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At least 181 records · Page 10

Can a shock-induced phonon up-pumping model relate to impact sensitivity of molecular crystals, polymorphs and cocrystals?

Impact sensitivity engineering of high-energy molecular crystals requires accurate predictive models. For this purpose, the promising multi-phonon based approach is selected, assessing a bit more its strengths and weaknesses. Presently used with high-quality phonon calculations of 22 molecular crystals, using a physics-based criterion to determine the phonon bath extent, the resulting intrinsic shock sensitivity index (SSI) is compared to the most common marker of impact sensitivity, h 50 , as determined from drop-weight impact tests. Selecting a data subset from experiments performed under very similar conditions (2.5 kg hammer with grit and 30–40 mg samples), the model can predict h 50 values for mono-molecular crystals with very good accuracy, including the ability to discriminate the polymorphs of HMX and CL20. This very good agreement validates an initial indirect up-pumping mechanism occurring under these conditions, where the doorway modes also interact with the phonon bath. However, the phonon bath criterion for mono-molecular crystals does not transfer well to cocrystals. Owing to the vibrational coupling of the co-molecules, it seems a broader phonon bath should be considered. Additionally recalling experimental uncertainty and various experimental factors affecting h 50 values for a given compounds, we recommend that the density of the sample, granularity and morphology be systematically considered and reported along with measurements, which will in turn allow for more systematic data and predictive capabilities for sensitivity models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fundamental Ice Crystal Accretion Physics Studies

Due to numerous engine power-loss events associated with high-altitude convective weather, ice accretion within an engine due to ice-crystal ingestion is being investigated. The National Aeronautics and Space Administration (NASA) and the National Research Council (NRC) of Canada are starting to examine the physical mechanisms of ice accretion on surfaces exposed to ice-crystal and mixed-phase conditions. In November 2010, two weeks of testing occurred at the NRC Research Altitude Facility utilizing a single wedge-type airfoil designed to facilitate fundamental studies while retaining critical features of a compressor stator blade or guide vane. The airfoil was placed in the NRC cascade wind tunnel for both aerodynamic and icing tests. Aerodynamic testing showed excellent agreement compared with CFD data on the icing pressure surface and allowed calculation of heat transfer coefficients at various airfoil locations. Icing tests were performed at Mach numbers of 0.2 to 0.3, total pressures from 93 to 45 kPa, and total temperatures from 5 to 15 C. Ice and liquid water contents ranged up to 20 and 3 grams per cubic meter, respectively. The ice appeared well adhered to the surface in the lowest pressure tests (45 kPa) and, in a particular case, showed continuous leading-edge ice growth to a thickness greater than 15 millimeters in 3 minutes. Such widespread deposits were not observed in the highest pressure tests, where the accretions were limited to a small area around the leading edge. The suction surface was typically ice-free in the tests at high pressure, but not at low pressure. The icing behavior at high and low pressure appeared to be correlated with the wet-bulb temperature, which was estimated to be above 0 C in tests at 93 kPa and below 0 C in tests at lower pressure, the latter enhanced by more evaporative cooling of water. The authors believe that the large ice accretions observed in the low pressure tests would undoubtedly cause the aerodynamic performance of a compressor component such as a stator blade to degrade significantly, and could damage downstream components if shed.

Currie, Tom↗

Recent Advances in the LEWICE Icing Model

This paper will describe two recent modifications to the Glenn ICE software. First, a capability for modeling ice crystals and mixed phase icing has been modified based on recent experimental data. Modifications have been made to the ice particle bouncing and erosion model. This capability has been added as part of a larger effort to model ice crystal ingestion in aircraft engines. Comparisons have been made to ice crystal ice accretions performed in the NRC Research Altitude Test Facility (RATFac). Second, modifications were made to the run back model based on data and observations from thermal scaling tests performed in the NRC Altitude Icing Tunnel.

fluid dynamics↗

Simultaneous Ice Water Content Measurements at Multiple Locations on the NASA DC-8 Aircraft during the 2018 HIWC RADAR Flight Campaign

