Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Unconventional”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 793 records · Page 44

Coherent approach to two-dimensional heterolayered oxychalcogenides using molten hydroxides.

Heterolayered structures consist of two or more different types of layer and can exhibit exceptional physical properties. Rational routes to synthesize new members of such compounds are required because most of these compounds have been discovered unintentionally. So far there is no generic method to vertically stack chemically different layers to form two-dimensional compounds owing to a lack of understanding of the synthesis of these materials. Here we report the use of molten hydroxides as unconventional solutions for the rapid stacking of oxide and chalcogenide layers with precise composition control. In addition, the crystal growth of heterolayered phases can be achieved by the reaction of different components at their diffusion front in molten hydroxides. This approach creates conditions in which the building blocks for each heterolayer can coexist, enabling heterolayered structures and bypassing the challenges of traditional solid-state chemistry methods where short reactant diffusion lengths predominate. This crystal growth methodology for heterolayers is also applicable to systems that do not form congruent melts at high temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A low temperature unitized regenerative fuel cell realizing 60% round trip efficiency and 10 000 cycles of durability for energy storage applications

Unitized regenerative fuel cells (URFC) convert electrical energy to and from chemical bonds in hydrogen. URFCs have the potential to provide economical means for efficient long-term, seasonal, energy storage and on-demand conversion back to electrical energy. We first optimize the catalyst layer for discrete electrolyzer and fuel cell and then configure the URFC. The goal is to identify a cost competitive configuration for URFCs, and demonstrate it in terms of upper limit of round trip efficiencies (RTEs). Two possible configurations of URFCs are compared via experiments and techno-economic analysis (TEA), which emphasize the advantages of the unconventional constant-electrode (CE) URFC over the traditional constant-gas (CG) configuration. We also study the stability via accelerated stress tests (ASTs) and demonstrate steady state operation in a daily cycle for day to night energy shifting. From the investigations, the optimum composition of the URFC anode catalyst layer is 90 at% Ir-black balanced by Pt-black for both CE and CG configurations. At 80 °C and 1 A cm -2 , the optimized CE URFC achieves 57% and 60% RTE with air and O 2 as the reductant gases, respectively. We then evaluated the differences in durability using an AST over 10k charge–discharge cycles; the results reveal that the wider potential window at the anode in CE (0.05–1.55 V) has minimal effect on catalyst layer stability compared to CG (0.55–1.55 V). Furthermore, there was no degradation up to the range of 2k–5k cycles; beyond that the fuel cell (discharge) performance degraded while the electrolyzer (charge) performance was still stable. Finally, the observations here indicate substantial potential to employ URFCs as efficient and cost-effective bidirectional energy-conversion devices within energy storage and utilization systems after appropriate technological and operational optimizations.

25 ENERGY STORAGE↗

Bio-inspired strategies for next-generation perovskite solar mobile power sources

Smart electronic devices are becoming ubiquitous due to many appealing attributes including portability, long operational time, rechargeability and compatibility with the user-desired form factor. Integration of mobile power sources (MPS) based on photovoltaic technologies with smart electronics will continue to drive improved sustainability and independence. With high efficiency, low cost, flexibility and lightweight features, halide perovskite photovoltaics have become promising candidates for MPS. Realization of these photovoltaic MPS (PV-MPS) with unconventionally extraordinary attributes requires new ‘out-of-box’ designs. Natural materials have provided promising designing solutions to engineer properties under a broad range of boundary conditions, ranging from molecules, proteins, cells, tissues, apparatus to systems in animals, plants, and humans optimized through billions of years of evolution. Applying bio-inspired strategies in PV-MPS could be biomolecular modification on crystallization at the atomic/meso-scale, bio-structural duplication at the device/system level and bio-mimicking at the functional level to render efficient charge delivery, energy transport/utilization, as well as stronger resistance against environmental stimuli (e.g., self-healing and self-cleaning). In this paper, we discuss the bio-inspired/-mimetic structures, experimental models, and working principles, with the goal of revealing physics and bio-microstructures relevant for PV-MPS. Here the emphasis is on identifying the strategies and material designs towards improvement of the performance of emerging halide perovskite PVs and strategizing their bridge to future MPS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metallofullerene photoswitches driven by photoinduced fullerene-to-metal electron transfer

