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At least 343 records · Page 19

Ultrathin VO 2 Films on Functional Substrates

The metal–insulator transition (MIT) in vanadium dioxide (VO 2 ) thin films is strongly affected by grain size, thickness, and interfacial properties. Typically, a minimum thickness around 50 nm is required for VO 2 to exhibit a significant MIT when functional substrates like sapphire and silicon are used. Several works have shown that thin films below 20 nm, with up to 2–3 decades of change in the resistance across the MIT, can be achieved but require complex pre- or postprocessing of the samples. We show that predeposition substrate condition control facilitates the direct growth of VO 2 ultrathin 15 nm films, exhibiting a resistance change between 3 and 4 decades across the MIT. Our findings indicate that the interface between the film and the substrate is crucial in determining the initial growth layers and the structural evolution. With appropriate substrate surface treatment, the desired VO 2 MIT can be enhanced regardless of the substrate crystallographic orientation. Moreover, we propose a novel approach to obtain large resistance changes across the MIT in ultrathin VO 2 films by incorporating a predeposited 1.5 nm vanadium oxide buffer layer, thereby eliminating the need to use different materials or complex pre- or postprocessing of the samples. Here we also demonstrate that this method improves the transition of 25–50 nm VO 2 thin films on silicon substrates. Our study reveals a simple approach for direct growth of ultrathin VO 2 films exhibiting a significant MIT, which is commonly accepted unattainable over substrates of technological importance, such as sapphire and silicon.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A constant heat flux model of the evaporating interline region

An approximate procedure is developed for determining the heat sink capability of an interline region (junction of vapor, evaporating thin film, and nonevaporating thin film), with consideration of the effect of resistance of the solid to heat transfer. The formulation is based on a simple one-dimensional constant heat flux model. The solution is directed toward a limiting case in which the thermal conductance of the solid is controlling. Since the value of the ideal liquid-vapor interfacial heat transfer coefficient is very large, conductance of the solid is found to dominate the overall heat transfer coefficient in the interline region after a small increase in film thickness.

Wayner, P. C., Jr.↗

Brazing of Stainless Steels to Yttria Stabilized Zirconia (YSZ) Using Silver -Base Brazes

Three silver-base brazes containing either noble metal palladium (Palcusil-10 and Palcusil-15) or active metal titanium (Ticusil) were evaluated for high-temperature oxidation resistance, and their effectiveness in joining yttria stabilized zirconia (YSZ) to a corrosion-resistant ferritic stainless steel. Thermogravimetric analysis (TGA), and optical- and scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS) were used to evaluate the braze oxidation behavior and the structure and chemistry of the YSZ/braze/steel joints. The effect of the braze type and processing conditions on the interfacial microstructure and composition of the joint regions is discussed with reference to the chemical changes that occur at the interface. It was found that chemical interdiffusion of the constituents of YSZ, steel and the brazes led to compositional changes and/or interface reconstruction, and metallurgically sound joints.

Singh, Mrityunjay↗

Spin Rectification and Electrically Controlled Spin Transport in Molecular-Ferroelectrics-Based Spin Valves

We report a spin-rectification effect in a spin-valve structure consisting of ferroelectric croconic acid (C 5 H 2 O 5 ) sandwiched between ferromagnetic electrodes La 0.7 Sr 0.3 MnO 3 and Co, which can be switched between a high-resistance (off ) and a low-resistance (on) state by a poling voltage. In the off state, the magnetoresistance (MR) sign reverses with the measurement voltage with a 0.1-V offset, suggesting a spin-rectification behavior, while in the on state the MR remains negative. These observations can be understood in terms of electrically controlled interfacial energy-band alignment either from the electrostatic effect or from the interfacial redox process. In conclusion, the observed spin-rectification effect suggests thepossibility of diodelike devices for spin-polarized current.

