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At least 1,747 records · Page 97

Metal DiSulfide thin films synthesized by pulsed ion beam ablation: Self-assembled structures with improved mechanical properties in humid conditions

Thin films composed of transition metal dichalcogenides such as molybdenum disulfide (MoS 2 ) or tungsten disulfide (WS 2 ) are well known for their solid lubricating behavior in dry environments such as space, but deteriorate rapidly in environments where oxygen is present. There have been many attempts over recent decades to improve MoS 2 lubricating performance in humid environments by addition of metals such as titanium to the film. The additions have come in the form of co-sputtering with the MoS 2 , or formation of nano multilayer coatings. We have previously reported on the synthesis of MoS 2 films by high-power ion beam ablation [Prasad et al, Matls. Lett. 65 (2010) 4–6]. The resulting films are observed to contain spheres of pure Mo of 10–100 nm size evenly dispersed throughout the ~1 μm-thick film, a form of self-assembly not before seen in films produced by sputtering or by pulsed laser deposition (PLD). The remaining Mosingle bondS matrix was observed to crystalize in situ under frictional contact into MoS 2 with the basal planes orienting themselves in the direction of sliding underneath the wear surface. The present study concerns metal additions in the form of alternating layers with MoS 2 deposited in between from an ablation target. The addition of Ti resulted in the extension of good tribological performance to humid air conditions, but the path to good performance appears to be relatively narrow. The same distributed Mo spheres were present in the new film, and similar self-assembled morphologies when V was substituted for the Ti, and when multilayers were formed of WS 2 with Zr additions. Furthermore, it appears that addition of Ti resulted in improvements in mechanical film strength that contributed to the wear ability in humid conditions.

Intense ion beams↗

Tribocorrosion of stainless steel sliding against graphite in FLiNaK molten salt

The molten salt reactor (MSR) concept recently gained renewed interest in developing Generation IV nuclear reactors. One MSR design uses fluoride molten salts to cool tri-structural isotropic particle fuel encapsulated by a carbon matrix into spherical pebbles, which would inevitably contact the reactor's stainless steel container wall during salt circulation. Characterizing this interaction is crucial for reactor safety. Here, in this work, we report the tribocorrosion behavior of graphite sliding against Type 316H stainless steel lubricated by a FLiNaK (LiF:NaF:KF; 46.5:11.5:42 mol %) molten salt in an argon environment. Accelerated wear loss was observed at a higher temperature because of a lower molten salt viscosity and a higher corrosion rate. The graphite had a more rapid material loss at a higher sliding speed than stainless steel because of its higher vulnerability to vibration-induced microfracture. The salt-starved condition caused more material loss than either the no-salt or the salt-flooded condition because neither a graphite transfer film nor stable boundary lubrication could be established at salt starvation. An interesting dual-layer surface film was discovered on the stainless steel worn surface: a chromium-rich top film and a nickel-accumulated but chromium-depleted interlayer. The film composition and structure provide fundamental insights to the mechanochemical interactions between stainless steel and graphite in a molten salt environment.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Elastohydrodynamics of roll-to-roll UV-cure imprint lithography

Inextensible cylindrical shell theory and lubrication theory combine into a model for the elastohydrodynamics of a rolling-imprint modality of nanoimprint lithography (NIL). Foil-bearing theory describes the formation of the lubrication gap due to relative motion between a tensioned substrate and a rigid, cylindrical surface. Reproduction of the results of foil-bearing theory for both stiff and perfectly-flexible substrates validates this coupled model and reveals a highly predictable region of uniformity that provides low shear stress conditions ideal for UV-cure. Here, these results show theoretical limitations that are used to construct an operating window for predicting rolling-mode NIL process feasibility.