We report on the discovery and detailed exploration of the unconventional photo-switching mechanism in metallofullerenes, in which the energy of the photon absorbed by the carbon cage π-system is transformed to mechanical motion of the endohedral cluster accompanied by accumulation of spin density on the metal atoms. Comprehensive photophysical and electron paramagnetic resonance (EPR) studies augmented by theoretical modelling are performed to address the phenomenon of the light-induced photo-switching and triplet state spin dynamics in a series of Y x Sc 3-x N@C 80 (x = 0–3) nitride clusterfullerenes. Variable temperature and time-resolved photoluminescence studies revealed a strong dependence of their photophysical properties on the number of Sc atoms in the cluster. All molecules in the series exhibit temperature-dependent luminescence assigned to the near-infrared thermally-activated delayed fluorescence (TADF) and phosphorescence. The emission wavelengths and Stokes shift increase systematically with the number of Sc atoms in the endohedral cluster, whereas the triplet state lifetime and S 1 –T 1 gap decrease in this row. For Sc 3 N@C 80 , we also applied photoelectron spectroscopy to obtain the triplet state energy as well as the electron affinity. Spin distribution and dynamics in the triplet states are then studied by light-induced pulsed EPR and ENDOR spectroscopies. The spin–lattice relaxation times and triplet state lifetimes are determined from the temporal evolution of the electron spin echo after the laser pulse. Well resolved ENDOR spectra of triplets with a rich structure caused by the hyperfine and quadrupolar interactions with 14 N, 45 Sc, and 89 Y nuclear spins are obtained. The systematic increase of the metal contribution to the triplet spin density from Y 3 N to Sc 3 N found in the ENDOR study points to a substantial fullerene-to-metal charge transfer in the excited state. These experimental results are rationalized with the help of ground-state and time-dependent DFT calculations, which revealed a substantial variation of the endohedral cluster position in the photoexcited states driven by the predisposition of Sc atoms to maximize their spin population.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Defect-free-induced Na + disordering in electrode materials

For reaching high-performance of electrode materials, it is generally believed that understanding the structure evolution and heterogeneous alignment effect is the key. Presently, a very simple and universally applicable self-healing method is investigated to prepare defect-free Prussian blue analogs (PBAs) that reach their theoretical capacity as cathode materials for sodium-ion batteries (SIBs). For direct imaging of the local structure and the dynamic process at the atomic scale, we deliver a fast ion-conductive nickel-based PBA that enables rapid Na + extraction/insertion within 3 minutes and a capacity retention of nearly 100% over 4000 cycles. This guest-ion disordered and quasi-zero-strain nonequilibrium solid–solution reaction mechanism provides an effective guarantee for realizing long-cycle life and high-rate capability electrode materials that operate via reversible two-phase transition reaction. Unconventional materials and mechanisms that enable reversible insertion/extraction of ions in low-cost metal–organic frameworks (MOFs) within minutes have implications for fast-charging devices, grid-scale energy storage applications, material discovery, and tailored modification.

36 MATERIALS SCIENCE↗

Intrinsic helical twist and chirality in ultrathin tellurium nanowires

Robust atomic-to-meso-scale chirality is now observed in the one-dimensional form of tellurium. This enables a large and counter-intuitive circular-polarization dependent second harmonic generation response above 0.2 which is not present in two-dimensional tellurium. Orientation variations in 1D tellurium nanowires obtained by four-dimensional scanning transmission electron microscopy (4D-STEM) and their correlation with unconventional non-linear optical properties by second harmonic generation circular dichroism (SHG-CD) uncovers an unexpected circular-polarization dependent SHG response from 1D nanowire bundles – an order-of-magnitude higher than in single-crystal two-dimensional tellurium structures – suggesting the atomic- and meso-scale crystalline structure of the 1D material possesses an inherent chirality not present in its 2D form; and which is strong enough to manifest even in the aggregate non-linear optical (NLO) properties of aggregates.