36 MATERIALS SCIENCE↗

Adverse Effects of Trace Non-polar Binder on Ion Transport in Free-standing Sulfide Solid Electrolyte Separators

Sulfide solid-state electrolyte (SE) possesses high room-temperature ionic conductivity. However, fabrication of the free-standing, sheet-type thin sulfide SE film electrolyte to enable all-solid-state batteries to deliver high energy and power density remains challenging. Herein we show that argyrodite sulfide (Li 6 PS 5 Cl) SE can be slurry cast to form free-standing films with low (≤5 wt%) loadings of poly(isobutylene) (PIB) binder. Two factors contribute to a lower areal specific resistance (ASR) of the thin film SEs benchmarked to the pristine powder pellet SSE counterparts: i) 1–2 orders reduced thickness and ii) reasonably comparable ionic conductivity at room temperature after the isostatic pressing process. Nevertheless, an increasing polymer binder loading inevitably introduced voids in the thin film SEs, compromising anode/electrolyte interfacial ion transport. Our findings highlight that electrolyte/electrode interfacial stability, as well as the selection of slurry components, including sulfide SE, binder, and solvent, play essential roles in thin film sulfide electrolyte development.

25 ENERGY STORAGE↗

Liquid crystal polyester-carbon fiber composites

Liquid crystal polymers (LCP) have been developed as a thermoplastic matrix for high performance composites. A successful melt impregnation method has been developed which results in the production of continuous carbon fiber (CF) reinforced LCP prepreg tape. Subsequent layup and molding of prepreg into laminates has yielded composites of good quality. Tensile and flexural properties of LCP/CF composites are comparable to those of epoxy/CF composites. The LCP/CF composites have better impact resistance than the latter, although epoxy/CF composites possess superior compression and shear strength. The LCP/CF composites have good property retention until 200 F (67 % of room temperature value). Above 200 F, mechanical properties decrease significantly. Experimental results indicate that the poor compression and shear strength may be due to the poor interfacial adhesion between the matrix and carbon fiber as adequate toughness of the LCP matrix. Low mechanical property retention at high temperatures may be attributable to the low beta-transition temperature (around 80 C) of the LCP matrix material.

Chung, T. S.↗

Surviving nanoscale interfacial stability in extreme thermal expansion contrast Zn(CN) 2 -epoxy resin matrix composites

Here, we report the remarkable stability at the nanoscale matrix-filler interface in a series of overall low coefficient of thermal expansion (CTE) zinc cyanide (ZC)/epoxy resin composites. These interfaces demonstrate the stability of highly contrasting materials. These composites are designed to optimize the properties of both materials: epoxy resins are valued for their high strength, superb chemical resistance, low dielectric properties, and adhesive abilities. ZC, a model flexible framework, exhibits negative thermal expansion (NTE) behavior and compensates for the epoxy resin’s detrimentally large thermal expansion values. Filled resins minimize the native 65 ppm/°C CTE values to 19 ppm/° C over a wide temperature range while maintaining linearity, yielding composites compatible with typical metal and ceramic substrates’—commonly bonded to the resin— 0–20 ppm/° C CTE values. Additionally, with significant intrinsic differences in the materials, we use wide-angle X-ray diffraction and atomic force microscopy to elucidate thermal movement. The ZC/epoxy interface is surprisingly resilient over 1,000 cycles between -55° C and 75° C, extremes typical to aerospace applications. Further, we show that the resin viscosity remains less than 21 Pa*s at up to 30 vol% ZC, an important consideration for workability. We also discuss settling distribution, glass transition temperature, flexural strength, and longevity. All results point favorably towards practical implementation in low thermal expansion application needs: filling the gap in component design.

42 ENGINEERING↗

Thermally Insulating, Thermal Shock Resistant Calcium Aluminate Phosphate Cement Composites for Reservoir Thermal Energy Storage

