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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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At least 73 records · Page 4

Phase Stability of Garnet Solid-Electrolyte Interfacing with Various Cathodes in All Solid-State Batteries

Garnet-structured Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 (LLZTO) is one of the most promising electrolyte materials for solid-state Li batteries (SS-LiB). The design and fabrication of a good cathode/electrolyte interface is an important criterion for the SS-LiB. In this work, we performed a systematic study on the impact of cathode crystal structure and chemical compositions on their chemical stabilities against the LLZTO at elevated temperatures, which are required for their adhesion during cell fabrication processes. X-ray Diffraction (XRD) and Rietveld refinement analyses revealed the chemical stabilities of various cathode materials in contact with the LLZTO. While layered LiCoO 2 cathode showed good stability in contact with LLZTO to 900 °C, LiNiO 2 or Ni-rich LiNi x Mn y Co 1–x–y O 2 (NMC) cathodes suffered from the formation of La 4 NiLiO 8 due to La-diffusion from LLZTO. Furthermore, Mn-rich LiMn 2 O 4 spinel and layered LiNi 1/3 Mn 1/3 Co 1/3 O 2 cathodes suffered from the formation of La 2 Zr 2 O 7 due to Li-diffusion and production of Li 2 MnO 3 . As a result, LiNi 0.6 Mn 0.2 Co 0.2 O 2 , having an ideal balance of Ni/Mn/Co composition, or Li 2 MnO 3 containing cathodes such as Li 1.2 Ni 0.15 Mn 0.55 Co 0.1 O 2 were found to have excellent phase stability as the cathodes for LLZTO-based SS-LiBs.

25 ENERGY STORAGE↗

Ceruloplasmin copper induces oxidant damage by a redox process utilizing cell-derived superoxide as reductant

Oxidative damage by transition metals bound to proteins may be an important pathogenic mechanism. Ceruloplasmin (Cp) is a Cu-containing plasma protein thought to be involved in oxidative modification of lipoproteins. We have previously shown that Cp increased cell-mediated low-density lipoprotein (LDL) oxidation by a process requiring cell-derived superoxide, but the underlying chemical mechanism(s) is (are) unknown. We now show that superoxide reduction of Cp Cu is a critical reaction in cellular LDL oxidation. By bathocuproine disulfonate (BCS) binding and by superoxide utilization, we showed that exogenous superoxide reduces a single Cp Cu atom, the same Cu required for LDL oxidation. The Cu atom remained bound to Cp during the redox cycle. Three avenues of evidence showed that vascular cells reduce Cp Cu by a superoxide-dependent process. The 2-fold higher rate of Cp Cu reduction by smooth muscle cells (SMC) compared to endothelial cells (EC) was consistent with their relative rates of superoxide release. Furthermore, Cp Cu reduction by cells was blocked by Cu,Zn superoxide dismutase (SOD1). Finally, the level of superoxide produced by EC and SMC was sufficient to cause the amount of Cu reduction observed. An important role of Cp Cu reduction in LDL oxidation was suggested by results showing that SOD1 inhibited Cp Cu reduction and LDL oxidation by SMC with equal potency, while tumor necrosis factor-alpha stimulated both processes. In summary, these results show that superoxide is a critical cellular reductant of divalent transition metals involved in oxidation, and that protein-bound Cu is a substrate for this reaction. The role of these mechanisms in oxidative processes in vivo has yet to be defined.

NASA Discipline Regulatory Physiology↗

Nanopinhole Passivating Contact Si Solar Cells Fabricated with Metal-Assisted Chemical Etching

Monocrystalline Si (c-Si) solar cells with passivating contacts based on doped polycrystalline Si (poly-Si) on ≈2.0 nm silicon oxide (SiO x ) require >1000 °C thermal processing to create conducting pinholes in the SiO x layer. However, this high thermal budget can induce bulk defects in the Czochralski c-Si wafers used as the cell absorber layer. We demonstrate that pinholes can instead be created using metal-assisted chemical etching on planar or textured morphologies, at room temperature. This wet process creates up to 200 nm wide conducting pinholes that are directly observed with transmission electron and atomic force microscopies. High-performance hole-selective poly-Si/SiN y /SiO x and electron-selective poly-Si/SiO x passivating contacts are fabricated and implemented in laboratory-scale solar cells. This process development significantly broadens the range of passivation layer materials, their thicknesses, and surface morphologies, which enables the design of poly-Si contacts with superior passivating quality.