42 ENGINEERING↗

Long-Term Static and Dynamic Corrosion Stability of Nonwetting Surfaces

Superhydrophobic surfaces (SHSs) and lubricant-infused surfaces (LISs) are two classes of nonwetting surfaces that have drawn attention due to their advanced functional properties including corrosion inhibition. Yet there is a conspicuous lack of corrosion study of SHSs and LISs with respect to their fabrication and material parameters, especially at high temperatures and under dynamic flow conditions over long durations, which is sought to be addressed in this article. Considering copper SHSs and LISs, a full factorial combinatorial study of two facile texturing processes, electrodeposition and etching, two different functionalization agents, stearic acid and mercaptan, and two types of infused lubricants, Krytox 104 and DOWSIL 510, is presented, encompassing over 650 measurements on 90 tested surfaces. All fabricated surfaces demonstrated water repellency with a contact angle above 150° and a sliding angle below 7°. For the first time, the study examines high-temperature corrosion stability and long-term corrosion durability of the nonwetting surfaces in both static fluid and dynamic turbulent flow conditions over a period of 30 days. Here, LISs and SHSs are shown to provide excellent corrosion inhibition over all tested corrosion conditions, with negligible presence of corrosion species on the surfaces and no deterioration of the texturing. The surfaces are also shown to rejuvenate easily to the initial wettability and corrosion resistance values. This study provides valuable insights into the selection of materials and processing parameters for the fabrication of nonwetting surfaces for the application of interest.

Copper↗

Interactions of Water with Pristine and Defective MoS 2

Molybdenum disulfide (MoS 2 ) is a lamellar solid lubricant often used in aerospace applications because of its extremely low friction coefficient (~0.01) in inert environments. The lubrication performance of MoS 2 is significantly impaired by exposure to even small amounts of water and oxygen, and the mechanisms behind this remain poorly understood. Here we use density functional theory calculations to study the binding of water on MoS 2 sheets with and without defects. In general, we find that pristine MoS 2 is slightly hydrophilic but that defects greatly increase the binding affinity for water. Intercalated water disrupts the crystal structure of bulk MoS 2 due to the limited space between lamellae (~3.4 Å), and this leads to generally unfavorable adsorption, except in the cases where water molecules are located on the sites of sulfur vacancies. We also find that water adsorption is more favorable directly below a surface layer of MoS 2 compared to in the bulk.

36 MATERIALS SCIENCE↗

Electrodeposited Mo x S y O z /Ni Tribological Coatings

Deposition of molybdenum disulfide (MoS 2 ) coatings using physical vapor deposition (PVD) and mechanical burnishing has been widely assessed for solid lubricants in space applications but still suffers from line-of-sight constraints on complex geometries. Here, we highlight one of the first demonstrations of electrodeposited Mo x S y O z and Mo x S y O z /Ni thin-film coatings from aqueous solutions of ammonium tetrathiomolybdate for solid lubricant applications and their remarkable ability to provide low coefficients of friction and high wear resistance. Characterization of the coating morphology shows amorphous microstructures with a high oxygen content and cracking upon drying. Even so, electrodeposited Mo x S y O z can achieve low steady-state coefficients of friction (μ ∼ 0.05–0.06) and wear rates (2.6 × 10 –7 mm 3 /(N m)) approaching those of physical vapor deposited coatings (2.3 × 10 –7 mm 3 /(N m)). Additionally, we show that adding dopants such as nickel increased the wear rate (7.5 × 10 –7 mm 3 /(N m)) and initial coefficient of friction (μ i = 0.23) due to compositional modifications such as dramatic sub-stoichiometry (S/Mo ∼ 1) and expression of a NiO x surface layer, although doping did reduce the degree of cracking upon drying.