This paper presents the use of hydrophobic silica aerogel (HSA) and hydrophilic fly ash cenosphere (FCS) aggregates for improvements in the thermal insulating and mechanical properties of 100- and 250 °C-autoclaved calcium aluminate phosphate (CaP) cement composites reinforced with micro-glass (MGF) and micro-carbon (MCF) fibers for deployment in medium- (100 °C) and high-temperature (250 °C) reservoir thermal energy storage systems. The following six factors were assessed: (1) Hydrothermal stability of HSA; (2) Pozzolanic activity of the two aggregates and MGF in an alkali cement environment; (3) CaP cement slurry heat release during hydration and chemical reactions; (4) Composite phase compositions and phase transitions; (5) Mechanical behavior; (6) Thermal shock (TS) resistance at temperature gradients of 150 and 225 °C. The results showed that hydrophobic trimethylsilyl groups in trimethylsiloxy-linked silica aerogel structure were susceptible to hydrothermal degradation at 250 °C. This degradation was followed by pozzolanic reactions (PR) of HSA, its dissolution, and the formation of a porous microstructure that caused a major loss in the compressive strength of the composites at 250 °C. The pozzolanic activities of FCS and MGF were moderate, and they offered improved interfacial bonding at cement-FCS and cement-MGF joints through a bridging effect by PR products. Despite the PR of MGF, both MGF and MCF played an essential role in minimizing the considerable losses in compressive strength, particularly in toughness, engendered by incorporating weak HSA. As a result, a FCS/HSA ratio of 90/10 in the CaP composite system was identified as the most effective hybrid insulating aggregate composition, with a persistent compressive strength of more than 7 MPa after three TS tests at a 150 °C temperature gradient. This composite displayed thermal conductivity of 0.28 and 0.35 W/mK after TS with 225 and 150 °C thermal gradients, respectively. These values, below the TC of water (TC water = 0.6 W/mK), were measured under water-saturated conditions for applications in underground reservoirs. However, considering the hydrothermal disintegration of HSA at 250 °C, these CaP composites have potential applications for use in thermally insulating, thermal shock-resistant well cement in a mid-temperature range (100 to 175 °C) reservoir thermal energy storage system.

58 GEOSCIENCES↗

Utilizing the unique charge extraction properties of antimony tin oxide nanoparticles for efficient and stable organic photovoltaics

Simultaneously enhancing device performance and longevity, as well as balancing the requirements on cost, scalability, and simplification of processing, is the goal of interface engineering of organic solar cells (OSCs). In our work, we strategically introduce antimony (Sb 3+ ) cations into an efficient and generic n-type SnO 2 nanoparticles (NPs) host during the scalable flame spray pyrolysis synthesis. Accordingly, a significant switch of conduction property from an n-type character to a p-type character is observed, with a corresponding shift in the work function (WF) from 4.01 ± 0.02 eV for pristine SnO 2 NPs to 5.28 ± 0.02 eV for SnO 2 NPs with 20 mol. % Sb content (ATO). Both pristine SnO 2 and ATO NPs with fine-tuned optoelectronic properties exhibit remarkable charge carrier extraction properties, excellent UV resistance and photo-stability being compatible with various state-of-the-art OSCs systems. The reliable and scalable pristine SnO 2 and ATO NPs processed by doctor-blading in air demand no complex post-treatment. Our work offers a simple but unique approach to accelerate the development of advanced interfacial materials, which could circumvent the major existing interfacial problems in solution-processed OSCs.