14 SOLAR ENERGY↗

The Pd2Si - /Pd/ - Ni - solder plated metallization system for silicon solar cells

The rationale and application of a plated metal system, Pd2Si Pd - Ni - solder, is presented. This metallization system is particularly useful on shallow p-n junction solar cells. The advantages of such plated solar cell contacts are discussed. A process sequence for applying the metallization system is outlined. A specific example is presented, including chemical plating solution formulations and detailed process step descriptions. Electrical test data for solar cells metallized with the palladium-nickel-solder system are provided.

Coleman, M. G.↗

FTO regulates myoblast proliferation by controlling CCND1 expression in an m6A-YTHDF2-dependent manner

Highlights: • Silencing FTO delays cell cycle and inhibits cell proliferation. • FTO regulates cell proliferation depending on its m{sup 6}A demethylation activity. • Silencing FTO suppresses CCND1 expression via YTHDF2-mediated mRNA degradation. • Knockdown YTHDF2 eliminates the cell cycle arrest in FTO-deficient cells. N6-Methyladenosine (m{sup 6}A) modification is the most abundant chemical modification in mRNA, and it participates in various biological processes, such as cell differentiation and proliferation. However, little is known about the function of m{sup 6}A demethylase fat mass and obesity-associated (FTO) in myoblast proliferation. Here, we demonstrated that knockdown of FTO can significantly inhibit myoblast proliferation and promote apoptosis. RNA sequencing analysis revealed that a lot of downregulated genes in FTO knockdown cells are associated with cell cycle and apoptosis. Furthermore, silencing FTO drastically decreased cyclin D1 (CCND1) expression through YTHDF2-mediated mRNA degradation, thereby delaying the progression of G1 phase, and leading to impaired myoblast proliferation. These findings unraveled that FTO regulates myoblast proliferation by controlling CCND1 expression in an m{sup 6}A-YTHDF2-dependent manner, which highlights the critical roles of m{sup 6}A modification in myoblast proliferation.

60 APPLIED LIFE SCIENCES↗

High-efficiency, deep-junction, epitaxial InP solar cells on (100) and (111)B InP substrates

We report on the development and performance of deep-junction (approximately 0.25 micron), graded-emitter-doped, n(sup +)-p InP solar cells grown by metallorganic chemical vapor deposition (MOCVD). A novel, diffusion-transport process for obtaining lightly-doped p-type base regions of the solar cell is described. The I-V data and external quantum-efficiency response of these cells are presented. The best active-area AMO efficiency for these deep-junction cells on (100)-oriented InP substrates is 16.8 percent, with a J(sub SC) of 31.8 mA/sq cm, a V(sub OC) of 0.843 V, and a fill-factor of 0.85. By comparison, the best cell efficiency on the (111)B-oriented InP substrates was 15.0 percent. These efficiency values for deep-junction cells are encouraging and compare favorably with performance of thin-emitter (0.03 micron) epitaxial cells as well as that of deep-emitter diffused cells. The cell performance and breakdown voltage characteristics of a batch of 20 cells on each of the orientations are presented, indicating the superior breakdown voltage properties and other characteristics of InP cells on the (111)B orientation. Spectral response, dark I-V data, and photoluminescence (PL) measurements on the InP cells are presented with an analysis on the variation in J(sub SC) and V(sub OC) of the cells. It is observed, under open-circuit conditions, that lower-V(sub OC) cells exhibit higher band-edge PL intensity for both the (100) and (111)B orientations. This anomalous behavior suggests that radiative recombination in the heavily-doped n(sup +)-InP emitter may be detrimental to achieving higher V(sub OC) in n(sup +)-p InP solar cells.

