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At least 253 records · Page 14

Design of a spaceworthy adiabatic demagnetization refrigerator

A spaceworthy adiabatic demagnetization refrigerator (ADR) under development at NASA-Goddard is presented. A baseline model heat switch was tested extensively with an on/off ratio of about 10,000 and a parasitic heat leak of 10 micro-W. Data obtained from the breadboard models were used to design an ADR with improved structural integrity. The core of the ADR is the salt pill which consists of the paramagnetic salt crystal and the thermal bus. When a magnetic field is applied to the salt it forces the alignment of the magnetic moments, thereby decreasing the entropy of the salt. Preliminary tests results showed a net crystal mass of 680 g instead of the expected 740 g, which indicate that there are gaps in the salt pill. A partial fix was accomplished by sealing helium gas in the salt pill at a pressure of 2 bar, which improved the thermal contact during salt magnetization, at about 2 K.

Serlemitsos, A. T.↗

Tomographic Location of Potential Melt-Bearing Phenocrysts in Lunar Glass Spherules

In 1971, Apollo 17 astronauts collected a 10 cm soil sample (74220) comprised almost entirely of orange glass spherules. Below this, a double drive-tube core sampled a 68 cm thick horizon comprised of orange glass and black beads (crystallized equivalents of orange glass). Primitive lunar glass spherules (e.g.-A17 orange glasses) are thought to represent ejecta from lunar mare fire fountains [1, 2]. The fire-fountains were apparently driven by a combination of C-O gas ex-solution from orange glass melt and the oxidation of graphite [3, 4]. Upon eruption, magmas lost their volatiles (e.g., S, CO, CO2) to space. Evidence for volatile escape remains as volatile-rich coatings on the exteriors of many spherules [e.g., 5,6]. Moreover, [7] showed that Type I and II Fe-Ni-rich metal particles found within orange glass olivine phenocrysts, or free-floating in the glass itself, are powerful evidence for the volatile driving force for lunar fire fountains.

Ebel, D. S.↗

An Overview of Mesoscale Convective Systems: Global Climatology, Satellite Observations, and Modeling Strategies

Deep convection is responsible for redistributing water as well as energy and providing vital water resources for many regions of the world. Cumulonimbus clouds aggregation into a single storm system develop mesoscale convective systems (MCS). MCSs have precipitation covering a horizontal region on the scale of 100?km or more. After more than the last seven decades, MCS has been gradually received wide attention in the scientific community as an important component of the Earth's hydrologic cycle and energy balance. MCSs differ from ordinary deep convection because of the mesoscale circulations consisting of a layer of air overturning on a scale much larger than those created by individual convective updrafts or downdrafts. Moreover, a key feature that separates MCS from ordinary deep convection is the significant portion of stratiform precipitation that results in the production and detrainment of a large number of ice particles from their organized convective cores and continues the mesoscale ascent that supports ice growth and aggregation as the crystals fall. This significant stratiform precipitation gives rise to top-heavy latent heating profiles that have substantial impacts on the upper-level global circulations, especially for those MCS that have a larger portion of stratiform rainfall. Top-heavy latent heating profiles are more frequent over the ocean than over the land. These unique features of MCS suggest that they are important for the hydrologic cycle, general circulation, and radiative balance of the climate system. In this chapter, we focus on the recent advances in the climatological perspective of MCS as well as the research tools used to better understand MCS after the advent of the satellite era. We will discuss both tropical and midlatitude MCS, the influence of modes of tropical climate variability on MCS, and the new insight from satellite observations on MCS interaction with the land surface.