Ice water content measurements were made simultaneously at three locations on the NASA DC-8 in natural, glaciated conditions during the 2018 High Ice Water Content RADAR flight campaign. The purpose of these measurements was to further evaluate efficiency factors of hot-wire total water content probes in glaciated conditions and investigate the enhancement of ice crystal concentrations near fuselage surfaces due to flow field inertial effects, and ice crystals impacting the nose, breaking up, and flowing downstream. The total water content measurements were made using either Science Engineering Associates Ice Crystal Detectors or Robust Probes. Three common sensors were mounted on an underwing canister considered to be in near free-flow conditions, a standoff from a fuselage window, and the nose of the fuselage near the pitot probes. The Ice Crystal Detector total water content sensor and Robust Probe sensor collection and retention efficiencies were evaluated through comparisons with the underwing Ice Crystal Detector and Robust Probe measurements to the IKP2 isokinetic evaporator probe, which provided the reference ice water content measurement. Local ice water content at the nose position was evaluated by comparing ratios of the nose and underwing ice crystal detectors to the IKP2. Local ice water content at the window-standoff location was also evaluated by comparing total water content sensor measurements from the window ice crystal detector to the measurements made with the underwing and nose Ice Crystal Detectors The key findings were: 1) the Ice Crystal Detector total water content sensor ice water content efficiency factor was similar to previous estimates, but reduced with increased ice crystal median mass diameter; 2) the ice water content at the fuselage nose location near the DC-8 pitot probes was approximately 2.5 times the freestream values – although this estimate is affected by a higher probe efficiency factor due to smaller particles in the debris cloud from impacts upstream of the probe; and 3) the ice water content at the 17” standoff from the port window varied from about 50% to 3 times freestream values in a complicated manner. Similar measurement locations are not uncommon on cloud research aircraft, where ice particle measurements may be subject to similar uncertainties.

Aircraft Icing↗

Simultaneous Ice Water Content Measurements at Multiple Locations on the NASA DC-8 Aircraft during the 2018 HIWC RADAR Flight Campaign

Ice water content measurements were made simultaneously at three locations on the NASA DC-8 in natural, glaciated conditions during the 2018 High Ice Water Content RADAR flight campaign. The purpose of these measurements was to further evaluate efficiency factors of hot-wire total water content probes in glaciated conditions and investigate the enhancement of ice crystal concentrations near fuselage surfaces due to flow field inertial effects, and ice crystals impacting the nose, breaking up, and flowing downstream. The total water content measurements were made using either Science Engineering Associates Ice Crystal Detectors or Robust Probes. Three common sensors were mounted on an underwing canister considered to be in near free-flow conditions, a standoff from a fuselage window, and the nose of the fuselage near the pitot probes. The Ice Crystal Detector total water content sensor and Robust Probe sensor collection and retention efficiencies were evaluated through comparisons with the underwing Ice Crystal Detector and Robust Probe measurements to the IKP2 isokinetic evaporator probe, which provided the reference ice water content measurement. Local ice water content at the nose position was evaluated by comparing ratios of the nose and underwing ice crystal detectors to the IKP2. Local ice water content at the window-standoff location was also evaluated by comparing total water content sensor measurements from the window ice crystal detector to the measurements made with the underwing and nose Ice Crystal Detectors The key findings were: 1) the Ice Crystal Detector total water content sensor ice water content efficiency factor was similar to previous estimates, but reduced with increased ice crystal median mass diameter; 2) the ice water content at the fuselage nose location near the DC-8 pitot probes was approximately 2.5 times the freestream values – although this estimate is affected by a higher probe efficiency factor due to smaller particles in the debris cloud from impacts upstream of the probe; and 3) the ice water content at the 17” standoff from the port window varied from about 50% to 3 times freestream values in a complicated manner. Similar measurement locations are not uncommon on cloud research aircraft, where ice particle measurements may be subject to similar uncertainties.

o Aircraft Icing↗

Simultaneous Ice Water Content Measurements at Multiple Locations on the NASA DC-8 Aircraft during the 2018 HIWC RADAR Flight Campaign

