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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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299 records · Page 17

Film Thickness and Composition Effects in Symmetric Ternary Block Copolymer/Homopolymer Blend Films: Domain Spacing and Orientation

We report thickness and homopolymer molar mass dependencies in thin film blends of a compositionally symmetric 75 kg/mol lamellar polystyrene-block-poly(methyl methacrylate) diblock copolymer (PS-b-PMMA) with near-equal volume fractions of PS and PMMA homopolymers on “neutral” surfaces that promote a vertical domain orientation. PS and PMMA homopolymers with equal molar masses of 1, 3, and 22 kg/mol are blended in a 1:1 mass ratio. To efficiently explore this parameter space, we prepared combinatorial samples with gradient homopolymer concentrations using electrospray deposition (ESD) and gradient film thicknesses using flow coating; these samples were subsequently characterized by grazing-incidence small-angle X-ray scattering and scanning electron microscopy, respectively. Our results demonstrate that the added homopolymers increase or reduce domain spacings with respect to the neat (unblended) block copolymer depending on their molar masses, in line with previous reports; a simple heuristic to estimate the domain scaling in ternary blends based on the homopolymer molar mass agrees well with data for the thinnest blend films studied here. More surprisingly, we observe that the measured domain spacing in blends also depends on film thickness, with thicker films exhibiting larger domain spacings than thinner films at the same homopolymer concentration. Furthermore, thickness gradients at fixed homopolymer concentrations reveal a change in lamellae orientation from vertical to horizontal as film thickness is increased beyond the nominal lamellar domain spacing. Coarse-grained molecular dynamics simulations indicate that this change in orientation is induced by homopolymer segregation to film surfaces. Finally, tying these effects together, we hypothesize that the observed dependence of domain spacing on film thickness is a consequence of changes in the vertical homopolymer composition profile in thicker films during lamellae reorientation and the conformational asymmetry between PMMA and PS segments.

36 MATERIALS SCIENCE↗

Molecular-Weight-Dependent Infiltration and Adsorption of Polymers into Nanochannels

The mesoporous silica shell coating hydrogenolysis nano-catalysts alters the molecular weight distributions of cleaved polymer chains compared to catalysts without a shell. The shell, composed of radially aligned narrow cylindrical nanopores, reduces the formation of low-valued gaseous products and increases the median molecular weight of the product, thus enhancing the value of the products for polymer upcycling. Here, to understand the role of the mesoporous shell, we have studied the spatial distribution of polystyrene chains, used as a model polymer, in the nanochannels in both the melt phase and solution phase. In the melt, we observed from small-angle X-ray scattering experiments that the infiltration rate of the polymer into the nanochannels is inversely proportional to the molecular weight, which is consistent with theory. In theta solution experiments using UV–vis spectroscopy, we found that the shell significantly enhances polymer adsorption compared to nanoparticles without pores. In addition, the degree of polymer adsorption is not a monotonic function of molecular weight but initially increases with the molecular weight before eventually decreasing. The molecular weight for the peak adsorption increases with the pore diameter. This adsorption behavior is rationalized as resulting from a balance between the mixing entropy gain by surface adsorption and the conformational entropy penalty incurred by chains confined in the nanochannels. The spatial distribution of polymer chains in the nanochannels is visualized by energy-dispersive X-ray spectroscopy (EDX), and inverse Abel-transformed data reveals a less uniform polymer distribution along the primary pore axis for longer chains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of film thickness on electrochemical properties of nanoscale polyethylenedioxythiophene (PEDOT) thin films grown by oxidative molecular layer deposition (oMLD)

