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NASA NTRS2000

Cell signaling by reactive nitrogen and oxygen species in atherosclerosis

The production of reactive oxygen and nitrogen species has been implicated in atherosclerosis principally as means of damaging low-density lipoprotein that in turn initiates the accumulation of cholesterol in macrophages. The diversity of novel oxidative modifications to lipids and proteins recently identified in atherosclerotic lesions has revealed surprising complexity in the mechanisms of oxidative damage and their potential role in atherosclerosis. Oxidative or nitrosative stress does not completely consume intracellular antioxidants leading to cell death as previously thought. Rather, oxidative and nitrosative stress have a more subtle impact on the atherogenic process by modulating intracellular signaling pathways in vascular tissues to affect inflammatory cell adhesion, migration, proliferation, and differentiation. Furthermore, cellular responses can affect the production of nitric oxide, which in turn can strongly influence the nature of oxidative modifications occurring in atherosclerosis. The dynamic interactions between endogenous low concentrations of oxidants or reactive nitrogen species with intracellular signaling pathways may have a general role in processes affecting wound healing to apoptosis, which can provide novel insights into the pathogenesis of atherosclerosis.

Review, Tutorial↗

DOE OSTI2025

Novel Zwitterionic Polyurethane-in-Salt Electrolytes with High Ion Conductivity, Elasticity, and Adhesion for High-Performance Solid-State Lithium Metal Batteries

This study presents a novel polymer-in-salt (PIS) zwitterionic polyurethane-based solid polymer electrolyte (zPU-SPE) that offers high ionic conductivity, strong interaction with electrodes, and excellent mechanical and electrochemical stabilities, making it promising for high-performance all solid-state lithium batteries (ASSLBs). The zPU-SPE exhibits remarkable lithium-ion (Li+) conductivity (3.7 × 10⁻⁴ S cm−1 at 25 °C), enabled by exceptionally high salt loading of up to 90 wt.% (12.6 molar ratio of Li salt to polymer unit) without phase separation. It addresses the limitations of conventional SPEs by combining high ionic conductivity with a Li+ transference number of 0.44, achieved through the incorporation of zwitterionic groups that enhance ion dissociation and transport. The high surface energy (338.4 J m−2) and elasticity ensure excellent adhesion to Li anodes, reducing interfacial resistance and ensuring uniform Li+ flux. When tested in Li||zPU||LiFePO₄ and Li||zPU||S/C cells, the zPU-SPE demonstrated remarkable cycling stability, retaining 76% capacity after 2000 cycles with the LiFePO4 cathode, and achieving 84% capacity retention after 300 cycles with the S/C cathode. Molecular simulations and a range of experimental characterizations confirm the superior structural organization of the zPU matrix, contributing to its outstanding electrochemical performance. The findings strongly suggest that zPU-SPE is a promising candidate for next-generation ASSLBs.

Wang, Kun↗

NASA NTRS1985

Bonding Heat-Resistant Fabric to Tile

Acid etching, densification, and silica cement ensure strong bond. Key step in preparation for bonding to glazed tile is etching quartz fabric and tile with acid. This increases adhesion of silica cement used to form bond. Procedures use high-temperature materials exclusively and therefore suitable for securing flexible seals and heat barriers around doors and viewing ports in furnaces and kilns.

Holt, J. W.↗

DOE OSTI2022

Size-Dependent Adsorption and Adhesion Energetics of Ag Nanoparticles on Graphene Films on Ni(111) by Calorimetry

Interest in the use of carbon supports for late transition metal nanoparticle catalysts has expanded rapidly due to the increasing importance of electrocatalysts for clean energy and environmental technologies and the use and storage of renewable electricity. Compared to oxide supports, almost nothing is known about the effect of metal nanoparticle size on the energies of the metal atoms within carbon-supported nanoparticles, yet these energies are crucial for understanding their surface reactivity and sintering kinetics. Here, the growth morphology and adsorption energetics of vapor-deposited Ag onto clean graphene/Ni(111) surfaces have been studied using a combination of single-crystal adsorption calorimetry (SCAC) and He + low-energy ion scattering (LEIS). The differential heat of Ag adsorption is 207 kJ/mol for making ~30 atom Ag particles on graphene terraces at 100 K and 16 kJ/mol higher for making ~9 atom Ag clusters at defect sites at the same temperature. The heat of adsorption increases rapidly with Ag coverage as 3D Ag nanoparticles nucleate and grow in size, asymptotically reaching within 5 kJ/mol of the bulk Ag sublimation enthalpy (285 kJ/mol) by 2 ML. The heats of adsorption and Ag nanoparticle densities from LEIS (~10 16 /m 2 ) were combined to provide the Ag/graphene adhesion energy (E adh = 1.8 J/m 2 in the large-particle limit) and the Ag chemical potential (μ) versus effective particle diameter (D). The Ag chemical potential was well-fitted by μ(D) = (3γ v /M – E adh )(1 + (1.5 nm)/D)(2V m /D), where γ v /M is the surface energy of bulk Ag and V m is its molar volume. The same equation is known to fit similar data for late transition metals on clean surfaces of metal oxide single crystals. The adhesion energy of Ag measured here on graphene falls within the wide range measured for Ag on those oxide surfaces and is almost as large as on the oxide that binds Ag particles most strongly, namely CeO 2 (111), which is well-known to be very effective at resisting catalyst deactivation by metal sintering. Furthermore, these results imply that carbon supports will be effective at resisting sintering and that Ag particles smaller than 6 nm on graphene will bind small adsorbed reaction intermediates more weakly than supports with weaker adhesion to Ag, like MgO(100).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1991