36 MATERIALS SCIENCE↗

Thermodynamic guiding principles of high-capacity phase transformation materials for splitting H 2 O and CO 2 by thermochemical looping

Here, thermochemical looping splitting of water and carbon dioxide (CO 2 ) with greenhouse-gas-free (GHG-free) energy has the potential to help address the Gt-scale GHG emissions challenge. Reaction thermodynamics largely contributes to the main bottlenecks of cost reduction for thermochemical looping water/CO 2 splitting cycle. Here, we analyze thermodynamic driving forces in such cycles with two-phase ternary ferrites as model systems. We find that cation configurational entropy chiefly determines the change of partial molar entropy with oxygen stoichiometry. In addition, our phase diagram analysis accurately predicts the optimal Fe ratio for maximal water/CO 2 splitting capacity in thermal reduction and in chemical reduction based cycles, underlining the significance of phase boundary positions. With chemical reduction, >10% CO 2 conversion and high oxygen exchange capacity can both be achieved. Furthermore, our reduced Gibbs free energy model illustrates critical thermodynamic factors that influence the water/CO 2 splitting capacity. Our research reveals the thermodynamic driving forces underlying the unconventional high-capacity Fe-poor ferrites, further explained via phase diagrams of Fe–Co–O, Fe–Ni–O and Fe–Mg–O. Future materials improvements can be guided by our reduced Gibbs free energy model.

08 HYDROGEN↗

Robust chain aggregation of low-entropy rigid ladder polymers in solution

Conjugated polymers have been widely investigated where ladder-type conjugated polymers receive more attention due to their rigid backbones and extraordinary properties. However, the understanding of how the rigid conformation of ladder polymers translates to material properties is still limited. Here, we systematically investigated the solution aggregation properties of a carbazole-derived conjugated ladder polymer (LP) and its analogous non-ladder control polymer (CP) via light scattering, neutron scattering, and UV-vis absorption spectroscopy characterization techniques, revealing a highly robust, temperature-insensitive aggregation behavior of the LP. The experimental findings were further validated by computational molecular dynamics simulations. Here we found that the peak positions and intensities of the UV spectra of the LP remained constant between 20 °C and 120 °C in chlorobenzene solution. The polymer also showed a stable hydrodynamic radius measured by dynamic light scattering from 20 °C to 70 °C in the chlorobenzene solution. Using small-angle neutron scattering, no Guinier region was reached in the measured q range down to 0.008 Å –1 , even at elevated temperature. In contrast, the non-ladder control polymer CP was fully soluble in the chlorobenzene solvent without the observation of any notable aggregates. The Brownian dynamics simulation showed that during polymer aggregation, the entropy change of the LP was significantly less negative than that of the non-ladder control polymer. These findings revealed the low entropy nature of rigid conjugated ladder polymers and the low entropy penalty for their aggregation, which is promising for highly robust intermolecular interactions at high temperatures. Such a unique thermodynamic feature of rigid ladder polymers can be leveraged in the design and application of next-generation electronic and optoelectronic devices that function under unconventional high temperature conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design of high polarization low switching barrier hybrid improper ferroelectric perovskite oxide superlattices

Hybrid improper ferroelectricity is a useful tool to design ABO 3 /A'BO 3 polar superlattices from non polar building blocks. In this study, we have designed high polarization-low switching barrier hybrid improper ferroelectric superlattices with efficient polarization, and polarization-magnetization switching properties above room temperature, using density functional theory and ab initio molecular dynamics simulations. Superlattices with a chemical formula of (AAlO 3 ) m /(A'AlO 3 ) n , where m/n = 1/1, 1/3, 3/1, 1/5 and 5/1, A, A' = Lanthanide and Y cations are considered to outline the design principles behind polarization switching and (LaFeO 3 ) 3 /(CeFeO 3 ) 1 is investigated for polarization-magnetization switching. We find that the unconventional switching paths via out-of-phase rotation Q R- (a 0 a 0 c - ) and tilt precession QTP always yield lower switching barrier compared to those via in-phase rotation Q R+ (a 0 a 0 c + ) and tilt QT (a - a - c 0 ) of BO 6 octahedra. Results from ab initio molecular dynamics simulations estimate the temperature at which the lowest energy barrier can be overcome. Furthermore, it is possible to tune the polarization switching barrier by tuning the tolerance factor, A,A' cation radius mismatch and super lattice periodicity. For switching via Q R- , the switching barrier varies exponentially with rotation angle, indicating how high switching barrier is expected for systems, away from cubic symmetry. We provide a recipe to overcome such a bottleneck by tuning superlattice periodicity. Finally, we have proposed the multiferroic device application concept through a proposed polarization-temperature hysteresis loop and magnetization switching.