Poly(3,4-ethylene dioxythiophene) (PEDOT) has a high theoretical charge storage capacity, making it of interest for electrochemical applications including energy storage and water desalination. Nanoscale thin films of PEDOT are particularly attractive for these applications to enable faster charging. Recent work has demonstrated that nanoscale thin films of PEDOT can be formed using sequential gas-phase exposures via oxidative molecular layer deposition, or oMLD, which provides advantages in conformality and uniformity on high aspect ratio substrates over other deposition techniques. But to date, the electrochemical properties of these oMLD PEDOT thin films have not been well-characterized. In this work, we examine the electrochemical properties of 5–100 nm thick PEDOT films formed using 20–175 oMLD deposition cycles. We find that film thickness of oMLD PEDOT films affects the orientation of ordered domains leading to a substantial change in charge storage capacity. Interestingly, we observe a minimum in charge storage capacity for an oMLD PEDOT film thickness of ~30 nm (60 oMLD cycles at 150 °C), coinciding with the highest degree of face-on oriented PEDOT domains as measured using grazing incidence wide angle X-ray scattering (GIWAXS). Thinner and thicker oMLD PEDOT films exhibit higher fractions of oblique (off-angle) orientations and corresponding increases in charge capacity of up to 120 mA h g -1 . Electrochemical measurements suggest that higher charge capacity in films with mixed domain orientation arise from the facile transport of ions from the liquid electrolyte into the PEDOT layer. Greater exposure of the electrolyte to PEDOT domain edges is posited to facilitate faster ion transport in these mixed domain films. In conclusion, these insights will inform future design of PEDOT coated high-aspect ratio structures for electrochemical energy storage and water treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Elucidation of the physical factors that control activated transport of penetrants in chemically complex glass-forming liquids

Understanding the activated transport of penetrant or tracer atoms and molecules in condensed phases is a challenging problem in chemistry, materials science, physics, and biophysics. Many angstrom- and nanometer-scale features enter due to the highly variable shape, size, interaction, and conformational flexibility of the penetrant and matrix species, leading to a dramatic diversity of penetrant dynamics. Based on a minimalist model of a spherical penetrant in equilibrated dense matrices of hard spheres, a recent microscopic theory that relates hopping transport to local structure has predicted a novel correlation between penetrant diffusivity and the matrix thermodynamic dimensionless compressibility, S 0 ( T ) (which also quantifies the amplitude of long wavelength density fluctuations), as a consequence of a fundamental statistical mechanical relationship between structure and thermodynamics. Moreover, the penetrant activation barrier is predicted to have a factorized/multiplicative form, scaling as the product of an inverse power law of S 0 ( T ) and a linear/logarithmic function of the penetrant-to-matrix size ratio. This implies an enormous reduction in chemical complexity that is verified based solely on experimental data for diverse classes of chemically complex penetrants dissolved in molecular and polymeric liquids over a wide range of temperatures down to the kinetic glass transition. The predicted corollary that the penetrant diffusion constant decreases exponentially with inverse temperature raised to an exponent determined solely by how S 0 ( T ) decreases with cooling is also verified experimentally. Our findings are relevant to fundamental questions in glassy dynamics, self-averaging of angstrom-scale chemical features, and applications such as membrane separations, barrier coatings, drug delivery, and self-healing.

Science & Technology - Other Topics↗

Ejecta patterns of Meteor Crater, Arizona derived from the linear un-mixing of TIMS data and laboratory thermal emission spectra

Accurate interpretation of thermal infrared data depends upon the understanding and removal of complicating effects. These effects may include physical mixing of various mineralogies and particle sizes, atmospheric absorption and emission, surficial coatings, geometry effects, and differential surface temperatures. The focus is the examination of the linear spectral mixing of individual mineral or endmember spectra. Linear addition of spectra, for particles larger than the wavelength, allows for a straight-forward method of deconvolving the observed spectra, predicting a volume percent of each endmember. The 'forward analysis' of linear mixing (comparing the spectra of physical mixtures to numerical mixtures) has received much attention. The reverse approach of un-mixing thermal emission spectra was examined with remotely sensed data, but no laboratory verification exists. Understanding of the effects of spectral mixing on high resolution laboratory spectra allows for the extrapolation to lower resolution, and often more complicated, remotely gathered data. Thermal Infrared Multispectral Scanner (TIMS) data for Meteor Crater, Arizona were acquired in Sep. 1987. The spectral un-mixing of these data gives a unique test of the laboratory results. Meteor Crater (1.2 km in diameter and 180 m deep) is located in north-central Arizona, west of Canyon Diablo. The arid environment, paucity of vegetation, and low relief make the region ideal for remote data acquisition. Within the horizontal sedimentary sequence that forms the upper Colorado Plateau, the oldest unit sampled by the impact crater was the Permian Coconino Sandstone. A thin bed of the Toroweap Formation, also of Permian age, conformably overlays the Coconino. Above the Toroweap lies the Permian Kiabab Limestone which, in turn, is covered by a thin veneer of the Moenkopi Formation. The Moenkopi is Triassic in age and has two distinct sub-units in the vicinity of the crater. The lower Wupatki member is a fine-grained sandstone, while the upper Moqui member is a fissile siltstone. Ejecta from these units are preserved as inverted stratigraphy up to 2 crater radii from the rim. The mineralogical contrast between the units, relative lack of post-emplacement erosion and ejecta mixing provide a unique site to apply the un-mixing model. Selection of the aforementioned units as endmembers reveals distinct patterns in the ejecta of the crater.

