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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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Survivability design for a hybrid underwater vehicle

A novel hybrid underwater robotic vehicle (HROV) capable of working to the full ocean depth has been developed. The battery powered vehicle operates in two modes: operate as an untethered autonomous vehicle in autonomous underwater vehicle (AUV) mode and operate under remote control connected to the surface vessel by a lightweight, fiber optic tether in remotely operated vehicle (ROV) mode. Considering the hazardous underwater environment at the limiting depth and the hybrid operating modes, survivability has been placed on an equal level with the other design attributes of the HROV since the beginning of the project. This paper reports the survivability design elements for the HROV including basic vehicle design of integrated navigation and integrated communication, emergency recovery strategy, distributed architecture, redundant bus, dual battery package, emergency jettison system and self-repairing control system.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Tribological Properties and Self-Repairing Functionality of Ti6Al4V-Multilayer Graphene-Ag Composites

Ti6Al4V alloy has broad application prospects in the aircraft industry. However, when it is served as frictional motion components, the poor friction and wear properties may greatly influence the reliability and working life of the entire mechanical system. Therefore, this paper mainly investigates the tribological performance and self-repairing functionality of Ti6Al4V-multilayer graphene (MLG)-Ag composites (TMAC) from 25 to 600 °C. The results show that TMAC obtains better tribological behavior in comparison with Ti6Al4V alloy (TC4), Ti6Al4V-MLG composites (TMC) and Ti6Al4V-Ag composites (TAC). It should be ascribed to the synergistic action of the reinforcement MLG and lubricant Ag, which are crushed and spread out by mechanical and thermal stress in the friction process, leading to the formation of a lubricating film on the wear scar. Along with the spreading of lubricating film, Ag and MLG can precipitate onto the microdefective areas, thus playing an important role in repairing the wear scar of TMAC.

36 MATERIALS SCIENCE↗

Polymethacrylamide and Carbon Composites that Grow, Strengthen, and Self-Repair using Ambient Carbon Dioxide Fixation

Plants accumulate solid carbon mass and self-repair using atmospheric CO 2 fixation from photosynthesis. Synthetic materials capable of mimicking this property can significantly reduce the energy needed to transport and repair construction materials. Here, a gel matrix containing aminopropyl methacrylamide (APMA), glucose oxidase (GOx), and nanoceria-stabilized extracted chloroplasts that is able to grow, strengthen, and self-repair using carbon fixation is demonstrated. Glucose produced from the embedded chloroplasts is converted to gluconolactone (GL) via GOx, polymerizing with APMA to form a continuously expanding and strengthening polymethacrylamide. The extracted spinach chloroplasts exhibit enhanced stability and produce 12 µg GL mg -1 Chl h -1 after optimization of the temporal illumination conditions and the glucose efflux rate, with the insertion of chemoprotective nanoceria inside the chloroplasts. This system achieves an average growth rate of 60 µm 3 h -1 per chloroplast under ambient CO 2 and illumination over 18 h, thickening with a shear modulus of 3 kPa. This material can demonstrate self-repair using the exported glucose from chloroplasts and chemical crosslinking through the fissures. These results point to a new class of materials capable of using atmospheric CO 2 fixation as a regeneration source, finding utility as self-healing coatings, construction materials, and fabrics.

36 MATERIALS SCIENCE↗

Engineered Living Materials For Sustainability

Recent advances in synthetic biology and materials science have given rise to a new form of materials, namely engineered living materials (ELMs), which are composed of living matter or cell communities embedded in self-regenerating matrices of their own or artificial scaffolds. Like natural materials such as bone, wood, and skin, ELMs, which possess the functional capabilities of living organisms, can grow, self-organize, and self-repair when needed. They also spontaneously perform programmed biological functions upon sensing external cues. Currently, ELMs show promise for green energy production, bioremediation, disease treatment, and fabricating advanced smart materials. This review first introduces the dynamic features of natural living systems and their potential for developing novel materials. We then summarize the recent research progress on living materials and emerging design strategies from both synthetic biology and materials science perspectives. Lastly, we discuss the positive impacts of living materials on promoting sustainability and key future research directions.