Chakraborty, Sudip↗

Asteroid 4 Vesta: A Fully Differentiated Dwarf Planet

One conclusion derived from the study of meteorites is that some of them - most irons, stony irons, some achondrites - hail from asteroids that were heated to the point where metallic cores and basaltic crusts were formed. Telescopic observations show that there remains only one large asteroid with a basaltic crust, 4 Vesta; present day mean radius 263 km. The largest clan of achondrites, the howardite, eucrite and diogenite (HED) meteorites, represent the crust of their parent asteroid. Diogenites are cumulate harzburgites and orthopyroxenites from the lower crust whilst eucrites are cumulate gabbros, diabases and basalts from the upper crust. Howardites are impact-engendered breccias of diogenites and eucrites. A strong case can be made that HEDs are derived from Vesta. The NASA Dawn spacecraft orbited Vesta for 14 months returning data allowing geological, mineralogical, compositional and geophysical interpretations of Vesta's surface and structure. Combined with geochemical and petrological observations of HED meteorites, differentiation models for Vesta can be developed. Proto-Vesta probably consisted of primitive chondritic materials. Compositional evidence, primarily from basaltic eucrites, indicates that Vesta was melted to high degree (>=50%) which facilitated homogenization of the silicate phase and separation of immiscible Fe,Ni metal plus Fe sulphide into a core. Geophysical models based on Dawn data support a core of ~110 km radius. The silicate melt vigorously convected and initially followed a path of equilibrium crystallization forming a harzburgitic mantle, possibly overlying a dunitic restite. Once the fraction of crystals was sufficient to cause convective lockup, the remaining melt collected between the mantle and the cool thermal boundary layer. This melt undergoes fractional crystallization to form a dominantly orthopyroxenite (diogenite) lower crust. The initial thermal boundary layer of primitive chondritic material is gradually replaced by a mafic crust through impact disruption and foundering. The quenched mafic crust thickens over time through magma extrusion/intrusion. Melt from the residual magma ocean intrudes and penetrates the mafic crust forming cumulate eucrite plutons, and dikes, sills and flows of basaltic eucrite composition. The post-differentiation vestan structure is thus not too dissimilar from that of terrestrial planets: (i) a metallic core; (ii) an ultramafic mantle comprised of a lower dunitic layer (if melting was substantially <100%) and an upper cumulate harzburgitic layer; (iii) a lower crust of harzburgitic and orthopyroxenitic cumulates; and (iv) an upper mafic crust of basalts and diabases (melt compositions) with cumulate gabbro intrusions. Impacts have excavated to the lower crust and delivered howardites, eucrites and diogenites to Earth, but there is yet no evidence demonstrating excavation of the vestan mantlle.

Mittlefehldt, David↗

Oxide-Free Three-Dimensional Germanium/Silicon Core–Shell Metalattice Made by High-Pressure Confined Chemical Vapor Deposition

Metalattices are crystalline arrays of uniform particles in which the period of the crystal is close to some characteristic physical length scale of the material. In this work, we explore the synthesis and properties of a germanium metalattice in which the similar to 70 nm periodicity of a silica colloidal crystal template is close to the similar to 24 nm Bohr exciton radius of the nanocrystalline Ge replica. The problem of Ge surface oxidation can be significant when exploring quantum confinement effects or designing electronically coupled nanostructures because of the high surface area to volume ratio at the nanoscale. To eliminate surface oxidation, we developed a coreshell synthesis in which the Ge metalattice is protected by an oxide-free Si interfacial layer, and we explore its properties by transmission electron microscopy (TEM), Raman spectroscopy, and electron energy loss spectroscopy (EELS). The interstices of a colloidal crystal film grown from 69 nm diameter spherical silica particles were filled with polycrystalline Ge by high-pressure confined chemical vapor deposition (HPcCVD) from GeH4. After the SiO2 template was etched away with aqueous HF, the Ge replica was uniformly coated with an amorphous Si shell by HPcCVD as confirmed by TEM-EDS (energy-dispersive X-ray spectroscopy) and Raman spectroscopy. Formation of the shell prevents oxidation of the Ge core within the detection limit of XPS. The electronic properties of the core-shell structure were studied by accessing the Ge 3d edge onset using STEM-EELS. A blue shift in the edge onset with decreasing size of Ge sites in the metalattices suggests quantum confinement of the Ge core. The degree of quantum confinement of the Ge core depends on the void sizes in the template, which is tunable by using silica particles of varying size. The edge onset also shows a shift to higher energy near the shell in comparison with the Ge core. This shift along with the observation of Ge-Si vibrational modes in the Raman spectrum indicate interdiffusion of Ge and Si. Both the size of the voids in the template and core-shell interdiffusion of Si and Ge can in principle be tuned to modify the electronic properties of the Ge metalattice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Morphology-controlled transformation of Cu@Au core-shell nanowires into thermally stable Cu 3 Au intermetallic nanowires