Ramsey, Michael S.↗

The Test and Evaluation of a Non-Chromate Finishing Agent

This research is focused on the design, development and implementation of an industry, military and commercial standard testing cell for surface coatings, which focuses on advanced non-chromate materials technology and their commercialization. Currently, within both private and commercial sectors, chromates are used in the corrosion prevention. processes. However, there is a great demand for chromate-free systems that are able to provide equal protection. At the end of this effort, it is intended that a patented alternative to chromate conversion coatings would be tested and processed for commercialization. Thus far, research studies have been concerned primarily with current corrosion knowledge and testing methods. Corrosion can be classified into five categories: The first type is uniform corrosion which is dominated by a uniform thinning due to an even and regular loss of metal. The second type is called localized corrosion in which most of the loss occurs in discrete areas. The third type, metallurgically influenced corrosion is a form of attack where metallurgy plays a significant role. The fourth type, titled mechanically assisted degradation is a form of attack where velocity, abrasion, and hydrodynamics control the corrosion process. The last type of corrosion is defined as environmentally induced cracking which occurs when cracks are produced under specific, premeditated stress. Oddly enough, with these varying classifications, there are not as many standardized corrosion testing sites. Two of the most common testing methods for corrosion are salt spray testing and filiform. Although neither has proven to be absolute, in terms of the resulting observations, our research aims to help provide data that may be used to support the standardization for corrosion testing. We would acquire and use a Singleton Cyclic Corrosion Testing Chamber. Singleton test chambers perform a wide range of commonly used catalytic corrosion tests. They are used throughout the industry, some of which are - automotive, aerospace, electronic and many more. In addition to this, Singleton test chambers are fully expandable to accommodate cyclic corrosion testing needs. Singleton chambers are also designed for complete compliance and conformity with ASTM (American Society for Testing and Materials), military and commercial standards.

Gulley, H.↗

Development of 3D electromagnetic modeling tools for airborne vehicles

The main goal of this project is to develop methodologies for scattering by airborne composite vehicles. Although our primary focus continues to be the development of a general purpose code for analyzing the entire structure as a single unit, a number of other tasks are also pursued in parallel with this effort. These tasks are important in testing the overall approach and in developing suitable models for materials coatings, junctions and, more generally, in assessing the effectiveness of the various parts comprising the final code. Here, we briefly discuss our progress on the five different tasks which were pursued during this period. Our progress on each of these tasks is described in the detailed reports (listed at the end of this report) and the memoranda included. The first task described below is, of course, the core of this project and deals with the development of the overall code. Undoubtedly, it is the outcome of the research which was funded by NASA-Ames and the Navy over the past three years. During this year we developed the first finite element code for scattering by structures of arbitrary shape and composition. The code employs a new absorbing boundary condition which allows termination of the finite element mesh only 0.3 lambda from the outer surface of the target. This leads to a remarkable reduction of the mesh size and is a unique feature of the code. Other unique features of this code include capabilities to model resistive sheets, impedance sheets and anisotropic materials. This last capability is the latest feature of the code and is still under development. The code has been extensively validated for a number of composite geometries and some examples are given. The validation of the code is still in progress for anisotropic and larger non-metallic geometries and cavities. The developed finite element code is based on a Galerkin's formulation and employs edge-based tetrahedral elements for discretizing the dielectric sections and the region between the target and the outer mesh termination boundary (ATB). This boundary is placed in conformity with the target's outer surface, thus resulting in additional reduction of the unknown count.