Babuska, Tomas F.↗

Influence of Surface Morphology on the Shear-Induced Wear of Alkylsilane Monolayers: Molecular Dynamics Study

Chemisorbed alkylsilane monolayer coatings have been shown to possess favorable lubrication properties; however, film degradation prevents the widespread use of these materials as lubricants in micro- and nanoelectromechanical systems (MEMS/NEMS). In this work, molecular dynamics (MD) simulations are used to provide insight into the conditions that promote the degradation and wear of these materials. This is achieved through removal of interfacial chain-substrate bonds during shear and the examination of the mobility of the resulting free, unbound chains. Specific focus is given to the effects of surface morphology, which has been shown previously to strongly influence frictional forces in monolayer systems. In-plane order of chain attachments is shown to lead to pressure-induced orientational ordering of monolayers, promoting film stability. This behavior is lost as nonideality is introduced into the substrate and chain patterning on the surface becomes disordered. The presence of surface roughness is found to reduce film stability, with localization of wear observed for chain attachment sites nearest the interface of contact. Furthermore, the influence of substrate nonideality on monolayer degradation is shown to diminish as chain length is increased.

99 GENERAL AND MISCELLANEOUS↗

Investigating Alkylsilane Monolayer Tribology at a Single-Asperity Contact with Molecular Dynamics Simulation

Chemisorbed monolayer films are known to possess favorable characteristics for nanoscale lubrication of micro- and nanoelectromechanical systems (MEMS/NEMS). Prior studies have shown that the friction observed for monolayer-coated surfaces features a strong dependence on the geometry of contact. Specifically, tip-like geometries have been shown to penetrate into monolayer films, inducing defects in the monolayer chains and leading to plowing mechanisms during shear, which result in higher coefficients of friction (COF) than those observed for planar geometries. In this work, we use molecular dynamics simulations to examine the tribology of model silica single-asperity contacts under shear with monolayer-coated substrates featuring various film densities. It is observed that lower monolayer densities lead to reduced COFs, in contrast to results for planar systems where COF is found to be nearly independent of monolayer density. This is attributed to a liquid-like response to shear, whereby fewer defects are imparted in monolayer chains from the asperity, and chains are easily displaced by the tip as a result of the higher free volume. This transition in the mechanism of molecular plowing suggests that liquid-like films should provide favorable lubrication at single-asperity contacts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tribochemical Conversion of Methane to Graphene and Other Carbon Nanostructures: Implications for Friction and Wear

Tribochemistry involves chemical reactions occurring at sliding contact interfaces in the presence of gaseous and/or liquid media. It often leads to the formation of a solid reaction film (also termed boundary film) which controls friction and wear and hence the efficiency and reliability of moving mechanical systems (such as engines). Here we demonstrate tribochemical conversion of methane to graphene, nano-onion, and disordered carbons on the sliding surfaces of Ni-, Cu-, and CuNi-containing VN coatings at atmospheric pressure and room temperature, providing 2-3 orders of magnitude reduction in wear and similar to 50% reduction in friction compared to those of the uncoated steels. Transmission electron microscopy confirms that graphene forms preferably on metal rich nanoclusters of the composite coatings, while the carbon nano-onions are scattered throughout the carbon tribofilm. Ab initio molecular dynamics simulations elucidate underlying mechanisms involved in the tribochemical conversion of methane to carbon- based nanostructures in support of microscopic observations. These scientific findings may lead to new materials technologies that can use methane as a source for continuous and in situ lubrication. For example, there is an urgent need to curtail the uses of lubricating oils in natural gas compressors and engines as they contaminate the natural gas being compressed or burnt.

36 MATERIALS SCIENCE↗

Techno-Economic and Life Cycle Assessment of Chemical Recycling and Upcycling of Mixed Plastics Waste Containing Poly-vinyl-chloride