Ice water content measurements were made simultaneously at three locations on the NASA DC-8 in natural, glaciated conditions during the 2018 High Ice Water Content RADAR flight campaign. The purpose of these measurements was to further evaluate efficiency factors of hot-wire total water content probes in glaciated conditions and investigate the enhancement of ice crystal concentrations near fuselage surfaces due to flow field inertial effects, and ice crystals impacting the nose, breaking up, and flowing downstream. The total water content measurements were made using either Science Engineering Associates Ice Crystal Detectors or Robust Probes. Three common sensors were mounted on an underwing canister considered to be in near free-flow conditions, a standoff from a fuselage window, and the nose of the fuselage near the pitot probes. The Ice Crystal Detector concave total water content sensor and Robust Probe sensor collection and retention efficiencies were evaluated through comparisons with the underwing Ice Crystal Detector and Robust Probe measurements to the Isokinetic Probe version 2 (IKP2), which provided the reference ice water content measurement. Local ice water content at the nose position was evaluated by comparing ratios of the nose and underwing ice crystal detectors to the IKP2. Local ice water content at the window-standoff location was also evaluated by comparing total water content sensor measurements from the window probes to the measurements made with the underwing and nose probes. The key findings were: (1) the Ice Crystal Detector concave water content sensor efficiency factor to glaciated conditions was similar to previous estimates, but reduced with increased ice crystal median mass diameter; (2) the ice water content at the fuselage nose location near the DC-8 pitot probes was approximately 2.5 times the freestream values—although this estimate is affected by a higher probe efficiency factor due to smaller particles in the debris cloud from impacts upstream of the probe; and (3) the ice water content at the 17 in. standoff from the port window varied from about 50 percent to nearly three times freestream values in a complicated manner. Similar measurement locations are not uncommon on cloud research aircraft, where ice particle measurements may be subject to similar uncertainties.

Aircraft Icing↗

Accurate computational design of three-dimensional protein crystals

Protein crystallization plays a central role in structural biology. Despite this, the process of crystallization remains poorly understood and highly empirical, with crystal contacts, lattice packing arrangements and space group preferences being largely unpredictable. Programming protein crystallization through precisely engineered side-chain-side-chain interactions across protein-protein interfaces is an outstanding challenge. Here, in this study, we develop a general computational approach for designing three-dimensional protein crystals with prespecified lattice architectures at atomic accuracy that hierarchically constrains the overall number of degrees of freedom of the system. We design three pairs of oligomers that can be individually purified, and upon mixing, spontaneously self-assemble into >100 µm three-dimensional crystals. The structures of these crystals are nearly identical to the computational design models, closely corresponding in both overall architecture and the specific protein-protein interactions. The dimensions of the crystal unit cell can be systematically redesigned while retaining the space group symmetry and overall architecture, and the crystals are extremely porous and highly stable. Our approach enables the computational design of protein crystals with high accuracy, and the designed protein crystals, which have both structural and assembly information encoded in their primary sequences, provide a powerful platform for biological materials engineering.

59 BASIC BIOLOGICAL SCIENCES↗

The microstructure and properties of rapidly solidified, dispersion-strengthened NiAl

An advanced rapid solidification technology for processing reactive and refractory alloys, utilized to produce large quantities of melt-spun filaments of NiAl, is presented. The melt-spun filaments are pulverized to fine particle sizes, and subsequently consolidated by hot extrusion or hot isostatic pressing. Rapid solidification process gives rise to very fine-grained microstructures. However, exposure to elevated temperature during hot consolidation leads to grain growth. Alloying agents such as borides, carbides, and tungsten can pin the grain boundaries and retard the grain growth. Various alloy compositions are investigated. The eventual goal is to utilize the hot-extruded and forged stock to grow single-crystal NiAl blades for advanced gas-turbine engine applications. Single-crystal NiAl, containing a uniform dispersion of carbide strengthening precipitates, is expected to lead to highly creep-resistant turbine blades, and is of considerable interest to the aerospace propulsion industry.