Venkatasubramanian, R.↗

Vapor Deposition Process for Engineering of Dispersed PEMFC ORR Pt/NbO x /C Catalysts

With support from the Department of Energy, and in partnership with Oak Ridge National Laboratory, Exothermics, Northeastern University, the University of Michigan, and IRD Fuel Cells, Ford has led an effort to use physical vapor deposition (PVD) to produce oxygen reduction reaction (ORR) catalysts for proton exchange membrane fuel cells (PEMFCs). Conventional ORR catalysts are made by wet chemical processes, and experience loss of electrochemical surface area and activity over voltage cycling due to Pt dissolution and Pt particle coalescence. Not only was PVD processing researched as a means to reduce solvent waste and enhance reproducibility in catalyst manufacturing, but it was also perceived as a means to deposit preferential phases of niobium oxide onto the catalyst, which would then serve to prevent Pt particle movement and extend PEMFC lifetime.

08 HYDROGEN↗

Leveraging Calibration Transfer Techniques for Remote Monitoring of Samarium and Europium in LiCl Using Laser-Induced Florescence Spectroscopy for Radioisotope Production Applications

Radioisotope production relies on complex chemical processes that must be performed in radiological hot cells or glove boxes because of the radioactive and otherwise hazardous materials being used. In these situations, optical sensors can provide real-time monitoring to users, which is unobtainable by more traditional methods. This study explores the use of calibration transfer methods to train a model on one instrument and date and then transfer it to another instrument of the same or different configuration on a different date. By performing laser-induced fluorescence measurements of Eu(III) and Sm(III) in 10 M LiCl over the course of 6 months using two disparate spectrometers and two different training sets, a strategy for calibrating and deploying models for online monitoring was established. Three transfer techniques were compared: direct standardization (DS), piecewise direct standardization (PDS), and external parameter orthogonalization (EPO). DS and PDS outperformed EPO for day-to-day transfers, and EPO was not effective for instrument-to-instrument transfers. Transferring the initial date’s full factorial model provided better prediction performance compared with retraining models the day of measurements using a D-optimal designed calibration set. For both day-to-day and instrument-to-instrument transfers, five Kennard–Stone selected samples were sufficient. Based on this choice, the initial-date, high-resolution spectrometer model was transferred to a lower-resolution, compact spectrometer 6 months later to monitor a simulated, real-time demonstration. Here, the combined predictions of the DS and PDS transferred models were able to accurately track the anticipated concentration profiles, maintaining root-mean-square error of prediction values below 10 ppm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Predicting Small Molecule Transfer Free Energies by Combining Molecular Dynamics Simulations and Deep Learning

Accurately predicting small molecule partitioning and hydrophobicity is critical in the drug discovery process. There are many heterogeneous chemical environments within a cell and entire human body. For example, drugs must be able to cross the hydrophobic cellular membrane to reach their intracellular targets, and hydrophobicity is an important driving force for drug–protein binding. Atomistic molecular dynamics (MD) simulations are routinely used to calculate free energies of small molecules binding to proteins, crossing lipid membranes, and solvation but are computationally expensive. Machine learning (ML) and empirical methods are also used throughout drug discovery but rely on experimental data, limiting the domain of applicability. We present atomistic MD simulations calculating 15,000 small molecule free energies of transfer from water to cyclohexane. This large data set is used to train ML models that predict the free energies of transfer. We show that a spatial graph neural network model achieves the highest accuracy, followed closely by a 3D-convolutional neural network, and shallow learning based on the chemical fingerprint is significantly less accurate. A mean absolute error of ~4 kJ/mol compared to the MD calculations was achieved for our best ML model. We also show that including data from the MD simulation improves the predictions, tests the transferability of each model to a diverse set of molecules, and show multitask learning improves the predictions. This work provides insight into the hydrophobicity of small molecules and ML cheminformatics modeling, and our data set will be useful for designing and testing future ML cheminformatics methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An In-Depth Exploration of the Electrochemical Oxygen Reduction Reaction (ORR) Phenomenon on Carbon-Based Catalysts in Alkaline and Acidic Mediums