14 SOLAR ENERGY↗

Theory and Simulation of Metal–Insulator–Semiconductor (MIS) Photoelectrodes

A metal–insulator–semiconductor (MIS) structure is an attractive photoelectrode-catalyst architecture for promoting photoelectrochemical reactions, such as the formation of H 2 by proton reduction. The metal catalyzes the generation of H 2 using electrons generated by photon absorption and charge separation in the semiconductor. The insulator layer between the metal and the semiconductor protects the latter element from photo-corrosion and, also, significantly impacts the photovoltage at the metal surface. Understanding how the insulator layer determines the photovoltage and what properties lead to high photovoltages is critical to the development of MIS structures for solar-to-chemical energy conversion. Herein, we present a continuum model for charge-carrier transport from the semiconductor to the metal with an emphasis on mechanisms of charge transport across the insulator. The polarization curves and photovoltages predicted by this model for a Pt/HfO 2 /p-Si MIS structure at different HfO 2 thicknesses agree well with experimentally measured data. The simulations reveal how insulator properties (i.e., thickness and band structure) affect band bending near the semiconductor/insulator interface and how tuning them can lead to operation closer to the maximally attainable photovoltage, the flat-band potential. This phenomenon is understood by considering the change in tunneling resistance with insulator properties. The model shows that the best MIS performance is attained with highly symmetric semiconductor/insulator band offsets (e.g., BeO, MgO, SiO 2 , HfO 2 , or ZrO 2 deposited on Si) and a low to moderate insulator thickness (e.g., between 0.8 and 1.5 nm). Beyond 1.5 nm, the density of filled interfacial trap sites is high and significantly limits the photovoltage and the solar-to-chemical conversion rate. These conclusions are true for photocathodes and photoanodes. This understanding provides critical insight into the phenomena enhancing and limiting photoelectrode performance and how this phenomenon is influenced by insulator properties. The study gives guidance toward the development of next-generation insulators for MIS structures that achieve high performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Review of Thermal Contact Resistance of Flexible Graphite Materials for Thermal Interfaces in High Heat Flux Applications

In this report the data is reviewed on thermal contact conductance (TCC) and/or thermal contact resistance (TCR) at material interfaces which employs flexible graphite (FG) materials as thermal interface materials (TIM). FG materials are often used as TIM due to their conforming nature. While the overall TCR can be estimated straightforward from measured data, the interface TCR is much more difficult to obtain. The report also discusses the interfacial thermal contact conductance between FG-tungsten and FG-Glidcop-Al15, which are envisioned for high-heat flux applications.

36 MATERIALS SCIENCE↗

An XPS study of the adherence of refractory carbide, silicide, and boride RF-sputtered wear-resistant coatings

Radio frequency sputtering was used to deposit refractory carbide, silicide, and boride coatings on 440-C steel substrates. Both sputter etched and pre-oxidized substrates were used and the films were deposited with and without a substrate bias. The composition of the coatings was determined as a function of depth by X-ray photoelectron spectroscopy combined with argon ion etching. Friction and wear tests were conducted to evaluate coating adherence. In the interfacial region there was evidence that bias may produce a graded interface for some compounds. Biasing, while generally improving bulk film stoichiometry, can adversely affect adherence by removing interfacial oxide layers. Oxides of all film constituents except carbon and iron were present in all cases but the iron oxide coverage was only complete on the preoxidized substrates. The film and iron oxides were mixed in the MoSi2 and Mo2C films but layered in the Mo2B5 films. In the case of mixed oxides, preoxidation enhanced film adherence. In the layered case it did not.

Brainard, W. A.↗

Multiscale Modeling of Grain Boundaries in ZrB2: Structure, Energetics, and Thermal Resistance

A combination of ab initio, atomistic and finite element methods (FEM) were used to investigate the structures, energetics and lattice thermal conductance of grain boundaries for the ultra high temperature ceramic ZrB2. Atomic models of idealized boundaries were relaxed using density functional theory. Information about bonding across the interfaces was determined from the electron localization function. The Kapitza conductance of larger scale versions of the boundary models were computed using non-equilibrium molecular dynamics. The interfacial thermal parameters together with single crystal thermal conductivities were used as parameters in microstructural computations. FEM meshes were constructed on top of microstructural images. From these computations, the effective thermal conductivity of the polycrystalline structure was determined.