Jha, S. C.↗

Ice Crystal Icing Physics Study using a NACA 0012 Airfoil at the National Research Council of Canada's Research Altitude Test Facility

This paper presents results from a study of the fundamental physics of ice-crystal ice accretion using a NACA 0012 airfoil at the National Research Council of Canada (NRC) Research Altitude Test Facility in August 2017. These tests were a continuation of work which began in 2010 as part of a joint collaboration between NASA and NRC. The research seeks to generate icing conditions representative of those that occur inside a jet engine when ingesting ice crystals. In this test, an airfoil was exposed to mixed-phase icing conditions and the resulting ice accretions were recorded and analyzed. This paper details the specific objectives, procedures, and measurements which included the aero-thermal and cloud measurements. The objectives were built upon observations and hypothesis generated from several previous test campaigns regarding mixed-phase ice-crystal icing. The specific objectives included (A) ice accretions under different wet-bulb temperatures, (B) investigations of steady-state ice shapes previously reported in the literature, (C) total water content variations in search of a threshold for accretion, and (D) probe characterization related to measuring melt fraction which is important to characterize the mixed-phase condition. The resulting ice accretions and conditions leading to such accretions are intended to help extend NASA’s predictive ice-accretion codes to include conditions occurring in engine ice-crystal icing.

Icing↗

Insights into the Biomimetic Synthesis of 2D ZnO Nanomaterials through Peptoid Engineering

Achieving predictable biomimetic crystallization using sequence-defined synthetic molecules in mild conditions represents a long-standing challenge in materials synthesis. Herein we report a peptoid-based approach for biomimetic control over the formation of nanostructured ZnO materials in ambient aqueous conditions. A series of two-dimensional (2D) ZnO nanomaterials have been successfully obtained using amphiphilic peptoids with different numbers, ratios, and patterns of various hydrophilic and hydrophobic side chains. By investigating the relationship between peptoid hydrophobicity and the thickness of the resultant ZnO nanomaterials, we found the critical role of peptoid hydrophobicity in the peptoid-controlled ZnO formation. Our results suggest that tuning the hydrophobicity of peptoids can be used to moderate peptoid–ZnO surface interactions, thus controlling the formation of ultrathin (<2.5 nm) 2D ZnO nanomaterials. Here, the peptoid-controlled formation of ZnO nanomaterials was further investigated using ultrasmall-angle X-ray scattering (USAXS). Our work suggests a new approach to synthesizing 2D metal oxide nanomaterials using sequence-defined synthetic molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unraveling Anion-Specific Inhibition and Structural Modulation of Gibbsite Crystallization: Implications for Aluminum Mobility in Natural and Engineered Systems

Gibbsite (α-Al(OH) 3 , sometimes designated as γ-Al(OH) 3 ) plays a crucial role in the chemistry of aluminum in the environment and industry, yet its crystallization behavior under multianionic conditions is not well understood. Here, in this study, we investigate how six common anions─fluoride (F – ), chloride (Cl – ), bromide (Br – ), nitrate (NO 3 – ), sulfate (SO 4 2– ), and phosphate (PO 4 3– )─influence the mineralization, structure, and morphology of gibbsite at room temperature. The results show that PO 4 3– , SO 4 2– , and F – strongly inhibit gibbsite formation, stabilizing amorphous or alternative crystalline phases such as nordstrandite and cryolite. On the contrary, Cl – , Br – , and NO 3 – allow partial to complete crystallization of gibbsite without significant morphological changes. Solid-state 27 Al magic angle spinning nuclear magnetic resonance provides crucial insight into aluminum coordination environments in both crystalline and amorphous phases, distinguishing between octahedral, pentahedral, and tetrahedral Al species. The density functional theory calculations reveal a direct correlation between the Al–X bond strength and the inhibition of crystallization, following the order: PO 4 3– > SO 4 2– > F – > NO 3 – > Cl – > Br – . These findings offer molecular-scale insights into anion-specific effects on aluminum hydroxide nucleation and transformation, improving the understanding of gibbsite formation and aluminum cycling in soils, phosphate retention, contaminant immobilization, and waste treatment strategies in nuclear and industrial settings. These insights can also guide the controlled synthesis of aluminum hydroxide materials with tailored crystallinity and morphology via liquid-assisted methods.