Developing technologies that completely remove chlorine from plastic waste can allow its chemical recycling and upcycling with catalytic methods. Here, this study compares eight processes involving different dechlorination methods (absorption columns, adsorption in beds of zeolites, catalytic dechlorination, and dissolution in ionic liquids) and chemical conversion technologies (incineration, pyrolysis, hydrogenolysis) to upgrade mixed plastics waste to various products (e.g., electricity, fuels, virgin polymers, and lubricant oil). The analysis determines that the absorption of chlorine in columns with basic aqueous solutions is limited to plastics waste with PVC concentrations below 0.1%. Dissolution in ionic liquids is not cost-competitive. On the contrary, two-step processes with catalytic dechlorination followed by thermochemical catalytic depolymerization, either pyrolysis or hydrogenolysis, significantly improve process economics and emissions. The most economically viable alternative is hydrogenolysis for producing lubricants, while the technology with the lowest global warming potential is chemical recycling via catalytic pyrolysis.

circular economy↗

Mobile Interfaces: Liquids as a Perfect Structural Material for Multifunctional, Antifouling Surfaces

Life creates some of its most robust, extreme surface materials not from solids but from liquids: a purely liquid interface, stabilized by underlying nanotexture, makes carnivorous plant leaves ultraslippery, the eye optically perfect and dirt-resistant, our knees lubricated and pressure-tolerant, and insect feet reversibly adhesive and shape-adaptive. Novel liquid surfaces based on this idea have recently been shown to display unprecedented omniphobic, self-healing, anti-ice, antifouling, optical, and adaptive properties. In this Perspective, we present a framework and a path forward for developing and designing such liquid surfaces into sophisticated, versatile multifunctional materials. Drawing on concepts from solid materials design and fluid dynamics, we outline how the continuous dynamics, responsiveness, and multiscale patternability of a liquid surface layer can be harnessed to create a wide range of unique, active interfacial functions able to operate in harsh, changing environments not achievable with static solids. We discuss how, in partnership with the underlying substrate, the liquid surface can be programmed to adaptively and reversibly reconfigure from a defect-free, molecularly smooth, transparent interface through a range of finely tuned liquid topographies in response to environmental stimuli. With nearly unlimited design possibilities and unmatched interfacial properties, liquid materials as long-term stable interfaces yet in their fully liquid state may potentially transform surface design everywhere from medicine to architecture to energy infrastructure.

Grinthal, A↗

A two-stage strategy for upcycling chlorine-contaminated plastic waste

Abstract Chemical upcycling of polyolefin plastic waste to lubricant, wax and fuel-range hydrocarbons over metal-based catalysts is a crucial technological solution to the enormous environmental threat posed by plastic waste. However, currently available methods are incompatible with chlorine-contaminated feedstocks. Here we report a two-stage strategy for upcycling chlorine-contaminated polypropylene. First, magnesia–alumina mixed oxide at 30 bar H 2 and 250 °C serves as a chlorine trap by rapidly forming solid chloride, resulting in nearly complete chlorine extraction from the polyolefin melt. This enables the upcycling of plastic waste with up to 10% polyvinyl chloride content to lubricants over ruthenium-based catalysts, in the second stage. The strategy is also applicable to chlorinated aromatics and alkanes. The proposed strategy renders hydrocracking and hydrogenolysis catalysts less sensitive to the chlorine impurities in feedstocks while eliminating HCl emissions and chlorine contamination in products. It could incentivize further progress in plastics upcycling.

Environmental Sciences & Ecology↗

Optimization of esterification of oleic acid and trimethylolpropane (TMP) and pentaerythritol (PE)

Vegetable oil (VO) is the most potential alternative to replace mineral oil for lubricant due to better lubricating properties and great physicochemical properties. Chemical modification has to be done to overcome low temperature performance and low oxidation instability due to the presence of β-hydrogen atoms of glycerol molecule. The optimization of esterification of oleic acid and polyhydric alcohol with sulfuric acid catalyst was carried out to find the optimum conditions with the highest yield. Reeaction variables such as; molar ratio, temperature, duration and catalyst concentration. Two types of polyhydric alcohol have been used; TMP and PE. The optimum results showed oleic acid successfully converted 91.2% ester TMP and 92.7% ester PE at duration: 5 hours (Ester TMP), 6 hours (Ester PE); temperature: 150°C (ester TMP), 180°C (Ester PE); catalyst concentration: 1.5% (w/w); and mol ratio: 3.9:1 (ester TMP), 4.9:1 (ester PE). From the data obtained, mole ratio showed most influenced factors to the increasing yields of ester conversions.. The TMP/PE ester was confirmed using gas chromatography (GC-FID), Fourier Transform Infrared Spectroscopy (FTIR) and Nuclear Magnetic Resonance (NMR)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and dynamics of hydrodynamically interacting finite-size Brownian particles in a spherical cavity: Spheres and cylinders

