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At least 109 records · Page 6

Gone But Not Forgotten: The Aeolian Modification of Fluvial Surfaces on Mars: Preliminary Results from Central Australia

MOC images indicate that aeolian ridges may mask and even obliterate primary depositional surfaces on Mars. This modification increases the difficulty in mapping the recent geological history of the planet. An analogue study in central Australia demonstrates how patterns in aeolian dunes, formed over abandoned fluvial surfaces, can be used to detect buried fluvial features.

Bourke, M. C.

Enhanced spectral purity of WSe 2 quantum emitters via conformal organic adlayers

Quantum emitters in solid-state materials are typically embedded in the bulk of their hosts, making their electronic transitions inaccessible to surface modification. In contrast, two-dimensional materials, with their all-surface nature, offer a platform for tuning quantum emitters via chemical functionalization. Because of its semiconducting properties that enable electrical addressability, monolayer WSe 2 is a promising candidate for quantum emission, although the complex interplay between point defects and the localized strain needed to activate quantum emission leads to poor spectral purity. Here, we demonstrate that functionalizing monolayer WSe 2 with conformal adlayers of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) improves quantum emission spectral purity. Optical spectroscopy reveals that PTCDA functionalization lowers defect activation energies by 10 meV and induces a 30 nm redshift in quantum emission wavelength, while preserving the bright and dark exciton energies of monolayer WSe 2 . First-principles calculations corroborate these findings, thus providing molecular-level insight into the underlying mechanism of enhanced spectral purity.

Ananth, Riddhi [Northwestern Univ., Evanston, IL (

Performance of thermal barrier coatings in high heat flux environments

Thermal barrier coatings were exposed to the high temperature and high heat flux produced by a 30 kW plasma torch. Analysis of the specimen heating rates indicates that the temperature drop across the thickness of the 0.038 cm ceramic layer was about 1100 C after 0.5 sec in the flame. An as-sprayed ZrO2-8%Y2O3 specimens survived 3000 of the 0.5 sec cycles with failing. Surface spalling was observed when 2.5 sec cycles were employed but this was attributed to uneven heating caused by surface roughness. This surface spalling was prevented by smoothing the surface with silicon carbide paper or by laser glazing. A coated specimen with no surface modification but which was heat treated in argon also did not surface spall. Heat treatment in air led to spalling in as early as 2 cycle from heating stresses. Failures at edges were investigated and shown to be a minor source of concern. Ceramic coatings formed from ZrO2-12%Y2O3 or ZrO2-20%Y2O3 were shown to be unsuited for use under the high heat flux conditions of this study.

Miller, R. A.

Performance of thermal barrier coatings in high heat flux environments

Thermal barrier coatings were exposed to the high temperature and high heat flux produced by a 30 kW plasma torch. Analysis of the specimen heating rates indicates that the temperature drop across the thickness of the 0.038 cm ceramic layer was about 1100 C after 0.5 sec in the flame. An as-sprayed ZrO2-8 percent Y2O3 specimens survived 3000 of the 0.5 sec cycles with falling. Surface spalling was observed when 2.5 sec cycles were employed but this was attributed to uneven heating caused by surface roughness. This surface spalling was prevented by smoothing the surface with silicon carbide paper or by laser glazing. A coated specimen with no surface modification but which was heat treated in argon also did not surface spall. Heat treatment in air led to spalling in as early as 1 cycle from heating stresses. Failures at edges were investigated and shown to be a minor source of concern. Ceramic coatings formed from ZrO2-12 percent Y2O3 or ZrO2-2O percent Y2O3 were shown to be unsuited for use under the high heat flux conditions of this study.

Miller, R. A.

Performance of thermal barrier coatings in high heat flux environments

Thermal barrier coatings were exposed to the high temperature and high heat flux produced by a 30 kW plasma torch. Analysis of the specimen heating rates indicates that the temperature drop across the thickness of the 0.038 cm ceramic layer was about 1100 C after 0.5 sec in the flame. An as-sprayed ZrO2-8 percent Y203 specimens survived 3000 of the 0.5 sec cycles with failing. Surface spalling was observed when 2.5 sec cycles were employed but this was attributed to uneven heating caused by surface roughness. This surface spalling was prevented by smoothing the surface with silicon carbide paper or by laser glazing. A coated specimen with no surface modification but which was heat treated in argon also did not surface spall. Heat treatment in air led to spalling in as early as 2 cycle from heating stresses. Failures at edges were investigated and shown to be a minor source of concern. Ceramic coatings formed from ZrO2-12 percent Y2O3 or ZrO2-20 percent Y2O3 were shown to be unsuited for use under the high heat flux conditions of this study.