Anions effect↗

PSL Icing Facility Upgrade Overview

The NASA Glenn Research Center Propulsion Systems Lab (PSL) was recently upgraded to perform engine inlet ice crystal testing in an altitude environment. The system installed 10 spray bars in the inlet plenum for ice crystal generation using 222 spray nozzles. As an altitude test chamber, the PSL is capable of simulating icing events at altitude in a groundtest facility. The system was designed to operate at altitudes from 4,000 to 40,000 ft at Mach numbers up to 0.8M and inlet total temperatures from -60 to +15 degF. This paper and presentation will be part of a series of presentations on PSL Icing and will cover the development of the icing capability through design, developmental testing, installation, initial calibration, and validation engine testing. Information will be presented on the design criteria and process, spray bar developmental testing at Cox and Co., system capabilities, and initial calibration and engine validation test. The PSL icing system was designed to provide NASA and the icing community with a facility that could be used for research studies of engine icing by duplicating in-flight events in a controlled ground-test facility. With the system and the altitude chamber we can produce flight conditions and cloud environments to simulate those encountered in flight. The icing system can be controlled to set various cloud uniformities, droplet median volumetric diameter (MVD), and icing water content (IWC) through a wide variety of conditions. The PSL chamber can set altitudes, Mach numbers, and temperatures of interest to the icing community and also has the instrumentation capability of measuring engine performance during icing testing. PSL last year completed the calibration and initial engine validation of the facility utilizing a Honeywell ALF502-R5 engine and has duplicated in-flight roll back conditions experienced during flight testing. This paper will summarize the modifications and buildup of the facility to accomplish these tests.

Griffin, Thomas A.↗

Self-Anchored Platinum-Decorated Antimony-Doped-Tin Oxide as a Durable Oxygen Reduction Electrocatalyst

The lifetime of commercial Proton Exchange Membrane Fuel Cells (PEMFCs) is circumscribed by the insufficient durability of commercial catalysts. The use of metal oxide supports in place of carbon significantly increases electrocatalyst durability. Herein, following density functional theory (DFT) predictions of improved Platinum (Pt) stability on antimony doped tin oxide (ATO) supports, we synthesized ATO whose morphology and crystal structure was engineered using a Pt anchoring technique. X-ray photoelectron spectroscopy (XPS) indicated that the Pt anchor sites aided in the reduction of Pt precursors to Pt on the ATO surface. X-ray absorption near-edge spectroscopy (XANES) revealed the existence of strong-metal-support interactions (SMSI) between Pt and ATO. The combination of SMSI and high control over Pt dispersion enabled the Pt/Pt-aerogel-ATO (Pt supported on aerogel ATO with Pt anchor sites) electrocatalyst to achieve 2x the area specific activity of Pt/C in ex-situ testing. In a H 2 /air PEMFC Pt/Pt-aerogel-ATO cathodes enabled 20% higher peak power density and <1/6 the loss of active surface area as compared to Pt/C. Notably, in a PEMFC under rigorous potential cycling, the Pt/Pt-aerogel-ATO retained its initial peak power density as opposed to a 58% loss for Pt/C. Further, cost models indicate that Pt/Pt-aerogel-ATO is 26% less expensive than Pt/C over its useful lifetime.

25 ENERGY STORAGE↗

Observation of formation and local structures of metal-organic layers via complementary electron microscopy techniques

Abstract Metal-organic layers (MOLs) are highly attractive for application in catalysis, separation, sensing and biomedicine, owing to their tunable framework structure. However, it is challenging to obtain comprehensive information about the formation and local structures of MOLs using standard electron microscopy methods due to serious damage under electron beam irradiation. Here, we investigate the growth processes and local structures of MOLs utilizing a combination of liquid-phase transmission electron microscopy, cryogenic electron microscopy and electron ptychography. Our results show a multistep formation process, where precursor clusters first form in solution, then they are complexed with ligands to form non-crystalline solids, followed by the arrangement of the cluster-ligand complex into crystalline sheets, with additional possible growth by the addition of clusters to surface edges. Moreover, high-resolution imaging allows us to identify missing clusters, dislocations, loop and flat surface terminations and ligand connectors in the MOLs. Our observations provide insights into controllable MOL crystal morphology, defect engineering, and surface modification, thus assisting novel MOL design and synthesis.