Stiff, Strong Splice For A Composite Sandwich Structure

New type of splice for composite sandwich structure reduces peak shear stress in structure. Layers of alternating fiber orientation interposed between thin ears in adhesive joint. Developed for structural joint in spar of helicopter rotor blade, increases precision of control over thickness of adhesive at joint. Joint easy to make, requires no additional pieces, and adds little weight.

Schmaling, D.↗

DOE OSTI2024

Dual material fused filament fabrication of composite core‐shell structures with improved impact resistance and interfacial adhesion

The mechanical performance of parts produced by fused filament fabrication (FFF) has been limited due to the presence of voids and poor interlayer welding. Recent advancements in FFF have enabled the fabrication of void-free objects with strong interlayer welding through the use of semicrystalline polymer shells such as high-density polyethylene (HDPE) along with a high viscosity core polymer like acrylonitrile-butadiene-styrene (ABS). Furthermore, the zero-shear viscosity (η0) of ABS is three orders of magnitude higher than HDPE making the ABS-HDPE core-shell configuration preferable. ABS holds the shape by preventing bulk flow and part bending while HDPE promotes full surface contact across the layers. Most polymers, however, are immiscible which causes a weak weld line along the core-shell interface. Herein, maleic anhydride (MAH) is grafted to the butadiene segment of the ABS core thereby compatibilizing the interface with HDPE, improving the interfacial adhesion. Attenuated total reflectance-Fourier transform infrared spectroscopy was employed to confirm successful grafting. Using a custom-made die affording the core-shell structure, the ABS-g-MAH is shown to improve the impact resistance by 253% and 16% compared to neat HDPE and ABS specimens, respectively. Additionally, a 10% increase compared to the unmodified ABS-HDPE core-shell configuration is observed.

36 MATERIALS SCIENCE↗

NASA NTRS1983

Diatomic molecules and metallic adhesion, cohesion, and chemisorption - A single binding-energy relation

Potential-energy relations involving a few parameters in simple analytic forms have been found to represent well the energetics of a wide variety of diatomic molecules. However, such two-atom potential functions are not appropriate for metals. It is well known that, in the case of metals, there exist strong volume-dependent forces which can never be expressed as pairwise interactions. The present investigation has the objective to show that, in spite of the observation concerning metals, a single binding-energy relation can be found which accurately describes diatomic molecules as well as adhesion, cohesion, and chemisorption on metals. This universality reveals a commonality between the molecular and metallic bond.

Ferrante, J.↗

DOE OSTI2025

Corrosion resistant hot melt adhesive to bind metals

Hot melt adhesives (HMAs) play an important role in many industries, and their demand is expected to grow. HMAs don't require any solvents, and their application results in the formation of strong bonds with the substrate upon cooling within seconds. These properties differentiate them from liquid glues and make them preferable for practical application. Currently, commercial HMAs are used in bonding lightweight materials such as paper, polymers, and cartons, and have limited usage in areas necessitating the bonding of heavier objects like metals. Here, in this study, we report a design and testing of versatile platform comprising an ion-coordinating polymer and ionic fillers for performance optimization and understanding of structure–property relationships, enabling the rational design of HMAs with improved adhesion to metal surfaces. All-atom Molecular dynamics (MD) simulations and various characterization methods are used to elucidate the adhesion mechanism in model composite system containing polyethylene oxide mixed with chemically diverse salt particles. The maximum adhesion strength is found in composites with Al(OH) 3 and FeCl 3 fillers. Interestingly, the presence of Al(OH) 3 also provides a multifunctional anticorrosion property as measured electrochemically using the Tafel method. The discovered path to formulations with improved adhesion to metal surfaces constitutes an important step toward advancing HMAs for use in the structural and semi-structural metal work domain.