The structure and dynamics of confined suspensions of particles of arbitrary shape are of interest in multiple disciplines from biology to engineering. Theoretical studies are often limited by the complexity of long-range particle-particle and particle-wall forces, including many-body fluctuating hydrodynamic interactions. Here, we report a computational study on the diffusion of spherical and cylindrical particles confined in a spherical cavity. We rely on an immersed-boundary general geometry Ewald-like method to capture lubrication and long-range hydrodynamics and include appropriate non-slip conditions at the confining walls. A Chebyshev polynomial approximation is used to satisfy the fluctuation-dissipation theorem for the Brownian suspension. We explore how lubrication, long-range hydrodynamics, particle volume fraction, and shape affect the equilibrium structure and the diffusion of the particles. It is found that once the particle volume fraction is greater than 10%, the particles start to form layered aggregates that greatly influence particle dynamics. Hydrodynamic interactions strongly influence the particle diffusion by inducing spatially dependent short-time diffusion coefficients, stronger wall effects on the particle diffusion toward the walls, and a sub-diffusive regime-caused by crowding-in the long-time particle mobility. The level of asymmetry of the cylindrical particles considered here is enough to induce an orientational order in the layered structure, decreasing the diffusion rate and facilitating a transition to the crowded mobility regime at low particle concentrations. Our results offer fundamental insights into the diffusion and distribution of globular and fibrillar proteins inside cells.

36 MATERIALS SCIENCE↗

Investigations in the tape-to-tape contact resistance and contact composition in superconducting CORC ® wires

Conductor on Round Core (CORC®) wires and cables, constructed from multiple layers of helically wound REBa 2 Cu 3 O 7–δ tapes, are a promising cable technology for high field magnet applications. An important feature of high-temperature superconductor cables is the ability to share current between conductors, allowing current to bypass drops in I c and minimizing the risk of hot spot formation, which could lead to potential burnout in the superconductor. In contrast to stacked-tape cables, which have continuous contact between tapes, in CORC® the transfer points occur at discrete tape crossovers. The tape-to-tape contact resistance, R c , plays a critical role in the current sharing capabilities and current distribution in cables. For the work reported here, special CORC® wires were manufactured using different winding parameters to investigate variations in R c . Variations comprised inclusion of a lubricant, different lubricant conductivity, inclusion of pre-tinning, and heating briefly to melt the solder. Cables were first tested as straight lengths, followed by bending to a 10 cm diameter. In straight cables R c values ranged from 1 to over 1000 μΩ cm 2 , depending on cabling parameters, with the highest values being found for cables made by the present 'standard' process. Bending the cables to a 10 cm diameter decreased R c by a factor 2–5. Tinning with PbSn decreased R c by three orders of magnitude compared to standard CORC® wires, and heat treating wires with tinned conductor resulted in only a small further decrease in R c . Based on the measured R c at an electric field of 1 μV cm –1 the resulting current transfer length between layers can range from a few millimeters to a tens of centimeters. Examination of contacts with a laser confocal microscope showed plastic deformation of the copper at the edges of the contact overlap area, apparently caused by thicker plating at tape edges digging into the copper of neighboring layers. These images reveal that only a fraction of the total contact surface may actually be touching when there is nothing to compensate for height differential. Images of the PbSn coated tapes indicated that application of solder produces a much more uniform contact surface and higher contact area. Furthermore, imaging of CORC® cross-sections confirmed that in the non-tinned cables there are many regions where tapes are not in contact, while in contrast the PbSn cable shows significantly more contact between the tapes. These different imaging techniques reveal that tape surface morphology is a significant parameter in determining R c .

