extraction to give colorless aerogels with densities ranging from 0.07 to 0.33 grams per cubic centimeter and surface areas as high as 440 square meters per gram. Statistical experimental design methodology has been utilized to investigate dependence of properties of these aerogels, such as density, compressive modulus, and surface area, on changes in fabrication parameters including formulated number of amide oligomer repeat units (n-value), acid chloride (meta, para or combination), and solids concentration of solution used for gelation. For example, the density of these materials was found to be dependent on the acid chloride type and the solids concentration, but n was not a significant variable. However, surface area was significantly influenced by all three parameters. The polyamide aerogels represent a potential cost savings over previously reported polyimide aerogels, since monomers are all inexpensive and commercially available. Surface area and density were both highest when 100 terephthaloyl chloride was used but a combination of 5 solid concentration, 100 terephthaloyl chloride and n of 20 gave the best combination of properties.

cross-linked↗
DOE OSTI2020

Thermal Properties of Sodium Borosilicate Glasses as a Function of Sulfur Content

SO3 additions, up to 3.0 wt%, were systematically investigated for effects on the physical properties of sodium borosilicate glass melted in air, with a sulfur-free composition of 50SiO2-10Al2O3-12B2O3-21Na2O-7CaO (wt%). Solubility measurements, using electron microscopy chemical analysis, determined the maximum loading to be ~1.5 wt% SO3. It was found that sulfur (here as sulfate) in this glass increased the glass transition temperature, thermal diffusivity, heat capacity, and thermal conductivity, and decreased the mass density. Structural analysis, performed with Raman spectroscopy, indicated that the borosilicate network polymerized with sulfur additions, presumably due to Na2O being required to charge compensate the ionic SO42- additions, thus becoming unavailable to form non-bridging oxygen in the silicate network. It is postulated that this increased crosslinking of the borosilicate backbone lead to a structure with higher dimensionality and average bond energy. This increased the mean free paths and vibration frequency of the phonons, which resulted in the observed increase in thermal properties.

Thermal properties, Borosilicate glass, Sulfur sol↗
NASA NTRS1990

Experiment K-6-01. Distribution and biochemistry of mineral and matrix in the femurs of rats

Previous analyses of the composition of mineral and matrix in the bone of young rats following space flight has revealed deficits in calcium, phosphorus, and osteocalcin, a non-collagenous protein, without an associated decrease in collagen. To characterize the location and nature of this mineralization defect in a weight bearing long bone, the femur, researchers attempted to relate the spatial distribution of mineral in situ in the proximal, central and distal thirds of the femoral diaphysis to the biochemical composition of bone from the same area. Biochemical analyses revealed lower concentrations of calcium, phosphorus and osteocalcin but not collagen only in the central third of the diaphysis of the flight animals (F) compared to synchronous controls (S). Collagen concentration was reduced only in the proximal third of the diaphysis, where all 3 crosslinks, expressed as nM/mol collagen were higher in F than S. A new technique, x ray microtomography, with a resolution of 26 microns, was used to obtain semi-quantitative data on mineral distribution in reconstructed sections of wet whole bone. To improve the resolution of the mineral density distribution, images of the surfaces of cut sections were analyzed by backscattered electrons in a scanning electron microscope (BSE). There was good agreement between the results of the two stereochemical techniques which revealed distinct patterns of mineralization in transverse and longitudinal directions of the diaphysis. The novel methodology developed for this flight experiment shows considerable promise in elucidating the biochemical nature of what appear to be regional alterations in the mineralization of long bones of animals exposed to spaceflight.

Arnaud, S.↗
DOE OSTI2021

Insights into the Physical-Chemical Properties of a CO2-Responsive Fracturing Fluid

Here we determine the phase behavior of StimuFrac, a CO2 responsive fracturing fluid, under geothermal wellbore conditions. StimuFrac is an aqueous poly(allylamine) fluid that crosslinks in the presence of CO2. StimuFrac significantly reduces the net pressure required to induce fractures, relative to other fracture fluids, and has potential to reduce water use. However, the phase behavior and equations of state to describe StimuFrac’s phase behavior remain unavailable. Here we determine the density and molar volume of the fluid as a function of geothermal relevant temperatures, pressures, and weight fractions of StimuFrac added. In general, experiments find that StimuFrac’s density decreases as temperature and pressure increase. Using these results, equations of saturated state and phase diagrams for different polymer concentrations are reported. These results are critical inputs for planned numerical simulation efforts.