Adhesive and cohesive forces↗

NASA NTRS2003

The Evaluation of High Temperature Adhesive Bonding Processes for Rocket Engine Combustion Chamber Applications

NASA Glenn Research Center is currently evaluating the possibility of using high- temperature polymer matrix composites to reinforce the combustion chamber of a rocket engine. One potential design utilizes a honeycomb structure composed of a PMR-II- 50/M40J 4HS composite facesheet and titanium honeycomb core to reinforce a stainless steel shell. In order to properly fabricate this structure, adhesive bond PMR-II-50 composite. Proper prebond surface preparation is critical in order to obtain an acceptable adhesive bond. Improperly treated surfaces will exhibit decreased bond strength and durability, especially in metallic bonds where interface are susceptible to degradation due to heat and moisture. Most treatments for titanium and stainless steel alloys require the use of strong chemicals to etch and clean the surface. This processes are difficult to perform due to limited processing facilities as well as safety and environmental risks and they do not consistently yield optimum bond durability. Boeing Phantom Works previously developed sol-gel surface preparations for titanium alloys using a PETI-5 based polyimide adhesive. In support of part of NASA Glenn Research Center, UDRI and Boeing Phantom Works evaluated variations of this high temperature sol-gel surface preparation, primer type, and primer cure conditions on the adhesion performance of titanium and stainless steel using Cytec FM 680-1 polyimide adhesive. It was also found that a modified cure cycle of the FM 680-1 adhesive, i.e., 4 hrs at 370 F in vacuum + post cure, significantly increased the adhesion strength compared to the manufacturer's suggested cure cycle. In addition, the surface preparation of the PMR-II-50 composite was evaluated in terms of surface cleanness and roughness. This presentation will discuss the results of strength and durability testing conducted on titanium, stainless steel, and PMR-II-50 composite adherends to evaluate possible bonding processes.

McCray, Daniel↗

NASA NTRS1973

Research study on materials processing in space experiment number M512

Adhesion of the melted metals to the adjacent solid metals, and cohesion of the liquid metal to itself appeared to be equally as strong in zero gravity as on earth. Similar cut edge bead periodicity in cut thin plate, and similar periodic chevron patterns in full penetration welds were seen. The most significant practical result is that the design of braze joints for near zero gravity can be very tolerant of dimensional gaps in the joint. This conclusion is based on a comparison of narrow, wide and variable gap widths. Brazing is very practical as a joining or repairing technique for metal structures at zero gravity. The operation of the hardware developed to locate successive small (0.6 cm) diameter cylinders in the focus of the battery powered EB unit, melt the various metal specimens and deploy some liquid metal drops to drift in space, was generally successful. However, the sphericity and surface roughness were far from those of ball bearings.

Tobin, J. M.↗

DOE OSTI2024

Adhesion in thermomechanically processed seaweed-lignocellulosic composite materials

The increasing concerns associated with petroleum-derived polymers motivate the development of sustainable, renewably sourced alternatives. In ubiquitous applications such as structural materials for infrastructure, the built environment as well as packaging, where natural materials such as wood are used, we rely on nonrenewable and nondegradable polymers to serve as adhesives. In wood panels, such as medium density fiberboards (MDFs), formaldehyde-based resins are predominantly used to bond wood fibers and to provide strength to the materials. To further mitigate the environmental impact of construction materials, more sustainable adhesives need to be investigated. Here, in this article, we introduce Ulva seaweed as an adhesive to enable cohesion and strength in hot-pressed wood panels. Upon hot-pressing, powdered Ulva flows in between the wood particles, generating a matrix, which provides strong binding. We show that the flexural strength of Ulva-bonded wood biocomposites increases with increasing Ulva concentrations. At an Ulva concentration of 40 wt%, our composites reach an average elastic modulus of 6.1 GPa, and flexural strength of 38.2 MPa (compared to 4.7 GPa and 22.6 MPa, respectively, for pure wood compressed at the same pressing conditions). To highlight the bonding mechanisms, we performed infrared and x-ray photoelectron spectroscopy and identified indications of fatty acid mobility during hot-pressing. In addition, we demonstrate that the presence of Ulva improves other properties of the composites such as water resistance and fame retardancy. Ulva is also shown to behave as an excellent adhesive agent between two prepressed beams. Finally, we perform an in-depth analysis of the environmental impact of wood-Ulva biocomposites.