Detailed studies of the electrochemical oxygen reduction reaction (ORR) on catalyst materials are crucial to improving the performance of different electrochemical energy conversion and storage systems (e.g., fuel cells and batteries), as well as numerous chemical synthesis processes. In the effort to reduce the loading of expensive platinum group metal (PGM)-based catalysts for ORR in the electrochemical systems, many carbon-based catalysts have already shown promising results and numerous investigations on those catalysts are in progress. Most of these studies show the catalyst materials’ ORR performance as current density data obtained through the rotating disk electrode (RDE), rotating ring-disk electrode (RRDE) experiments taking cyclic voltammograms (CV) or linear sweep voltammograms (LSV) approaches. However, the provided descriptions or interpretations of those data curves are often ambiguous and recondite which can lead to an erroneous understanding of the ORR phenomenon in those specific systems and inaccurate characterization of the catalyst materials. In this paper, we presented a study of ORR on a newly developed carbon-based catalyst, the nitrogen-doped graphene/metal-organic framework (N-G/MOF), through RDE and RRDE experiments in both alkaline and acidic mediums, taking the LSV approach. The functions and crucial considerations for the different parts of the RDE/RRDE experiment such as the working electrode, reference electrode, counter electrode, electrolyte, and overall RDE/RRDE process are delineated which can serve as guidelines for the new researchers in this field. Experimentally obtained LSV curves’ shapes and their correlations with the possible ORR reaction pathways within the applied potential range are discussed in depth. We also demonstrated how the presence of hydrogen peroxide (H2O2), a possible intermediate of ORR, in the alkaline electrolyte and the concentration of acid in the acidic electrolyte can maneuver the ORR current density output in compliance with the possible ORR pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanotransduction: all signals point to cytoskeleton, matrix, and integrins

Mechanical stresses modulate cell function by either activating or tuning signal transduction pathways. Mechanotransduction, the process by which cells convert mechanical stimuli into a chemical response, occurs both in cells specialized for sensing mechanical cues and in parenchymal cells whose primary function is not mechanosensory. However, common among the various responses to mechanical stress is the importance of direct or indirect connections between the internal cytoskeleton, the extracellular matrix (ECM), and traditional signal transducing molecules. In many instances, these elements converge at focal adhesions, sites of structural attachment between the cytoskeleton and ECM that are anchored by cell surface integrin receptors. Alenghat and Ingber discuss the accumulating evidence for the central role of cytoskeleton, ECM, and integrin-anchored focal adhesions in several mechanotransduction pathways.

Review, Tutorial↗

P/N InP solar cells on Ge wafers

Indium phosphide (InP) P-on-N one-sun solar cells were epitaxially grown using a metalorganic chemical vapor deposition process on germanium (Ge) wafers. The motivation for this work is to replace expensive InP wafers, which are fragile and must be thick and therefore heavy, with less expensive Ge wafers, which are stronger, allowing use of thinner, lighter weight wafers. An intermediate InxGs1-xP grading layer starting as In(0.49)Ga(0.51) at the GaAs-coated Ge wafer surface and ending as InP at the top of the grading layer (backside of the InP cell) was used to attempt to bend some of the threading dislocations generated by lattice-mismatch between the Ge wafer and InP cell so they would be harmlessly confined in this grading layer. The best InP/Ge cell was independently measured by NASA-Lewis with a one-sun 25 C AMO efficiently measured by NASA-Lewis with a one-circuit photocurrent 22.6 mA/sq cm. We believe this is the first published report of an InP cell grown on a Ge wafer. Why get excited over a 9 percent InP/Ge cell? If we look at the cell weight and efficiency, a 9 percent InP cell on an 8 mil Ge wafer has about the same cell power density, 118 W/kg (BOL), as the best InP cell ever made, a 19 percent InP cell on an 18 mil InP wafer, because of the lighter Ge wafer weight. As cell panel materials become lighter, the cell weight becomes more important, and the advantage of lightweight cells to the panel power density becomes more important. In addition, although InP/Ge cells have a low beginning-of-life (BOL) efficiency due to dislocation defects, the InP/Ge cells are very radiation hard (end-of-life power similar to beginning-of-life). We have irradiated an InP/Ge cell with alpha particles to an equivalent fluence of 1.6 x 10(exp 16) 1 MeV electrons/sq cm and the efficiency is still 83 percent of its BOL value. At this fluence level, the power output of these InP/Ge cells matches the GaAs/Ge cell data tabulated in the JPL handbook. Data are presented indicating InP/Ge has more power output than GaAs/Ge cells at fluences in excess of this value.