36 MATERIALS SCIENCE↗

Resilient Hydrogels from the Nanoscale to the Macroscale

Biological systems illustrate how a material composed of fragile molecular components can collectively be highly resilient. While the average protein, cell, or even tissue may not last more than a few weeks, many animals and plants live for more than a century. Continual component regeneration and multiple systems to resist mechanical and chemical damage together make this longetivity possible. This project sought to develop biomimetic methods to enable a specific type of material, a hydrogel, to resist damage across multiple scales using distinct, modular damage protection mechanisms. Because hydrogels share many features with biological tissues, they are an ideal substrate for exploring biomimetic strategies for designing resilience and self-repair. We specifically focused in this study on DNA-crosslinked hydrogels, which contain DNA strands that can serve as material to link it together or to control its current state or properties. We investigated how new tools from dynamic DNA nanotechnology could make it possible to actively recover from damage by continually growing and forming a materials shape, or by identifying damage and directing an adaptive response to that damage involving chemical synthesis to reconstruct a structure. We developed embedded molecular sensors able to detect and strain of the gel before damage occurred and react to counteract damage. We also developed methods to continually create shapes and patterns using chemical processes that will allow those patterns to reform when they are damaged. The ability to design resilient materials capable of self-repair has important implications for materials engineering. Instead of designing a material to withstand the worst stresses it may encounter, we could instead design a material to survive under average conditions, but self-repair or reconfigure to resist impending damage. Resilient, self-repairing hydrogels will also have diverse applications such as sensors or actuators.

36 MATERIALS SCIENCE↗

Evolution of size-selected Pt cluster catalysts on prototypical oxide supports

The current quest for new pathways into sustainable, efficient and durable energy conversion technologies makes the used for a fundamental understanding of the atomic-scale phenomena underlying catalytic processes ever more pressing. In this context, characterizing catalyst particles in situ provides valuable information about the evolution of their composition, structure, oxidation state and charge state during an ongoing process. To disentangle the influence of individual parameters – temperature, pressure, gas composition, cluster size, as well as support acidity, redox state and defect density – it is crucial to control them precisely and separately in experiments. At the example of size-selected Pt n clusters – i.e. sub-nm particles defined to the exact number of atoms – on flat oxide supports, we follow their rich evolution phenomena via (synchrotron-based) X-ray photoelectron spectroscopy (XPS) and scanning tunnelling microscopy (STM) during temperature ramps and in various gas environments. Here, we present our experience with these highly defined, yet complicated-to-create samples in ultra-high vacuum (UHV) and at mbar pressures. We discuss their stability during transport to synchrotrons and under reaction conditions on three prototypical oxide supports and show the various phenomena that can be disentangled. Ptn clusters on the non-reducible silicon dioxide, SiO 2 , remain size-selected and show remarkable stability. Doping strongly influences the size-dependent binding energy shifts and changes the Pt response to oxidative and reaction conditions, which we attribute to different cluster geometries: p-type doping leads to wetting, enhanced sinter resistance and a diminished response to oxidative environments, compared to clusters on n-type doped samples. We compare the system with our previous findings of a similar change in dimensionality for Pt 20 clusters on the reducible ceria, CeO 2 (111), support, induced by modulation of its O vacancy density. The Pt n /CeO 2 system is particularly interesting for strategies to stabilize and redisperse Pt clusters dynamically. Finally, we study the evolution of Pt n clusters on another reducible oxide support, magnetite, Fe 3 O 4 (001), in 0.1 mbar alternating redox conditions at RT and elevated temperature. In analogy to findings previously reported for Pt/TiO 2 (110), the clusters either become encapsulated by a thin oxide film via strong metal–support interaction (SMSI) or deeply buried in the magnetite. Overall, our approach of following the evolution of size-selected clusters on oxide supports leads to fundamental atomic-scale insights on nano-scale catalyst materials, on our path to sustainable, dynamic and self-repairing catalysts.

Falling, Lorenz J. [Technical Univ. of Munich (Ger↗

Experiments and Simulation of a Borehole in Salt to Understand Heat, Brine, and Vapor Migration - 19192