36 MATERIALS SCIENCE↗

NASA NTRS1999

Soil Analysis Micro-Mission Concepts Derived from the MSP 2001 Mars Environmental Compatibility Assessment (MECA)

The Mars Environmental Compatibility Assessment (MECA) will evaluate the Martian environment for soil and dust-related hazards to human exploration as part of the Mars Surveyor Program 2001 Lander. The integrated MECA payload contains a wet-chemistry laboratory, a microscopy station, an electrometer to characterize the electrostatic environment, and arrays of material patches to study abrasion and adhesion. Heritage will be all-important for low cost micro-missions, and adaptations of instruments developed for the Pathfinder, '98 and '01 Landers should be strong contenders for '03 flights. This talk has three objectives: (1) Familiarize the audience with MECA instrument capabilities; (2) present concepts for stand-alone and/or mobile versions of MECA instruments; and (3) broaden the context of the MECA instruments from human exploration to a comprehensive scientific survey of Mars. Due to time limitations, emphasis will be on the chemistry and microscopy experiments. Ion-selective electrodes and related sensors in MECA's wet-chemistry laboratory will evaluate total dissolved solids, redox potential, pH, and the concentration of many soluble ions and gases in wet Martian soil. These electrodes can detect potentially dangerous heavy-metal ions, emitted pathogenic gases, and the soil's corrosive potential, and experiments will include cyclic voltammetry and anodic stripping. For experiments beyond 2001, enhancements could allow multiple use of the cells (for mobile experiments) and reagent addition (for quantitative mineralogical and exobiological analysis). MECA's microscopy station combines optical and atomic-force microscopy (AFM) in an actively focused, controlled illumination environment to image particles from millimeters to nanometers in size. Careful selection of substrates allows controlled experiments in adhesion, abrasion, hardness, aggregation, magnetic and other properties. Special tools allow primitive manipulation (brushing and scraping) of samples. Soil particle properties including size, shape, color, hardness, adhesive potential (electrostatic and magnetic), will be determined using an array of sample receptacles and collection substrates. The simple, rugged atomic-force microscope will image in the submicron size range and has the capability of performing a particle-by-particle analysis of the dust and soil. Future implementations might enhance the optical microscopy with spectroscopy, or incorporate advanced AFM techniques for thermogravimetric and chemical analysis.

Hecht, M. H.↗

DOE OSTI2021

Engineering Thermal Transport across Layered Graphene–MoS 2 Superlattices

Layering two-dimensional van der Waals materials provides a high degree of control over atomic placement, which could enable tailoring of vibrational spectra and heat flow at the sub-nanometer scale. In this work, using spatially resolved ultrafast thermoreflectance and spectroscopy, we uncover the design rules governing cross-plane heat transport in superlattices assembled from monolayers of graphene (G) and MoS 2 (M). Using a combinatorial experimental approach, we probe nine different stacking sequences, G, GG, MG, GGG, GMG, GGMG, GMGG, GMMG, and GMGMG, and identify the effects of vibrational mismatch, interlayer adhesion, and junction asymmetry on thermal transport. Pure G sequences display evidence of quasi-ballistic transport, whereas adding even a single M layer strongly disrupts heat conduction. The experimental data are described well by molecular dynamics simulations, which include thermal expansion, accounting for the effect of finite temperature on the interlayer spacing. The simulations show that an increase of ~2.4% in the layer separation of GMGMG, relative to its value at 300 K, can lead to a doubling of the thermal resistance. Using these design rules, we experimentally demonstrate a five-layer GMGMG superlattice “thermal metamaterial” with an ultralow effective cross-plane thermal conductivity comparable to that of air.

2D materials↗

NASA NTRS1976

The nature of surfaces and their influence in wear mechanisms

The wear of materials is strongly dependent upon the nature of the solid surfaces in contact, their properties and the nature of their films. Oxide films, orientation, crystal transformations, adhesive binding, crystal structure, hardness, and the presence of alloying agents are all shown to affect one or more of the forms of wear. The three most common forms of wear, adhesive, abrasive, and corrosive, are discussed in terms of the way each is affected by various material properties. Results presented indicate how wear can be optimized by concern for properties of materials.