Wojtczuk, Steven↗

Hybrid nanocapsules for in situ TEM imaging of gas evolution reactions in confined liquids

Liquid cell transmission electron microscopy (TEM) enables the direct observation of dynamic physical and chemical processes in liquids at the nanoscale. Quantitative investigations into reactions with fast kinetics and/or multiple reagents will benefit from further advances in liquid cell design that facilitate rapid in situ mixing and precise control over reagent volumes and concentrations. This work reports the development of inorganic–organic nanocapsules for high-resolution TEM imaging of nanoscale reactions in liquids with well-defined zeptoliter volumes. These hybrid nanocapsules, with 48 nm average diameter, consist of a thin layer of gold coating a lipid vesicle. As a model reaction, the nucleation, growth, and diffusion of nanobubbles generated by the radiolysis of water is investigated inside the nanocapsules. When the nanobubbles are sufficiently small (10–25 nm diameter), they are mobile in the nanocapsules, but their movement deviates from Brownian motion, which may result from geometric confinement by the nanocapsules. Gases and fluids can be transported between two nanocapsules when they fuse, demonstrating in situ mixing without using complex microfluidic schemes. The ability to synthesize nanocapsules with controlled sizes and to monitor dynamics simultaneously inside multiple nanocapsules provides opportunities to investigate nanoscale processes such as single nanoparticle synthesis in confined volumes and biological processes such as biomineralization and membrane dynamics.

36 MATERIALS SCIENCE↗

Cell movement is guided by the rigidity of the substrate

Directional cell locomotion is critical in many physiological processes, including morphogenesis, the immune response, and wound healing. It is well known that in these processes cell movements can be guided by gradients of various chemical signals. In this study, we demonstrate that cell movement can also be guided by purely physical interactions at the cell-substrate interface. We cultured National Institutes of Health 3T3 fibroblasts on flexible polyacrylamide sheets coated with type I collagen. A transition in rigidity was introduced in the central region of the sheet by a discontinuity in the concentration of the bis-acrylamide cross-linker. Cells approaching the transition region from the soft side could easily migrate across the boundary, with a concurrent increase in spreading area and traction forces. In contrast, cells migrating from the stiff side turned around or retracted as they reached the boundary. We call this apparent preference for a stiff substrate "durotaxis." In addition to substrate rigidity, we discovered that cell movement could also be guided by manipulating the flexible substrate to produce mechanical strains in the front or rear of a polarized cell. We conclude that changes in tissue rigidity and strain could play an important controlling role in a number of normal and pathological processes involving cell locomotion.

NASA Discipline Cell Biology↗

Quantization effects in semiconductor nanostructures and singlet fission in molecular chromophores for photovoltaics and solar fuels

Hot carriers in semiconductors are electrons and/or holes that have energies greater than carriers that reside at the top and bottom of the conduction and valence bands, respectively; the latter carriers are in equilibrium with the lattice and have a temperature equal to the lattice (ambient) temperature. Hot carriers are created in semiconductors upon the absorption of photons with energies greater than the bandgap. The excess energy above the bandgap energy is in the form of kinetic energy. The hot carriers can cool to the lattice temperature via electron–phonon scattering and establish separate Boltzmann distributions for electrons and holes at the band edges. Thus, upon cooling, the excess kinetic energy of the hot carriers is transformed into heat and is unavailable to be converted into electrical or chemical free energy in a solar photon-converting cell. This hot-carrier cooling process significantly limits the maximum possible power conversion efficiency (PCE) of the free energy of solar photons into electrical free energy or chemical free energy in chemical bonds of fuels. However, if hot-carrier cooling can be slowed such that the hot carriers can be extracted before cooling to create higher photovoltages, or utilized to create additional electron-hole pairs through carrier multiplication, then beneficial use can be made of the excess energy of hot carriers and the maximum thermodynamic PCE can be dramatically increased. Quantization effects in semiconductor nanostructures, unique properties of some bulk semiconductors, and exciton multiplication in both semiconductors and molecular chromophores that undergo singlet fission have shown a path forward for potential dramatic increases in the PCEs of solar photons into electricity and solar fuels. The status, history, and future promise of the science and technology of these future approaches for different types of photovoltaic cells and cells for solar fuels will be discussed.