Volakis, John L.↗

Enhanced Light Outcoupling from OLEDs Fabricated on Novel Low-Cost Patterned Plastic Substrates of Varying Periodicity

OLEDs continue to make strides in display applications, but their commercial utilization in solid-state lighting (SSL) is lagging. An ongoing challenge, in particular for manufacturing, is the need for enhanced efficiency and hence the necessity to increase in an inexpensive approach the extraction of the light generated inside the OLED into the forward (viewing) hemisphere. In conventional OLEDs fabricated on a transparent flat anode coated on glass, the external quantum efficiency (EQE) is only ~20%. About 50% of the light is lost to internal waveguiding in the high refractive index (RI) organic + ITO anode layers and to surface plasmon polaritons (SPPs) at the organic/metal cathode interface. Another ~30% of the light is externally waveguided in the substrate to its edges. While extraction of the externally waveguided light is commonly addressed by adding a microlens array (MLA) or a scattering layer at the substrate’s air-side, light outcoupling increases by only ~1.6-1.7x (vs up to 2.5x in improving from ~20% to ~50%). The use of a hemispherical lens or an index matching fluid (IMF) at the substrate/photodetector (PD) interface increases the outcoupling by at least 2x; these approaches however, are not viable industrially, and even a MLA is sometimes undesirable due to its non-planar, scattering structure. In multi-stack tandem OLEDs, where the metal cathode is far from the emitting zone(s), the impact of photons loss to SPPs decreases. Our project addressed the ~50% loss to the internally waveguided light and SPPs. We evaluated OLEDs fabricated on patterned or planarized plastic substrates manufactured in a cost-effective approach compatible with a roll-to-roll (R2R) process. The OLEDs were either (i) patterned to various degrees depending on the pitch a and height or depth h of the pattern features or (ii) planar, with a pattern buried under a flat high RI planarization layer. We demonstrated that the outcoupling from green patterned OLEDs reaches ~50% by mitigating plasmon–related loss and internal waveguiding, even without the addition of a MLA, a hemispherical lens, or IMF. Simulations conducted in parallel with the experimental effort demonstrated how diffraction by conformally corrugated OLEDs increases the outcoupling to >60%. Structures with varying pitch values were also simulated indicating that combining domains of varying pitch could increase outcoupling to 55-60%. Experimentally, we additionally assessed the role a and h in determining not only the OLED efficiencies, but also their structural properties, i.e., the uniformity and conformality throughout the OLED stack. As planar OLEDs are preferred over corrugated devices, we studied different patterns in plastic substrates that were planarized by a high RI formulation. Planar green OLEDs on such structures showed enhanced efficiencies with EQEs larger than 60% with the addition of an IMF (to extract the substrate mode) at the substrate/Si PD interface. White OLEDs showed EQEs of 45.5%. Plastic substrates are currently less attractive than glass substrates due to drawbacks such as permeability to water vapor and oxygen, and in some cases thermal instability. Plastic substrates however, are flexible and easy to handle unlike thin flexible glass, and once transparent thin barrier films are available, they will become more attractive; they are already of interest in medical applications. Importantly, as it is easy to generate various patterns in different plastic materials, they provide excellent means for assessing and optimizing enhancing extracting structures. Such structures can also be transferred to glass substrates with some process modifications. The technical effectiveness and economic feasibility of the project lie in the patterning of the extracting plastic substrates in an approach that is scalable to R2R manufacturing. R2R processes are of drastically lower-cost than batch or single-unit fabrication. The patterned plastic can be a part of an integrated substrate either plastic or glass, which includes also a MLA or a planar layer with embedded scattering particles, as well as a conductive metal mesh/electrode design. SSL is environmentally-friendly and as OLED SSL becomes more efficient it will reduce electricity consumption, and hence lighting cost, as well as produce less expensive attractive lighting fixtures. Our university-industry collaboration is hence of major benefit to the public as it demonstrates the feasibility of manufacturing optimized extracting substrates for highly efficient OLEDs for SSL in a future R2R process, which would drastically reduce the manufacturing cost and increase production in the USA. Moreover, newly developed methods by our team allow low-cost roll manufactured substrates to be transferred to flexible or rigid glass substrates, which solves the plastic substrate barrier issues, and when combined with device encapsulation will increase the OLEDs’ environmental stability.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Supercomputer-Based Ensemble Docking Drug Discovery Pipeline with Application to Covid-19