36 MATERIALS SCIENCE↗

Lithium crystallization at solid interfaces

Understanding the electrochemical deposition of metal anodes is critical for high-energy rechargeable batteries, among which solid-state lithium metal batteries have attracted extensive interest. A long-standing open question is how electrochemically deposited lithium-ions at the interfaces with the solid-electrolytes crystalize into lithium metal. Here, using large-scale molecular dynamics simulations, we study and reveal the atomistic pathways and energy barriers of lithium crystallization at the solid interfaces. In contrast to the conventional understanding, lithium crystallization takes multi-step pathways mediated by interfacial lithium atoms with disordered and random-closed-packed configurations as intermediate steps, which give rise to the energy barrier of crystallization. This understanding of multi-step crystallization pathways extends the applicability of Ostwald’s step rule to interfacial atom states, and enables a rational strategy for lower-barrier crystallization by promoting favorable interfacial atom states as intermediate steps through interfacial engineering. Our findings open rationally guided avenues of interfacial engineering for facilitating the crystallization in metal electrodes for solid-state batteries and can be generally applicable for fast crystal growth.

25 ENERGY STORAGE↗

Photoinduced chemomimetic biocatalysis for enantioselective intermolecular radical conjugate addition

Exploiting nature’s catalysts for non-natural transformations that are inaccessible to chemocatalysis is highly desirable but challenging. On the one hand, the widespread nicotinamide-dependent oxidoreductases have not been utilized for single-electron-transfer-induced bimolecular cross-couplings; on the other, the addition of catalytic asymmetric radical con- jugate to terminal alkenes remains a challenge owing to strong racemic background reaction and unselective termination of prochiral radical species. Here we report a chemomimetic biocatalysitic approach for construction of alpha-carbonyl stereocentres via an unnatural intermolecular conjugate addition of N-(acyloxy)phthalimides-derived radicals with acceptor-substituted terminal alkenes, by combination of visible-light excitation and nicotinamide-dependent ketoreductases (KREDs). Based on protein crystal structure, we engineered KREDs via a semi-rational mutagenesis strategy to improve reaction outcomes with a small and high-quality variants library. Here, mechanistic investigations combining wet experiments, crystallographic studies and computational simulations demonstrate that the repurposed biocatalyst can suppress racemic background reaction and unselected side reactions, yielding enantioselectivity that is challenging to achieve by chemocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Engineering tertiary chirality in helical biopolymers

Tertiary chirality describes the handedness of supramolecular assemblies and relies not only on the primary and secondary structures of the building blocks but also on topological driving forces that have been sparsely characterized. Helical biopolymers, especially DNA, have been extensively investigated as they possess intrinsic chirality that determines the optical, mechanical, and physical properties of the ensuing material. Here, we employ the DNA tensegrity triangle as a model system to locate the tipping points in chirality inversion at the tertiary level by X-ray diffraction. We engineer tensegrity triangle crystals with incremental rotational steps between immobile junctions from 3 to 28 base pairs (bp). We construct a mathematical model that accurately predicts and explains the molecular configurations in both this work and previous studies. Our design framework is extendable to other supramolecular assemblies of helical biopolymers and can be used in the design of chiral nanomaterials, optically active molecules, and mesoporous frameworks, all of which are of interest to physical, biological, and chemical nanoscience.

Science & Technology - Other Topics↗

State-dependent motion of a genetically encoded fluorescent biosensor

Genetically encoded biosensors can measure biochemical properties such as small-molecule concentrations with single-cell resolution, even in vivo. Despite their utility, these sensors are “black boxes”: Very little is known about the structures of their low- and high-fluorescence states or what features are required to transition between them. We used LiLac, a lactate biosensor with a quantitative fluorescence-lifetime readout, as a model system to address these questions. X-ray crystal structures and engineered high-affinity metal bridges demonstrate that LiLac exhibits a large interdomain twist motion that pulls the fluorescent protein away from a “sealed,” high-lifetime state in the absence of lactate to a “cracked,” low-lifetime state in its presence. Understanding the structures and dynamics of LiLac will help to think about and engineer other fluorescent biosensors.

Rosen, Paul C. (ORCID:000000017414454X)↗