36 MATERIALS SCIENCE↗

Effect of rare earth size on network structure and glass forming ability in binary aluminum garnets

Rare earth aluminate glasses are potentially useful for optical, luminescence, and laser applications. As reluctant glass formers, these materials exhibit unconventional atomic structures. To better understand how their structures correlate with glass formation, we investigate two rare earth aluminum garnet melts, La 3 Al 5 O 12 (LAG) and Yb 3 Al 5 O 12 (YbAG), which represent the relative extremes of good and poor glass forming ability in rare earth aluminates. Structural models have been refined to high-energy X-ray diffraction data over 1340–2740 K. Both melts contain mixtures of AlO 4 , AlO 5 , and AlO 6 polyhedra, with larger fractions of [5] Al and [6] Al in YbAG. Extrapolation of the Al–O coordination distributions to the glass transition match closely with 27 Al nuclear magnetic resonance measurements of (La 1−z Y z ) 3 Al 5 O 12 glasses, z = 0 to 1. During cooling, the mean coordination numbers increase for La–O in LAG from 6.45(8) to 6.98(8) and for Yb–O in YbAG from 6.02(8) to 6.21(8). Linkedness among Al–O polyhedra at ∼2450 K is mostly corner-sharing, with 9% edge-sharing in LAG and 19% in YbAG. Among [4] Al units, both melts have 6% edge-sharing that convert to all corner-sharing upon cooling. Network connectivity is compared using a newly defined metric, K n , that is similar to the Q n distribution but that accounts for the edge-sharing and triply bonded oxygen present in these melts. The lower glass forming ability in YbAG as compared to LAG correlates with more edge-sharing, associated with the larger fractions of [5] Al and [6] Al, and lower connectivity among [4] Al units.

Wilke, Stephen K. [Materials Development, Inc., Ar↗

Elucidating molecular level interfacial interactions between a de novo protein and nucleated calcite with solid-state NMR

Biomineralization is the process by which organisms use biomolecules to produce hierarchically structured organic–inorganic composites. Using biology as inspiration, a protein construct (FD31) was previously designed to accelerate formation of nano-calcite with an unconventional {110} face. Here, to understand the molecular interactions essential for protein aided calcite nucleation, solid-state nuclear magnetic resonance (ssNMR) spectroscopy was used in this work to characterize the FD31–calcite interface at the atomic level. Glutamic acid side chains designed to interact directly with calcium ions on the surface were found to have dynamics on the sub-millisecond timescale, indicating possible interactions between the protein and surface waters that were not included in the original model. Dipolar ssNMR recoupling techniques also showed that the protein backbone is ∼2 Å closer to the surface than in the original docking model. Refined molecular simulations were done in the presence of explicit waters, which resulted in the protein backbone closer to the surface than in the original docking structure, providing better agreement with experiment and highlighting the important role played by water in FD31–calcite interactions. While this work provides the first experimental confirmation that FD31 interactions with calcite are localized to the surface of the protein designed to serve as a template, these studies do indicate a more dynamic binding and closer binding mode between FD31 and the nucleated surface than originally proposed. In all, this enhanced molecular insight into the FD31–calcite interface has advanced our fundamental understanding of the atomic interactions at the organic–inorganic interface and will aid in the design of biological templates for the nucleation of inorganic crystals.