In this work, we present a supercomputer-driven pipeline for in silico drug discovery using enhanced sampling molecular dynamics (MD) and ensemble docking. Ensemble docking makes use of MD results by docking compound databases into representative protein binding-site conformations, thus taking into account the dynamic properties of the binding sites. We also describe preliminary results obtained for 24 systems involving eight proteins of the proteome of SARS-CoV-2. The MD involves temperature replica exchange enhanced sampling, making use of massively parallel supercomputing to quickly sample the configurational space of protein drug targets. Using the Summit supercomputer at the Oak Ridge National Laboratory, more than 1 ms of enhanced sampling MD can be generated per day. We have ensemble docked repurposing databases to 10 configurations of each of the 24 SARS-CoV-2 systems using AutoDock Vina. Comparison to experiment demonstrates remarkably high hit rates for the top scoring tranches of compounds identified by our ensemble approach. We also demonstrate that, using Autodock-GPU on Summit, it is possible to perform exhaustive docking of one billion compounds in under 24 h. Finally, we discuss preliminary results and planned improvements to the pipeline, including the use of quantum mechanical (QM), machine learning, and artificial intelligence (AI) methods to cluster MD trajectories and rescore docking poses.

60 APPLIED LIFE SCIENCES↗

Near-Net-Shape Processing of Sintered Fibrous Ceramics Achieved

A variety of sintered fibrous ceramic (SFC) materials have been developed over the last 50 years as thermal barrier materials for reentry applications. SFC materials typically exhibit very low thermal conductivities combined with low densities and good thermal stability up to 2500 F. These materials have flown successfully on the space shuttle orbiters since the 1960's. More recently, the McDonnell Douglas Corporation successfully used SFC tiles as a heat shield on the underside of its DC X test vehicle. For both of these applications, tiles are machined from blocks of a specific type of SFC called an alumina-enhanced thermal barrier (AETB). The sizes of these blocks have been limited by the manufacturing process. In addition, as much as 80 to 90 percent of the material can be lost during the machining of tiles with significant amounts of curvature. To address these problems, the NASA Glenn Research Center at Lewis Field entered a cooperative contract with the Boeing Company to develop a vacuum-assisted forming process that can produce large (approximately 4 square feet), severely contoured panels of AETB while saving costs in comparison to the conventional cast-and-machine billet process. For shuttle use, AETB is slurry cast, drained, and fired to form square billets conforming to the shape of the filtration box. The billets are then cut into tiles of the appropriate size for thermally protecting the space shuttle. Processing techniques have limited the maximum size of AETB billets to 21.5 square inches by 6.5-in. thick, but the space shuttles use discrete heat shield tiles no more than 8 to 12 square inches. However, in other applications, large, complex shapes are needed, and the tiling approach is undesirable. For such applications, vacuum-assisted forming can produce large parts with complex shapes while reducing machining waste and eliminating cemented joints between bonded billets. Because it allows contoured shapes to be formed, material utilization is inherently high. Initial estimates show that the amount of material lost during machining can be reduced by 50 percent or more. In addition, a fiber alignment favorable for minimum heat transfer is maintained for all panel shapes since the fibers are aligned parallel to the contoured surface of the forming tool or mold. The vacuum-assisted forming process can complete the entire forming operation in a matter of minutes and can produce multiple parts whose size is limited only by the size of the forming tool. To date, panels as large as 2 square feet have been demonstrated The vacuum-assisted forming process starts with the fabrication of a permeable forming tool, or mold, with the proper part contour. This reusable tool is mounted over an internal rib support structure, as depicted in the diagram, such that a vacuum can be pulled on the bottom portion of the tool. AETB slurry is then poured over and around the tool, liquid is drawn from the slurry, and the part forms over the tool surface. The part is then dried, fired, and finished machined. Future plans include an evaluation of the need for additional coatings and surface-toughness treatments to extend the durability and performance of this material.

Angel, Paul W.↗