Lawson, John W.↗

Rheo–Electric Foundations and Engineering of Carbon Slurry Flow Electrodes

Flowable carbon slurry electrodes promise continuous, scalable electrochemical desalination and energy storage when their rheology (flow and stability) and electronic connectivity are jointly optimized. This report integrates six complementary thrusts that we executed under the Laboratory Directed Research and Development (LDRD) project: (i) a fast, ex situ, centrifuge-compatible method to quantify pellet (packed slurry) electronic conductivity, with a validated cell constant (“shape factor”) and quantitative structure–property insights for carbon mixtures; (ii) a controlled circulation study showing that peristaltic pumping can irreversibly alter particle size and morphology over laboratory-relevant durations; (iii) development of a miniature jet pump that preserves particle integrity while achieving entrainment ratios of 2–4 at practical flow rates; (iv) a comprehensive mapping of how a representative non-ionic surfactant (Tween 20) collapses the carbon gel network, separating network-percolation losses from intrinsic particle contact resistance; (v) in-situ visualization revealing how gravitational settling and flow-driven mixing compete to control charge transport, with dynamic bed layers preventing saturation while achieving 30-fold local concentration enhancement; and (vi) a simple, widely adoptable fabrication route to structured, gas-nitrided titanium nitride (TiN) titanium current collectors that dramatically lower interfacial losses and enable geometry-driven performance gains. Together, these results provide a coherent toolchain and design rules to accelerate formulation screening, de-risk device prototyping, and standardize characterization for carbon slurry electrodes in flow-electrode capacitive deionization (FCDI), electrochemical flow capacitor (EFC), and related systems.

25 ENERGY STORAGE↗

Effect of Environmental Exposures on Fatigue Life of P/M Disk Superalloys

As the temperature capability of Ni-base superalloy powder metallurgy disks is steadily increased, environmental resistance and protection of advanced nickel-based turbine disk components are becoming increasingly important. Localized surface hot corrosion attack and damage from oxidation have been shown to impair disk fatigue life and may eventually limit disk operating temperatures. NASA Research Announcement (NRA) contracts have been awarded to GE Aviation and Honeywell Aerospace to separately develop fatigue resistant metallic and ceramic coatings for corrosion resistance and the corrosion/fatigue results of selected coatings will be presented. The microstructural response of a bare ME3 disk superalloy has been evaluated for moderate (704 C) and aggressive (760-816 C) oxidizing exposures up to 2,020 hours. Cross section analysis reveals sub-surface damage (significant for aggressive exposures) that consists of Al2O3 "fingers", interfacial voids, a recrystallized precipitate-free layer and GB carbide dissolution. The effects of a Nichrome corrosion coating on this microstructural response will also be presented.

Draper, Susan↗

Microsample Characterization of Coatings for GRCop-84 for High Temperature High Heat Flux Application

NASA's Glenn Research Center has developed GRCop-84 (Cu-8at.%Cr-4% Nb), a high conductivity, high strength copper alloy for use as liners in rocket engine combustion chambers, nozzle ramps and other actively-cooled components subject to high heat fluxes. Two metallic coatings, NiCrAlY and Cu-26%Cr, are being considered for preventing blanching, reducing 'dog- house' failures and providing better environmental resistance to the GRCop-84 liners. This presentation will outline a study of coating-substrate interactions that occur as a result of thermal cycling and coating specific properties at different temperatures. A furnace has been built to thermally cycle the samples under argon. The microsample testing approach is being used to measure the coating-substrate interfacial strength. Cu-26Cr/GRCop-84 samples did not show any obvious interdiffusion after 300 thermal cycles. Interfacial strength tests of these samples were affected by porosity present in the samples. A complete set of observations and results for Cu-26Cr and NiCrAlY coatings will be presented.

Jain, Piyush↗

Time- and strain-dependent nanoscale structural degradation in phase change epitaxial strontium ferrite films

Topotactic phase transition between metallic, perovskite SrFeO 3 and insulating, Brownmillerite SrFeO 2.5 has been extensively studied due to the potential applications in resistive switching devices for neuromorphic computing. However, its practical utilization as memristors has been hindered by the structural instability of SrFeO 3 , which is often ascribed to the generation of oxygen vacancies to form SrFeO 3-δ . Here we reveal the dominating defects generated in SrFeO 3 epitaxial thin films are atomic scale gaps as a result of interfacial strain. Our correlated time- and strain-dependent measurements show that tensile strained SrFeO 3 films form vertical, nanoscale gaps that are SrO-rich, which are accountable for the observed metal-to-insulator transition over time. While compressively strained or small lattice mismatched SrFeO 3 films mainly yield horizontal gaps with a smaller impact on the in-plane transport. The atomic scale origin of such defects and their impact on device performance need to be further understood in order to integrate phase change materials in oxide electronics.

36 MATERIALS SCIENCE↗