Miller, R. A.

Thermal emittance enhancement of graphite-copper composites for high temperature space based radiators

Graphite-copper composites are candidate materials for space based radiators. The thermal emittance of this material, however, is a factor of two lower than the desired emittance for these systems of greater than or equal to 0.85. Arc texturing was investigated as a surface modification technique for enhancing the emittance of the composite. Since the outer surface of the composite is copper, and samples of the composite could not be readily obtained for testing, copper was used for optimization testing. Samples were exposed to various frequencies and currents of arcs during texturing. Emittances near the desired goal were achieved at frequencies less than 500 Hz. Arc current did not appear to play a major role under 15 amps. Particulate carbon was observed on the surface, and was easily removed by vibration and handling. In order to determine morphology adherence, ultrasonic cleaning was used to remove the loosely adherent material. This reduced the emittance significantly. Emittance was found to increase with increasing frequency for the cleaned samples up to 500 Hz. The highest emittance achieved on these samples over the temperature range of interest was 0.5 to 0.6, which is approximately a factor of 25 increase over the untextured copper emittance.

Rutledge, Sharon K.

Thermal emittance enhancement of graphite-copper composites for high temperature space based radiators

Graphite-copper composites are candidate materials for space based radiators. The thermal emittance of this material, however, is a factor of two lower than the desired emittance for these systems of greater than or equal to 0.85. Arc texturing was investigated as a surface modification technique for enhancing the emittance of the composite. Since the outer surface of the composite is copper, and samples of the composite could not be readily obtained for testing, copper was used for optimization testing. Samples were exposed to various frequencies and currents of arcs during texturing. Emittances near the desired goal were achieved at frequencies less than 500 Hz. Arc current did not appear to play a major role under 15 amps. Particulate carbon was observed on the surface, and was easily removed by vibration and handling. In order to determine morphology adherence, ultrasonic cleaning was used to remove the loosely adherent material. This reduced the emittance significantly. Emittance was found to increase with increasing frequency for the cleaned samples up to 500 Hz. The highest emittance achieved on these samples over the temperature range of interest was 0.5 to 0.6, which is approximately a factor of 25 increase over the untextured copper emittance.

Rutledge, Sharon K.

Self-Healing Nanocomposites for Reusable Composite Cryotanks

Composite cryotanks, or composite overwrapped pressure vessels (COPVs), offer advantages over currently used aluminum-lithium cryotanks, particularly with respect to weight savings. Future NASA missions are expected to use COPVs in spaceflight propellant tanks to store fuels, oxidizers, and other liquids for launch and space exploration vehicles. However, reliability, reparability, and reusability of the COPVs are still being addressed, especially in cryogenic temperature applications; this has limited the adoption of COPVs in reusable vehicle designs. The major problem with composites is the inherent brittleness of the epoxy matrix, which is prone to microcrack formation, either from exposure to cryogenic conditions or from impact from different sources. If not prevented, the microcracks increase gas permeation and leakage. Accordingly, materials innovations are needed to mitigate microcrack damage, and prevent damage in the first place, in composite cryotanks. The self-healing technology being developed is capable of healing the microcracks through the use of a novel engineered nanocomposite, where a uniquely designed nanoparticle additive is incorporated into the epoxy matrix. In particular, this results in an enhancement in the burst pressure after cryogenic cycling of the nanocomposite COPVs, relative to the control COPVs. Incorporating a novel, self-healing, epoxy-based resin into the manufacture of COPVs allows repeatable self-healing of microcracks to be performed through the simple application of a low-temperature heat source. This permits COPVs to be reparable and reusable with a high degree of reliability, as microcracks will be remediated. The unique phase-separated morphology that was imparted during COPV manufacture allows for multiple self-healing cycles. Unlike single-target approaches where one material property is often improved at the expense of another, robustness has been introduced to a COPV by a combination of a modified resin and nanoparticle additives. Unique nanoparticles were used that have been surface-functionalized to be compatible with the resin. Both organic and inorganic components toughen the matrix and result in a more impact-resistant COPV. In one resin system containing an inorganic nanomaterial additive, a significant improvement in burst performance was observed after the COPV was cryo-impact-damaged and then self-healed, with a greater than 10% improvement in burst pressure after the self-healing process was performed. Initial cross-sectional analysis via microscopy showed good resin infiltration of the carbon fibers and without voids. To further enhance the capability between the nanomaterial additives and the resin, a surface modification was successfully performed. A second specialty epoxy resin was prepared using a surface modified nanomaterial additive, and COPVs were fabricated. Steps were taken to improve the mechanical properties of the COPVs by using a low-viscosity resin system that contained a different curing agent. This lower viscosity improves the processing of the COPV, and preliminary results show that the burst pressure of these new vessels is 20 to 25% higher than that of the original. The self-healing concept demonstrated in this research and development effort represents a platform technology, and the self-healing property is neither restricted to the particular epoxy system used here, nor to the COPV application. Self-healing is a direct result of a unique phase separated morphology created via the resin and is aided by the nanoparticles. The self-healing function can be introduced to other customer-specific resin systems in coating, bulk, or composite applications provided that the unique phase separated morphology can be enabled in those systems.