Disposition of heat-generating nuclear waste (HGNW) remains a continuing technical and sociopolitical challenge. Numerous concepts for HGNW management have been proposed and examined internationally, including an extensive focus on geologic disposal. One proposed geologic material is salt because of its low permeability and viscoplastic deformation that causes self-repair of damage done to the salt by waste emplacement activities. Evaluating the safety and technical challenges of storing HGNW in a salt repository is an ongoing process involving experiments and supporting numerical simulation. Currently an experiment is underway at the Waste Isolation Pilot Plant (WIPP) to explore how the presence of a heat generating source affects phenomena such as brine migration, vapor transport, and mechanical changes to the bedded salt. A sub-horizontal heated borehole test is in progress in the underground at the WIPP that includes a centrally located 10.2 cm diameter borehole with an adjustable heater surrounded with smaller diameter boreholes instrumented with thermocouples. The central borehole contains an inflatable packer, heating block, brine sampler, and constantly flowing nitrogen gas circulation system. Air-injection tests performed in the central borehole provide pressure measurements that are used to constrain permeability of the system. The steady-state temperatures, as well as the rise and fall of temperature when the heater is cycled on and off, have been measured for up to 60 days. In the borehole, dry nitrogen gas circulation evaporates water and outflows to a desiccant container where water mass is measured daily during the experiment to quantify vapor removal. Although this test is a 'shake-down' for a planned second round of fresh borehole testing, we have gathered a rich dataset. These data allow us to build simulations using the Finite Element Heat and Mass transfer code (FEHM) to evaluate the experimental results, determine field-scale parameters, and identify code improvements to reproduce important physical processes that may not be accounted for at present. A 3-D numerical mesh, built using LaGrit software (lagrit.lanl.gov; Miller et al., 2007), includes increasing resolution around the central borehole. Modeling of the experiment allows for determining the local thermal conductivity and permeability of any damaged bedded salt around the borehole, where damage from drilling may change the permeability, porosity and saturation conditions, by parameter testing and inverse methods. Additionally, assumptions about brine and vapor flow and transport are being tested by comparing measured and simulated results. The combination of experimental data and model results provide additional data to help support the safety case for safe and effective HGNW disposition in bedded salt formations. Initial results from this experiment show that water flow into the borehole is within previous experimental results. Further, we have found that the design of the heater block is restricting energy to flow into the rock salt. Thus, this test has proven useful in design of the next generation experiment where infrared heating may be used to bypass issues caused by air gaps located around the current stainless steel block heater. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Self-Repair of Structure and Bioactivity in a Supramolecular Nanostructure

Supramolecular nanostructures formed through self-assembly can have energy landscapes, which determine their structures and functions depending on the pathways selected for their synthesis and processing and on the conditions they are exposed to after their initial formation. We report here on the structural damage that occurs in supramolecular peptide amphiphile nanostructures, during freezing in aqueous media, and the self-repair pathways that restore their functions. We found that freezing converts long supramolecular nanofibers into shorter ones, compromising their ability to support cell adhesion, but a single heating and cooling cycle reverses the damage and rescues their bioactivity. Thermal energy in this cycle enables noncovalent interactions to reconfigure the nanostructures into the thermodynamically preferred long nanofibers, a repair process that is impeded by kinetic traps. In addition, we found that nanofibers disrupted during freeze-drying also exhibit the ability to undergo thermal self-repair and recovery of their bioactivity, despite the extra disruption caused by the dehydration step. Following both freezing and freeze-drying, which shorten the 1D nanostructures, their self-repair capacity through thermally driven elongation is inhibited by kinetically trapped states, which contain highly stable noncovalent interactions that are difficult to rearrange. These states decrease the extent of thermal nanostructure repair, an observation we hypothesize applies to supramolecular systems in general and is mechanistically linked to suppressed molecular exchange dynamics.

36 MATERIALS SCIENCE↗

Electric field stimulates production of highly conductive microbial OmcZ nanowires

Multifunctional living materials are attractive due to their powerful ability to self-repair and replicate. However, most natural materials lack electronic functionality. Here we show that an electric field, applied to electricity-producing Geobacter sulfurreducens biofilms, stimulates production of cytochrome OmcZ nanowires with 1,000-fold higher conductivity (30 S cm -1 ) and threefold higher stiffness (1.5 GPa) than the cytochrome OmcS nanowires that are important in natural environments. Using chemical imaging-based multimodal nanospectroscopy, we correlate protein structure with function and observe pH-induced conformational switching to β-sheets in individual nanowires, which increases their stiffness and conductivity by 100-fold due to enhanced π-stacking of heme groups; this was further confirmed by computational modeling and bulk spectroscopic studies. These nanowires can transduce mechanical and chemical stimuli into electrical signals to perform sensing, synthesis and energy production. Overall, these findings of biologically produced, highly conductive protein nanowires may help to guide the development of seamless, bidirectional interfaces between biological and electronic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