Close, Emily G. S. [Pacific Northwest National Lab↗

Direct measurement of covalent three-center, two-electron M–H–B bonding in Zr and Hf borohydrides using B K-edge XAS

Metal borohydride complexes have long been the subject of intense fundamental interest because of their unconventional metal–ligand bonding that occurs via three-center, two-electron M–H–B bonds. This type of bonding implies significant delocalization of electron density over all three atoms, but the degree of orbital mixing between the metal and boron has been difficult to assess by direct experimental means. Herein, we demonstrate how ligand K-edge X-ray absorption spectroscopy (XAS) conducted at the B K-edge yields evidence of significant covalent M–H–B bonding with Zr and Hf. To accommodate the B K-edge XAS studies, which were conducted under ultra-high vacuum (<10 −8 torr), we prepared a series of new [Zr(RBH 3 ) 4 ] and [Hf(RBH 3 ) 4 ] complexes with substituents that attenuate volatility (R = benzyl, phenyl, mesityl, 2,4,6-triisopropylphenyl, and anthryl). 1 H and 11 B NMR spectroscopy, IR spectroscopy, and single-crystal X-ray diffraction (XRD) studies revealed metal and ligand dependent differences in the BH 3 chemical shifts that correlate to changes in M−B distances and select B–H vibrational stretching modes. The B K-edge XAS spectra of the Zr and Hf complexes yielded a pre-edge feature that was assigned as B 1s → M–H–B π* based on comparison to time-dependent density functional theory (TDDFT) calculations. The pre-edge transitions appear due to covalent mixing between boron and the metal, thereby demonstrating how B K-edge XAS can provide direct evidence of covalent three-center, two electron M–H–B bonding in borohydride complexes using boron as a spectroscopic reporter.

Hansen, Hannah M. [University of Iowa, Iowa City, ↗

Molecular orbital symmetry-driven trimer formation in Kagome correlated electron materials

Correlated electron materials with molecular orbital states extending over transition metal clusters can host multiferroicity, spin frustration, and unconventional insulating phases. However, the fundamental criteria that govern cluster formation and stability remain unclear. Here, we identify a symmetry, correlation, and electron-filling-driven criteria that stabilize triangular metal trimers in materials displaying transition metal Kagome patterns. Using density functional theory and chemical bonding analysis, we show that trimer formation emerges when 6–8 electrons occupy molecular orbitals derived from transition metal d-states, achieving near-complete filling of bonding states while avoiding antibonding occupation, and correlations are of intermediate strength. This principle explains the stability of Nb 3 X 8 (X = Cl, Br, I), and more broadly, our findings offer a general design rule to obtain quantum materials with quantum states extended across transition metal clusters.

Kumari, Varsha [Indiana Univ., Bloomington, IN (Un↗

Improved nylon polymerization using amide diads

Nylons, a major class of synthetic polyamides, are widely used due to their excellent mechanical strength, thermal stability, and chemical resistance. Conventional nylon production relies on the polymerization of lactams or stoichiometric nylon salts. However, applying these approaches to unconventional precursors such as bio-derived glutaric acid produces polymers with low molecular weight and limited applications. To address these challenges, we demonstrated that chemically-synthesized nylon diads enable the production of higher-molecular-weight polyamides compared with traditional salts. We then identified a biosynthetic approach using amide synthetases to convert unprotected bifunctional substrates into nylon-relevant diads. Using a cofactor regeneration system, enzymatic diad synthesis was scaled to produce sufficient material for laboratory-scale characterization and solid-state polymerization. Amide synthetases demonstrated broad substrate scope, catalyzing the regioselective assembly of diverse nylon-relevant diacids, diamines, and ω-amino acids. This strategy offers a novel route to synthesize challenging nylon monomers and advances production of bioderived nylons.

Qian, Liangyu [Oak Ridge National Laboratory (ORNL↗

Tunneling electroresistance effects in epitaxial complex oxides on silicon

Complex oxide-based ferroelectric tunnel junctions (FTJs) show excellent nonvolatile memory characteristics promising for emerging technology. However, integration of these epitaxially grown FTJs electrically with a silicon substrate remains challenging due to their incompatible lattice structures and poor electronic interfaces resulting from the direct synthesis techniques. Here, we present an epitaxial SrRuO 3 /PbZr 0.2 Ti 0.8 O 3 /SrRuO 3 FTJ integrated electrically with a doped silicon substrate after a layer transfer process. The tunnel currents of the FTJ on silicon show a large tunneling electroresistance (~1×10 5 %) effect, which is explained by a numerical FTJ model incorporating pinned dipoles at the interfaces. This proof of concept of the integration of functional oxide heterostructures with silicon opens a pathway to beyond-CMOS computing devices using unconventional materials.

36 MATERIALS SCIENCE↗