Pease, Leonard F.↗
DOE OSTI2022

Development of Gelatin-Coated Hydrogel Microspheres for Novel Bioink Design: A Crosslinker Study

The development of vascularized tissue is a substantial challenge within the field of tissue engineering and regenerative medicine. Studies have shown that positively-charged microspheres exhibit dual-functions: (1) facilitation of vascularization and (2) controlled release of bioactive compounds. In this study, gelatin-coated microspheres were produced and processed with either EDC or transglutaminase, two crosslinkers. The results indicated that the processing stages did not significantly impact the size of the microspheres. EDC and transglutaminase had different effects on surface morphology and microsphere stability in a simulated colonic environment. Incorporation of EGM and TGM into bioink did not negatively impact bioprintability (as indicated by density and kinematic viscosity), and the microspheres had a uniform distribution within the scaffold. These microspheres show great potential for tissue engineering applications.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

A Nonaqueous Redox‐Matched Flow Battery with Charge Storage in Insoluble Polymer Beads**

Abstract We describe the nonaqueous redox‐matched flow battery (RMFB), where charge is stored on redox‐active moieties covalently tethered to non‐circulating, insoluble polymer beads and charge is transferred between the electrodes and the beads via soluble mediators with redox potentials matched to the active moieties on the beads. The RMFB reported herein uses ferrocene and viologen derivatives bound to crosslinked polystyrene beads. Charge storage in the beads leads to a high (approximately 1.0–1.7 M) effective concentration of active material in the reservoirs while preventing crossover of that material. The relatively low concentration of soluble mediators (15 mM) eliminates the need for high‐solubility molecules to create high energy density batteries. Nernstian redox exchange between the beads and redox‐matched mediators was fast relative to the cycle time of the RMFB. This approach is generalizable to many different redox‐active moieties via attachment to the versatile Merrifield resin.

25 ENERGY STORAGE↗
DOE OSTI2023

Regulation of hair cell and stomatal size by a hair cell-specific peroxidase in the grass Brachypodium distachyon

The leaf epidermis is the outermost cell layer forming the interface between plants and the atmosphere that must both provide a robust barrier against (a)biotic stressors and facilitate carbon dioxide uptake and leaf transpiration. To achieve these opposing requirements, the plant epidermis developed a wide range of specialized cell types such as stomata and hair cells. While factors forming these individual cell types are known, it is poorly understood how their number and size is coordinated. Here, in this study, we identified a role for BdPRX76/BdPOX, a class III peroxidase, in regulating hair cell and stomatal size in the model grass Brachypodium distachyon. In bdpox mutants prickle hair cells were smaller and stomata were longer. Because stomatal density remained unchanged, the negative correlation between stomatal size and density was disrupted in bdpox and resulted in higher stomatal conductance and lower intrinsic water-use efficiency. BdPOX was exclusively expressed in hair cells suggesting that BdPOX cell autonomously promotes hair cell size and indirectly restricts stomatal length. Cell wall autofluorescence and lignin stainings indicated a role for BdPOX in lignification or crosslinking of related phenolic compounds at the hair cell base. Ectopic expression of BdPOX in the stomatal lineage increased phenolic autofluorescence in guard cell walls and restricted stomatal elongation in bdpox. Together, we highlight a developmental interplay between hair cells and stomata that optimizes epidermal functionality. We propose that cell-type-specific changes disrupt this interplay and lead to compensatory developmental defects in other epidermal cell types.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Enhanced rare earth element recovery with cross-linked glutaraldehyde-lanthanide binding peptides in foam-based separations

Lanthanide Binding Tag (LBT) peptides that coordinate selectively with lanthanide ions can be used to replace the energy intensive processes used for the separation of rare earth elements (REEs). These surface-active biomolecules, once selectively complexed with the trivalent REE cations, can adsorb to air/aqueous interfaces of bubbles for foam-based REEs recovery. Glutaraldehyde, an organic compound that is a homobifunctional crosslinker for proteins and peptides, can be used to enhance the adsorption and interfacial stabilization of lanthanide-bound peptides films. The stability of the interfacial cross-linked films was tested by measuring their dilational and shear surface rheological properties. Surface activity of the adsorbed species was analyzed using pendant drop tensiometry, while surface density and molecular arrangement were determined using x-ray reflectivity and x-ray fluorescence near total reflection. Glutaraldehyde cross-linked REE-peptide complexes enhance the adsorption of lanthanides to air-water interfaces, resulting in thicker interfacial structures. Subsequently, these thicker layers enhance the dilational and shear interfacial rheological properties. The interfacial film stabilization and REEs extraction promoted by the cross-linker presented in this work provides an approach to integrate glutaraldehyde as a substitute of common foam stabilizers such as polymers, surfactants, and particles to optimize the recovery of REEs when using biomolecules as extractants.