Eberly, Daniel

Crystallization of nanopore-confined imidazolium ionic liquids probed by temperature-resolved in situ grazing-incidence wide angle X-ray scattering (GIWAXS)

The crystallization behavior of ionic liquids (ILs) 1-butyl-3-methylimidazolium [BMIM] hexafluorophosphate [PF 6 ] and chloride [Cl] is investigated upon confinement in 2.3 or 8.2 nm diameter silica nanopore arrays, along with the effects of covalently modifying the pore walls with 1-(3-trimethoxysilylpropyl)3-methylimidazolium [TMS-MIM] + groups. In situ grazing-incidence wide angle x-ray scattering (GIWAXS) is performed during heating from as low as -110 °C to room temperature. Partially ordered “nanodomains” are observed in both ILs in the bulk molten state, but they are disrupted by nanoconfinement. Melting point depression consistent with capillary effects is observed for [BMIM][PF 6 ] in 2.3 nm pores. However, the melting point is elevated for [BMIM][PF 6 ] in 8.2 nm pores, which provide sufficient space to stabilize the crystalline phase. For [BMIM][Cl], crystallization is observed only in 8.2 nm bare silica pores, but the melting point is severely depressed. Tethering with IL-like [TMS-MIM + ] also promotes the crystallization of [BMIM][PF 6 ], resulting in elevated melting points. The combined effects of a larger pore size and pore surface tethering on [BMIM][PF 6 ] result in a single stable crystal phase that persists from -140 °C to 25 °C (vs. the bulk melting point of -11 °C). These results show that when ILs are used in confined systems, complex crystallization behavior can emerge depending on the counterion, pore size, and surface modification that require consideration of ion layering in the confined space in addition to surface free energy effects.

He, Yuxin [University of Kentucky, Lexington, KY (

Concerning Apparent Similarity of Structures of Fluoropolymer Surfaces Exposed to an Argon Plasma or Argon Ion Beam

X-ray photoelectron spectroscopy (XPS) C(sub 1s) spectra of fluoropolymers exposed to either an argon plasma or argon ion beam show remarkable similarity, implying that the surface-modification reactions for these two processes likely proceed through comparable mechanisms, revolving predominantly ion-surface interactions. The importance of working with a monochromatized x-ray source for XPS analysis of the surface-modified fluoropolymers is once again emphasized.

Golub, Morton A.

Toward Lithium Recovery Using Modular (and Membraneless) Phase Separation and Extraction (MPSE) Technology with Ionic Liquid (IL) Solvents: Effect of Coatings

In this work, a single-channel slope-plate Modular and Membrane-less Phase Separation and Extraction (MPSE) device was fabricated using 3D printing. The slope-plate was designed with an insertable glass slide to enable surface modification with coatings. Self-assembled monolayers (SAMs) and perfluoropolyether (Zdol) coatings were applied to tailor surface wettability and enhance phase separation. Using a model biphasic system of water and hexadecane, both coatings significantly improved the separation efficiency compared to the uncoated device by promoting selective wetting. Building on these results, lithium extraction from a simulated saline solution was investigated using 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf₂]) as the ionic liquid (IL) extractant. The IL effectively extracted Li⁺ from the aqueous phase in bulk extraction, demonstrating its potential for lithium recovery. However, the low interfacial tension between the IL and aqueous phases posed challenges for phase separation. The application of SAM and Zdol coatings effectively mitigated this issue. Overall, integrating tailored surface chemistry with the slope-plate MPSE design shows great promise as an efficient and scalable platform for studying liquid–liquid separation and optimizing ionic liquid–based extraction processes for lithium recovery from saline sources.