14 SOLAR ENERGY↗

Microfluidic cells for the 1–10 2 MPa pressure range

Thin membrane-delimited fluid cells supporting up to 1 at (0.1 MPa) of pressure are well known and commercially available for use in vacuum chambers of electron, photon, or various particle beam microscopies or spectroscopies. Hereby, we report on the development of fluid cells capable of working at 1–10 MPa, extending the analysis domain for investigating chemical, biochemical, or physical processes at pressures of interest in chemical synthesis, underwater biochemistry studies or underground geology. We explored ways to optimize cell membranes to better resist pressure beyond simply increasing the thickness or decreasing the size of the membranes, using finite element analysis and experimental validation via membrane bulging experiments and failure statistics. Fluid cell prototypes were fabricated using ∼75 nm-thick SiN x membranes, engineered to withstand 4.7 MPa (average value), compared to regular (un-engineered) membranes withstanding only 3.4 MPa (average value). The fluid cell prototypes include eight microchannels for feeding/evacuating the fluids and applying pressure into micro-reaction chambers, two electrodes for electrochemical or conduction measurements in the sample, and a possible pressure or temperature sensor, customizable for specific experiments.

hi-pressure↗

Vacuum MOCVD fabrication of high efficience cells

Vacuum metal-organic-chemical-vapor-deposition (MOCVD) is a new fabrication process with improved safety and easier scalability due to its metal rather than glass construction and its uniform multiport gas injection system. It uses source materials more efficiently than other methods because the vacuum molecular flow conditions allow the high sticking coefficient reactants to reach the substrates as undeflected molecular beams and the hot chamber walls cause the low sticking coefficient reactants to bounce off the walls and interact with the substrates many times. This high source utilization reduces the materials costs power device and substantially decreases the amounts of toxic materials that must be handled as process effluents. The molecular beams allow precise growth control. With improved source purifications, vacuum MOCVD has provided p GaAs layers with 10-micron minority carrier diffusion lengths and GaAs and GaAsSb solar cells with 20% AMO efficiencies at 59X and 99X sunlight concentration ratios. Mechanical stacking has been identified as the quickest, most direct and logical path to stacked multiple-junction solar cells that perform better than the best single-junction devices. The mechanical stack is configured for immediate use in solar arrays and allows interconnections that improve the system end-of-life performance in space.

Partain, L. D.↗

Functional lipid pairs as building blocks of phase-separated membranes

Biological membranes exhibit a great deal of compositional and phase heterogeneity due to hundreds of chemically distinct components. As a result, phase separation processes in cell membranes are extremely difficult to study, especially at the molecular level. It is currently believed that the lateral membrane heterogeneity and the formation of domains, or rafts, are driven by lipid–lipid and lipid–protein interactions. Nevertheless, the underlying mechanisms regulating membrane heterogeneity remain poorly understood. In the present work, we combine inelastic X-ray scattering with molecular dynamics simulations to provide direct evidence for the existence of strongly coupled transient lipid pairs. These lipid pairs manifest themselves experimentally through optical vibrational (a.k.a. phononic) modes observed in binary (1,2-dipalmitoyl- sn -glycero-3-phosphocholine [DPPC]–cholesterol) and ternary (DPPC–1,2-dioleoyl- sn -glycero-3-phosphocholine/1-palmitoyl-2-oleoyl-glycero-3-phosphocholine [DOPC/POPC]–cholesterol) systems. The existence of a phononic gap in these vibrational modes is a direct result of the finite size of patches formed by these lipid pairs. The observation of lipid pairs provides a spatial (subnanometer) and temporal (subnanosecond) window into the lipid–lipid interactions in complex mixtures of saturated/unsaturated lipids and cholesterol. Our findings represent a step toward understanding the lateral organization and dynamics of membrane domains using a well-validated probe with a high spatial and temporal resolution.

60 APPLIED LIFE SCIENCES↗