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

The surface stress of biomedical silicones is a stimulant of cellular response

Silicones are commonly used for lubrication of syringes, encapsulation of medical devices, and fabrication of surgical implants. While silicones are generally viewed as relatively inert to the cellular milieu, they can mediate a variety of inflammatory responses and other deleterious effects, but the mechanisms underlying the bioactivity of silicones remain unresolved. Here, we report that silicone liquids and gels have high surface stresses that can strongly resist deformation at cellular length scales. Biomedical silicones, including syringe lubricants and fillings from FDA-approved breast implants, readily adsorb matrix proteins and activate canonical rigidity sensing pathways through their surface stresses. In 3D culture models, liquid silicone droplets support robust cellular adhesion and the formation of multinucleated monocyte-derived cell masses that recapitulate phenotypic aspects of granuloma formation in the foreign body response. Together, our findings implicate surface stress as a cellular stimulant that should be considered in application of silicones for biomedical purposes.

60 APPLIED LIFE SCIENCES↗

RESULTS OF ACCELERATED LIFE TESTING OF LCLS-II CAVITY TUNER MOTOR

An Accelerated Life Test (ALT) of the Phytron stepper motor used in the LCLS-II cavity tuner has been conducted at JLab. Since the motor will reside inside the cryomodule, any failure would lead to a very costly and arduous repair. As such, the motor was tested for the equivalent of 30 lifetimes before being approved for use in the production cryomodules. The 9-cell LCLS-II cavity is simulated by disc springs with an equivalent spring constant. Plots of the motor position vs. tuner position ' measured via an installed linear variable differential transformer (LVDT) ' are used to measure motor motion. The titanium spindle was inspected for loss of lubrication. The motor passed the ALT, and is set to be installed in the LCLS-II cryomodules.

Huque, Naeem↗

Sandy Soil Microaggregates: Rethinking Our Understanding of Hydraulic Function

Core Ideas Sandy soil microaggregates are comprised of a solid sand core encrusted with fines. Thick films control a significant proportion of water retention in coarse sandy soil. Three water pools drain sequentially: capillary water, thick films, and adsorptive films. Film seepage rates should be considered when irrigating sandy soil. This study investigated the peculiar structure of microaggregates in coarse sandy soils that exhibit only external porosity and investigated their control on soil hydrology. The microstructure underpins a hydrologic existence that differs from finer textured soils where aggregates have internal porosity. Understanding the impact of these microaggregates on soil hydrology will permit improved agricultural irrigation management and estimates associated with ecosystem capacity and resiliency. Microstructure was investigated using a digital microscope, and aspects of the structure were quantified by sedimentation and computed microtomography. Sandy soil microaggregates were observed to be comprised of a solid sand‐grain core that is coated with fines, presumably cemented by organic media. This microstructure leads to three distinct water pools during drainage: capillary water, followed by thick films (1–20 μm) enveloping the outer surfaces of the crusted microaggregates, followed by adsorbed thin films (<1 μm). The characteristics of the thick films were investigated using an analytical model. These films may provide as much as 10 to 40% saturation in the range of plant‐available water. Using lubrication theory, it was predicted that thick film drainage follows a power law function with an exponent of 2. Thick films may also have a role in the geochemical evolution of soils and in ecosystem function because they provide contiguous water and gas phases at relatively high moisture contents. And, because the rough outer crust of these microaggregates can provide good niches for microbial activity, biofilm physics will dominate thick film processes, and consequently hydrologic, biologic, and geochemical functions for coarse sandy soils.

Paradiś, Ashley↗