3D printing

Engineering diamond interfaces free of dark spins

Nitrogen-vacancy (NV) centers in diamond are utilized extensively as quantum sensors for imaging fields at the nanoscale. The ultrahigh sensitivity of NV magnetometers has enabled the detection and spectroscopy of individual electron spins, with potentially far-reaching applications in condensed matter physics, spintronics, and molecular biology. However, the surfaces of these diamond sensors naturally contain electron spins, which create a background signal that can be hard to differentiate from the signal of the target spins. In this study, we develop a surface modification approach that eliminates the unwanted signal of these so-called dark electron spins. Our surface passivation technique, based on coating diamond surfaces with a thin titanium oxide (Ti⁢O 2 ) layer, reduces the dark spin density. The observed reduction in dark spin density aligns with our findings on the electronic structure of the diamond-Ti⁢O 2 interface. The reduction, from a typical value of 2000 μm −2 to a value below that set by the detection limit of our NV sensors (200 μm −2 ), results in a twofold increase in Hahn-echo coherence time of near surface NV centers. Furthermore, we derive a comprehensive spin model that connects dark spin relaxation with NV coherence, providing additional insights into the mechanisms behind the observed spin dynamics. Our findings are directly transferable to other quantum platforms, including nanoscale solid-state qubits and superconducting qubits.

74 ATOMIC AND MOLECULAR PHYSICS

Transfer Casting From Ion-Beam-Textured Surfaces

Textured surfaces created on metals, ceramics, and polymers. Electron-bombardment ion thrustor used as neutralized-ion-beam source. Beam of directed, energetic ions alter surface chemistry and/or morphology of many materials. By adjusting ion energy and ion-beam current density impinging upon target, precise surface modifications obtained without risk of targetmaterial melting or bulk decomposition. Technique developed to generate precise, controllable, surface microstructures on metals, ceramics, and polymers.

Banks, B. A.

Bio-inspired Surface Structures to Mitigate Interfacial Particle Adhesion and Erosion - A Review

Lunar dust known as regolith is a huge challenge for lunar exploration missions. Formed over millennia by a complex process involving impacts of meteoroids and micrometeoroids on the lunar surface, lunar dust is porous, highly abrasive with sharp jagged edges, chemically reactive, electrostatically charged and sometimes magnetic. The chemical composition and thickness of the dust layer also varies in different regions of the lunar surface. From samples obtained by previous lunar missions, the average particle size is below 100 microns. This dust has the tendency to strongly adhere to any exposed surfaces, and often degrades the material functionality to eventually cause failure. Any material on the lunar surface is also subject to harsh temperature cycles ranging from -178 ̊C to + 123 ̊C and extreme ultraviolet radiation. While on the lunar surface, different classes of materials would be required for different applications. Advanced materials have been and will be used throughout the lunar lander, habitat, and mission equipment. Examples include: polymeric materials for astronaut protective clothing; metals and ceramics for the lunar lander legs and habitats, and excavating equipment; and semiconductors for solar panels and on-board electronics. In all these applications, the surfaces of the materials are expected or understood to be exposed to the extreme lunar environment condition that includes the regolith dust. During the Apollo missions, the dust clung to and abraded the astronaut’s suits, degraded seals, optics, clogged sensors and reduced performance of thermal radiators. The lunar dust adheres to the surface by various mechanisms, which include electrostatic and Coulombic interactions, Van-der-Waals forces, magnetic forces, mechanical interlocking, chemical bonding and donor-acceptor interactions. There are three primary strategies for developing technologies to minimize the lunar dust adhesion: active, passive and a combination of active and passive. In the active approach, an external energy is needed to prevent or remove particles from collecting on the surface. Mechanically powered brushes and electrodynamic dust screens are two examples. In the passive approach, no external power is needed, and the material surface properties are able to mitigate dust adhesion. A well-known example of this strategy is the low work function coatings for non-stick surfaces. In most cases a combination of active and passive methods might be needed to optimally manage the lunar regolith. The passive method is significantly more attractive as it does not require any external power or an additional control subsystem. These approaches optimize the mission payload and reduce risk. Surface modification to minimize the dust adhesion is thus very important to lunar missions. Here, naturally evolved surface structures might provide guidance for solutions. There are several factors that have to be considered for minimizing particle adhesion to a surface. These include the substrate material properties, surface topography, chemistry, and the characteristics of the adhering particles. When engineering a surface, the substrate material chosen would be dependent on the needs of the application. Tailoring the surface microstructure or chemistry opens up more possibilities for its optimal utilization