36 MATERIALS SCIENCE↗
DOE OSTI2020

On the nature of macroradicals formed upon radiolysis of aqueous poly(N-vinylpyrrolidone) solutions

Herein we have explored the nature of macroradicals formed upon radiolysis of aqueous poly(N-vinylpyrrolidone) (PVP) solutions using pulse radiolysis, density functional theory (DFT) and literature data. On the basis of literature data on site-specific kinetics of hydrogen abstraction from simple amides and spectra corresponding to specific radical sites on the same amides we have assessed the distribution of H-atom abstraction by • OH radicals from different positions on the pyrrolidone ring and the polymer backbone. Pulse radiolysis experiments performed at different doses per pulse and different PVP concentrations demonstrate that the H-abstracting radiolysis products are not quantitatively scavenged by the polymer when the dose per pulse exceeds ≈40 Gy. The implications of this are discussed in the context of radical-initiated crosslinking reactions. At a mass fraction of 0.1% PVP and doses per pulse ranging from 7 Gy to 117 Gy, the overall radical decay observed at 390 nm follows second order kinetics with rate constants on the order of 10 9 dm 3 mol -1 s -1 .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Relationship between microporous structure and light gas transport through glassy polymeric membranes revealed by molecular simulations

Microporous glassy polymers are attractive materials for gas separation membranes, due to their high permeability and tailorable selectivity, provided physical aging can be delayed. The archetypal microporous glassy polymer, PTMSP, can be blended with a hyper-crosslinked isatin–triptycene porous polymer network (PPN) to delay physical aging. However, while PPN is effective at reducing physical aging, it also affects the permeability of light gases through PTMSP. Molecular dynamics simulations were used here to shed fundamental light on the mechanisms responsible for these effects. Atomistic models are developed that satisfactorily reproduce experimental observations such as matrix density and cavity size distributions for neat PTMSP as well as for PTMSP–PPN blends. Analysis of the simulation results suggests that physical aging is delayed because the PPN inclusions slow down PTMSP relaxation while reducing the connectivity between free volume pockets. To understand how PPN inclusions affect light gas permeability, the atomistic models developed are used to probe CO 2 and CH 4 diffusion and sorption. These simulations are conducted for PTMSP matrices exhibiting varying density, towards reproducing experimental permeability data. Interrogating the simulation trajectories, it is discovered that while CH 4 travels preferentially through the free volume cavities, CO 2 preferentially interacts with the available surfaces, especially in the presence of PPN. These differences help interpret experimental observations. The transport of C 2 H 6 and H 2 S through PTMSP matrices was also investigated. These gases, and in particular H 2 S, were found to absorb within PTMSP, yielding very low diffusion coefficients. The ability to predict differences in diffusion pathways for various natural gas components unveils the possibility of engineering membranes to control permeability and selectivity towards large-scale applications.

Bao Le, Tran Thi [Univ. of Oklahoma, Norman, OK (U↗
DOE OSTI2024

A self-healing plastic ceramic electrolyte by an aprotic dynamic polymer network for lithium metal batteries

Abstract Oxide ceramic electrolytes (OCEs) have great potential for solid-state lithium metal (Li 0 ) battery applications because, in theory, their high elastic modulus provides better resistance to Li 0 dendrite growth. However, in practice, OCEs can hardly survive critical current densities higher than 1 mA/cm 2 . Key issues that contribute to the breakdown of OCEs include Li 0 penetration promoted by grain boundaries (GBs), uncontrolled side reactions at electrode-OCE interfaces, and, equally importantly, defects evolution (e.g., void growth and crack propagation) that leads to local current concentration and mechanical failure inside and on OCEs. Here, taking advantage of a dynamically crosslinked aprotic polymer with non-covalent –CH 3 ⋯CF 3 bonds, we developed a plastic ceramic electrolyte (PCE) by hybridizing the polymer framework with ionically conductive ceramics. Using in-situ synchrotron X-ray technique and Cryogenic transmission electron microscopy (Cryo-TEM), we uncover that the PCE exhibits self-healing/repairing capability through a two-step dynamic defects removal mechanism. This significantly suppresses the generation of hotspots for Li 0 penetration and chemomechanical degradations, resulting in durability beyond 2000 hours in Li 0 -Li 0 cells at 1 mA/cm 2 . Furthermore, by introducing a polyacrylate buffer layer between PCE and Li 0 -anode, long cycle life >3600 cycles was achieved when paired with a 4.2 V zero-strain cathode, all under near-zero stack pressure.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Imaging APO-BMI with Micro X-ray Computed Tomography (CT)