Buckley, D. H.↗

NASA NTRSDate not supplied

Charge Deposition/Neutralization and Dust Removal via Plasma Interactions

Electrically charged and chemically reactive lunar dust can cause serious problems to spacecraft, surface equipment, and astronaut health, so understanding its interaction with and transport through the lunar plasma environment is important to dust mitigation efforts. We explore the charging of granular material in the natural environment of the Moon, recreate those conditions in the laboratory under high vacuum, and examine dust transport and charge neutralization for application in future lunar missions. Phenomena such as charge deposition via electron and ion beams, photoionization through ultraviolet light exposure, neutralization of charge through impingement by an ionized compressed gas, and tribocharging during dust liberation from surfaces will be presented. Surface materials of interest such as floating/grounded conductors and orthofabric for spacesuits are the preliminary focus of this effort. An electrometer is used to characterize currents interacting with the surfaces in the case of the electron/ion/UV source exposure, an electrostatic voltmeter is used to measure the potential on the surfaces without inadvertently discharging them, and a charge plate monitor is used to verify the efficiency of discharging the surfaces via ionized gas impingement. After setup of the initial charge conditions on the surfaces, a quick burst of high-pressure gas is used to overcome adhesion forces and initially dislodge the dust from the surfaces, followed by a low flow of gas that is ionized via application of a strong electric field. The gas is released in a high vacuum environment so as the pressure drops from the initial compressed state through to the vacuum state, the mean free path reaches a point where ionization can occur before all the gas disperses into the vacuum. This ionized gas can then neutralize both the dust and the surface to ensure minimal resettling. Several parameters such as gas composition, electrode geometry, high voltage waveform shape/polarity, and pulse timing have been explored and will be presented here.

electrostatics↗

NASA NTRS1977

The nature of surfaces and their influence in wear mechanisms

The wear of materials is strongly dependent upon the nature of the solid surfaces in contact, their properties and the nature of the films on them. Oxide films, orientation, crystal transformations, adhesive binding, crystal structure, hardness and the presence of alloying agents are all shown to effect one or more of the forms of wear. The three most common forms of wear, adhesive, abrasive, and corrosive, are discussed in terms of the way each is affected by various material properties. Results presented indicate how wear can be optimized by concern for properties of materials.

Buckley, D. H.↗

DOE OSTI2022

Metal–ceramic composite structures for fabrication of high power density plasmonic devices

The recent decade brought many advances to plasmonics, but high power density plasmonic antennas designed to behave as heaters or operate in high temperature environments are still facing material stability challenges preventing their ultimate use. Gold has been the optimal choice among plasmonic materials but experiences morphology changes at temperature that result in device efficiency reduction and failure. Bulk titanium nitride has been explored as a solution but has deal-breaking tradeoffs in device quality factor. In this paper, we explore via proof-of-concept the use of a metal–ceramic composite structure to determine whether a bulk Au nanorod can provide strong plasmonic resonances while coated with an ultrathin conformal layer of titanium nitride or silica to provide morphological stability and sufficient plasmonic activity without excessive resonance quality degradation. We show SEM-level morphological stability for temperatures up to 500 °C with coatings below 4 nm. Computer modeling suggests the ultrathin titanium nitride has detrimental effects on the strong plasmonic resonances of a Au nanorod. Here, we then looked into other possible coatings for solutions to stabilize high power density plasmonic antennas including plasmonic oxides, metal adhesion layers, and silica, the latter appearing to be the best option while lowering the overall peak electric field intensity, the silica increases the electric field intensity at its boundary.

36 MATERIALS SCIENCE↗

NASA NTRS1988

The effects of atomic oxygen on polymeric materials

At the altitudes of low-earth orbit (LEO), atomic oxygen (AO) is the most abundant chemical species. This strong oxidizing agent reacts with virtually any organic material that is not already fully oxidized. Erosion by AO can be extensive and jeopardizes any protective coatings, thermal blankets, adhesives, and structural composites exposed on the exterior of satellites in LEO. Researchers prepared and tested organic materials for their susceptibility to AO using a commercial plasma asher which approximately simulates the oxygen effects in LEO. Experiments were performed on a polyimide, a polysulfone, and two epoxy adhesives into which low molecular-weight additives have been dissolved. Incorporated in the molecular structure of these additives are elements such as silicon whose nonvolatile oxides, which are formed on exposure to AO, remain as a coating on the surface to create a barrier between the remainder of the organic material and the AO. We find that the additives protect the materials, but the low solubility of some limit their utility. Concurrent studies are underway to measure the effect of the additives on the thermal expansion coefficients of the materials. Tows of aramid fibers, which are important components in the proposed tether satellite systems, have been eroded in the asher. The results which show that the square root of the mass remaining decreases linearly with the time of exposure (see the figure) are consistent with a constant rate of surface erosion. The tensile strength of these eroded tows decreases with time of exposure also; additional measurements are in progress.

Orwoll, Robert A.↗