Lunar Dust

Surface and bulk two-level-system losses in lithium niobate acoustic resonators

Lithium niobate (LN) is a promising material for building acoustic resonators used in quantum applications, but its performance is limited by poorly understood material defects called two-level systems (TLSs). Here, in this work, we fabricate high-performance acoustic resonators from LN with quality factors up to 6 ×10 7 and use them to separate bulk and surface contributions to TLS loss. By comparing these bulk acoustic wave (BAW) resonators with previous surface-acoustic-wave and phononic-crystal studies, we show that devices with high surface-participation ratios are limited by surface TLSs, while our BAW devices reveal an intrinsic bulk TLS limit. Through systematic surface treatments and microscopy, we demonstrate that BAW resonator performance remains unchanged despite surface modifications, confirming operation in a bulk-limited regime. Here, our work establishes quantitative bounds on both surface and bulk TLS losses in LN within the context of the material growth and fabrication approaches we have pursued, and it provides guidance for future device engineering and materials development.

acoustic wave phenomena

Tuning the Molecular Structure and Reaction Mechanism of Olefin Metathesis by Model Bilayered Supported MoO x /AlO x /SiO 2 Catalysts

The molecular structure and activity of supported MoO x olefin metathesis catalysts are heavily impacted by the choice of catalyst support. In this study, surface modification of the SiO 2 support with AlO x and selective anchoring of the MoO x on the surface AlO x sites were used to tune the structure, activation, and reactivity of the resulting surface MoO x sites. Extensive in situ molecular characterization, chemical probe studies, and density functional theory (DFT) calculations reveal that the enhanced activity of the supported MoO x /AlO x /SiO 2 catalyst over the MoO x / SiO 2 catalyst is associated with more favorable activation and kinetics of surface MoO x anchored at AlO x sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Polyimides containing pendent siloxane groups

The incorporation of siloxane units into the backbone of aromatic polyimides has been shown to impart certain advantages over the unmodified polyimides. These include enhanced solubility, lower moisture adsorption, lower dielectric constant, improved toughness and surface modification. Also, when exposed to an atomic oxygen environment these materials form an in-situ silicate (SiO2) surface coating which protects the underlying material from further erosion. These unique advantages make polyimide-siloxanes useful in a variety of electronic and aerospace applications. As part of an effort on high performance polymeric materials for potential aerospace applications, polyimides containing pendent siloxane groups are under study. These materials were prepared by reacting a functionalized siloxane compound with polyimides containing benzhydrol groups. Thin films of the polymers exhibited glass transition temperatures ranging from 167 to 235 C. Tensile strengths and moduli measured at 23 C ranged from 11 to 14 ksi and 250 to 450 ksi, respectively. The dielectric constant was lowered substantially from that of the unmodified polyimide.

Connell, John W.

The Ductility of 49Fe-49Co-2V Soft Magnetic Alloy Bar: Surface Effects and Test Methods

The tensile ductility of 49Fe-49Co-2V (Hiperco® 50A) bar was investigated in both as-received and heat-treated conditions. The as-received/machined specimens exhibit very low ductility compared to samples where heat treatment was the final step prior to testing. Microstructural characterization showed that internal residual strain from bar processing and, most importantly, surface machining damage, cause lower elongation in the as-received material. Because fracture of this intermetallic alloy initiates at the surface, it is particularly susceptible to surface machining damage, i.e., the near-surface region has already exhausted most of its ability to accumulate tensile strain. During heat treatment, the internal residual strain and near-surface machining damage are eliminated and ductility is improved, despite a higher degree of crystallographic ordering in the heat-treated condition (which typically lowers ductility). Furthermore, if machining is again performed after heat treatment, the material again exhibits brittle behavior, even with only light touch-up machining passes. Here, in this work, methods of tensile strain measurement were investigated, namely conventional knife-edge extensometry and noncontact digital image correlation (DIC) on heat-treated material. For clip-on knife-edge extensometry, the range of failure strain was 2.5-5.5% for heat-treated Hiperco. For noncontact methods, ductility up to 7% was observed. The results highlight the tendency for the alloy to fail at surface imperfections, even those produced by application of the extensometer itself. Noncontact laser extensometry is recommended for determining the intrinsic ductility of the alloy. A method of laser surface modification was developed which increased ductility by ~ 100% compared to unmodified samples. The high cooling rates achieved during laser surface processing can bypass the ordering reaction and produce a ductile disordered structure at the surface that exhibits ductile fracture characteristics.

EBSD