APO-BMI is a high-strength, high-temperature, and low-density foam comprised of 1,2-bis(2-aminophenylthio) ethane (APO-Link, formerly Apocure-601) and 4,4’-bismaleimidodiphenylmethane (BMI) that is used structural applications within the aerospace and weapons manufacturing sectors. APO-link is the diamine reagent used to synthesize BMI, a thermosetting resin. This resin can remain in a molten, flowing state for an extended period of time before crosslinking, allowing addition of glass or carbon microballoons to form its final structure. A portion of the current project was to observe the thermal effects on the structural integrity of the foam associated with exposure to an ion beam. Features within the foam were imaged using micro X-ray computed tomography (CT). The resulting imaging provided evidence that microballoon structure remained mostly intact at the points of failure, indicating that the failure of the material was occurring in the binder material.

36 MATERIALS SCIENCE↗
NASA NTRS1991

Polycrystalline SiC fibers from organosilicon polymers

Various organosilicon polymers have been converted into small diameter, fine-grained silicon carbide fibers by melt spinning, crosslinking, and pyrolyzing to greater than 1600 C. The high pyrolysis temperature densifies the fiber and causes CO evolution which removes nearly all oxygen. An additive prevents the loss of strength normally associated with such treatments. Silicon carbide fibres with up to 2.6 GPa (380 ksi) tensile strength, greater than 420 GPa (greater than 60 Msi) elastic modulus, and 3.1-3.2 mg/cu m density have been prepared via this process. Their microstructure consists of greater than 95 wt pct B-SiC crystallites averaging 30-40 nm diameter, with varying amounts of graphitic carbon between the SiC grains. Under inert conditions, the fibers can be thermally aged at least 12 h/1800 C with minimal change in properties.

Lipowitz, Jonathan↗
NASA NTRS1999

Engineering of Novel Biocolloid Suspensions

Colloidal suspensions are materials with a variety of uses from cleaners and lubricants to food, cosmetics, and coatings. In addition, they can be used as a tool for testing the fundamental tenets of statistical physics. Colloidal suspensions can be synthesized from a wide variety of materials, and in the form of monodisperse particles, which can self-assemble into highly ordered colloidal crystal structures. As such they can also be used as templates for the construction of highly ordered materials. Materials design of colloids has, to date, relied on entropic self-assembly, where crystals form as result of lower free energy due to a transition to order. Here, our goal is to develop a completely new method for materials fabrication using colloidal precursors, in which the self-assembly of the ordered colloidal structures is driven by a highly controllable, attractive interaction. This will greatly increase the range of potential structures that can be fabricated with colloidal particles. In this work, we demonstrate that colloidal suspensions can be crosslinked through highly specific biological crosslinking reactions. In particular, the molecules we use are protein-carbohydrate interactions derived from the immune system. This different driving force for self-assembly will yield different and novel suspensions structures. Because the biological interactions are heterotypic (A binding to B), this chemical system can be used to make binary alloys in which the two colloid subpopulations vary in some property - size, density, volume fraction, magnetic susceptibility, etc. An additional feature of these molecules which is unique - even within the realm of biological recognition - is that the molecules bind reversibly on reasonable time-scales, which will enable the suspension to sample different configurations, and allow us to manipulate and measure the size of the suspension dynamically. Because of the wide variety of structures that can be made from these novel colloids, and because the suspension structure can be altered dynamically, we believe this biocolloid system will yield a novel set of materials with many technological applications, including sensors (both biological and non-biological), optical filters and separation media.

Hammer, D. A.↗
DOE OSTI2023

Mechanistic insights into the pyrolysis of poly (vinyl chloride)

The accumulation of unmanaged plastic waste in the environment has a devastating impact upon marine life and human health. Catalytic and thermal pyrolysis are promising technologies toward the efficient utilization of plastic waste. Yet, the processing of polymers, such as polyvinyl chloride (PVC), that decompose into corrosive compounds remains a major challenge. In this work, we employ density functional theory (DFT) and thermogravimetric analysis (TGA) to explore the elementary chemical steps that underpin the thermal decomposition of PVC. We determine that the dehydrochlorination reaction (i.e., 1 st stage of thermal decomposition) begins in tertiary chloride defects and propagates via HCl–mediated autocatalysis of internal allylic (IA) chloride groups. The latter groups, when in the vicinity of π–conjugated polymer segments, release HCl in a facile manner. We predict that other compounds, including hydrogen halides and H 2 O could also catalyze PVC’s dehydrochlorination. We suggest that hydrogen halides are the most efficient catalysts for this process, while other compounds like H 2 O may slow down the dehydrochlorination compared to purely HCl-catalyzed process, because of the dilution of the produced HCl. This result is corroborated by TGA experiments. Additionally, we study the thermochemistry and kinetics of polyene chain crosslinking and the formation of aromatics. The former reaction proceeds in parallel with the dehydrochlorination process (i.e., during the 1st stage of thermal decomposition), whilst the latter may occur at high temperatures (i.e., during the 2 nd stage of thermal decomposition). Furthermore, this work contributes to the fundamental understanding of molecular scale phenomena that take place during PVC pyrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Characterizing Porous and Nonporous Phenolic Resins from Molecular Dynamics Simulations

Phenolic resins are an important component of many ablative heat shield materials, which protect spacecrafts from the extreme temperatures reached during atmospheric entry. Examples include the high-density Heritage Carbon Phenolic (HCP) used in the Pioneer-Venus and Galileo missions, as well as the low-density Phenolic Impregnated Carbon Ablator (PICA) used in the Mars Science Laboratory and Mars 2020 missions. Additionally, recent developments within NASA have produced the mid-density Heatshield for Extreme Entry Environment Technology (HEEET) and its derivative 3D Woven Mid-Density Carbon Phenolic (3MDCP). Unlike the nonporous phenolic in HCP, PICA and HEEET/3MDCP are fabricated by infusing preforms with diluted phenolic formulations to obtain a lower density porous matrix. Despite the importance of the phenolic phase to the material response during entry, the variation in properties of porous and nonporous phenolic is not well understood. Here, we present an investigation of porous and nonporous phenolic resins using molecular dynamics (MD) simulations. Resin cure is mimicked in the simulations through the inclusion of representative reaction templates to generate accurate models of the complex crosslinked structures. To create porous models, explicit solvent molecules are included during the cure simulations. We observe nanoscale separation of the phenolic and solvent phases, which results in significant differences in the final structures of porous and nonporous models. In addition to a quantitative assessment of the network structure and porosity, we elucidate the effects of the phenolic formulation on the final material properties. These results are compared with experimental data as appropriate.

phenolic↗
DOE OSTI2020

Thermal and Electrical Properties of Isocyanate Derived Organic Aerogels for Cryogenic Insulation Applications

The use and storage of cryogens such as liquefied nitrogen, helium, hydrogen among others requires reliable and efficient thermal insulation systems. Passive insulation from high performance materials that are well-known for their inherent low thermal conductivity would reduce the overall costs involved in design, manufacture and maintenance of such systems. One such class of materials are referred to as aerogels. These materials are known for their low density, high mesoporosity, high surface areas, low thermal conductivity and high acoustic impedance. Aerogels were invented by S.S. Kistler in 1931 and the most common type are those made of silica. However, the inherent fragility of silica aerogels makes them hard to mass produce, and therefore applications have been limited. A major breakthrough was introduced by our team almost 20 years ago with the invention of polymer crosslinked silica aerogels. Those materials shifted attention to all-polymer aerogels that have overcome all fragility issues associated with their inorganic counterparts. This study focuses on such polymeric aerogels that can be mass produced as large monoliths while maintaining the low thermal conductivity of traditional silica aerogels over a wide temperature range. Manufacturing flexibility of polymeric aerogels allows fabrication of blocks and sheets that can be applied in various configurations to insulate cryogenic and superconducting devices. The thermal conductivity with 80 K and room temperature boundary are reported as well as other properties (electrical), that need to be considered when designing devices for cryogenic applications.

Churu, Gitogo↗
NASA NTRS2000

How Molecular Structure Affects Mechanical Properties of an Advanced Polymer

density was performed over a range of temperatures below the glass transition temperature. The physical characterization, elastic properties and notched tensile strength all as a function of molecular weight and test temperature were determined. For the uncrosslinked SI material, it was shown that notched tensile strength is a strong function of both temperature and molecular weight, whereas stiffness is only a strong function of temperature. For the crosslinked PETI-SI material, it was shown that the effect of crosslinking significantly enhances the mechanical performance of the low molecular weight material; comparable to that exhibited by the high molecular weight material.

Nicholson, Lee M.↗