Multimetallic nanowires with long-range atomic ordering hold the promise of unique physicochemical properties in many applications. Here we demonstrate the synthesis and study the stability of Cu 3 Au intermetallic nanowires. The synthesis is achieved by using Cu@Au core-shell nanowires as precursors. With appropriate Cu/Au stoichiometry, the Cu@Au core-shell nanowires are transformed into fully ordered Cu 3 Au nanowires under thermal annealing. Thermally-driven atom diffusion accounts for this transformation as revealed by X-ray diffraction and electron microscopy studies. The twin boundaries abundant in the Cu@Au core-shell nanowires facilitate the ordering process. The resulting Cu 3 Au intermetallic nanowires have uniform and accurate atomic positioning in the crystal lattice, which enhances the nobility of Cu. No obvious copper oxides are observed in fully ordered Cu 3 Au nanowires after annealing in air at 200 °C, a temperature that is much higher than those observed in Cu@Au core-shell and pure Cu nanowires. This work opens up an opportunity for further research into the development and applications of intermetallic nanowires.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Electrical Impact of SiC Structural Crystal Defects on High Electric Field Devices (Invited)

As illustrated by the invited paper at this conference and other works, SiC wafers and epilayers contain a variety of crystallographic imperfections, including micropipes, closed-core screw dislocations, grain boundaries, basal plane dislocations, heteropolytypic inclusions, and surfaces that are often damaged and contain atomically rough features like step bunching and growth pits or hillocks. Present understanding of the operational impact of various crystal imperfections on SiC electrical devices is reviewed, with an emphasis placed on high-field SiC power devices and circuits.

Neudeck, Philip G.↗

A general solution for accelerating screw dislocations in arbitrary slip systems with reflection symmetry

Solutions to the differential equations of linear elasticity in the continuum limit in arbitrary crystal symmetry are known only for steady-state dislocations of arbitrary character, i.e. line defects moving at constant velocity. Troubled by singularities at certain ‘critical’ velocities (typically close to certain sound speeds), these dislocation fields are thought to be too idealized, and divergences are usually attributed to neglecting the finite size of the core and to the restriction to constant velocity. In the isotropic limit, accelerating pure screw and edge dislocations were studied some time ago. A generalization to anisotropic crystals has been attempted for pure screw and edge dislocations only for some special cases. This work aims to fill the gap of deriving a general anisotropic solution for pure screw dislocations applicable to slip systems featuring a reflection symmetry, a prerequisite to studying pure screw dislocations without mixing with edge dislocations. Finally, further generalizations to arbitrary mixed dislocations as well as regularizations of the dislocation core are beyond the scope of this paper and are left for future work.

42 ENGINEERING↗

Minor Elements in Nakhlite Pyroxenes: Does Cr Record Changes in REDOX Conditions during Crystallization?

Nakhlites are olivine-bearing clinopyroxene cumulates. Based on petrographic characteristics, they may be divided into groups that cooled at different rates and may have been formed at different depths in a single flow. The order of cooling rate from slowest to fastest is NWA998<Lafayette < Governador Valadares approx. Nakhla < Yamato000593 < NWA817 approx. MIL03346. Nakhlite cumulus pyroxene grains consist of large cores that are nearly homogeneous in major element composition surrounded by thin rims that are zoned to Fe-rich compositions. Detailed study of these pyroxenes is important because they retain a record of the crystallization history of the nakhlite magma. Moreover, because the composition of the nakhlite parent melt cannot be directly determined, inversion of the major and minor element composition of the cumulate pyroxene cores can be used to estimate the composition of that melt. Moreover, minor and trace element zoning of pyroxenes can provide information about the oxidation conditions under which these samples crystallized. Thus it is important to understand the major and minor element zoning in the cumulus pyroxenes. While major elements are nearly homogeneous, minor elements exhibit distinctive zoning patterns that vary from one nakhlite to another. This abstract reports unusual Cr zoning patterns in pyroxenes from MIL03346 (MIL) and contrast these with pyroxenes from Y593 and Nakhla.

McKay, G.↗

Tuning Anisotropic Optical Properties of Inorganic and Hybrid Organic–Inorganic MXenes via Topochemical Surface Modification

Surface groups are central to the properties of MXenes, yet their role in optical anisotropy remains largely unexplored. Here, we use a topochemical route to synthesize single crystals of stacked Ti 3 C 2 Cl 2 and hybrid organic–inorganic MXenes (h-MXenes) with lateral sizes of 38–75 μm, rotational registry, and tunable interlayer spacing. Solid-state NMR spectroscopy shows that topochemical substitution generates mixed amido, imido, and hydride surface motifs, which modify the electronic structure of the Ti 3 C 2 inorganic core. Imaging spectroscopic ellipsometry with micron-scale spatial resolution enables reconstruction of the complex dielectric tensor of individual multilayer crystals. Ti 3 C 2 Cl 2 exhibits a type-II hyperbolicity above 930 nm, whereas h-MXenes do not display hyperbolicity within the measured 300–1700 nm window, instead showing reduced in-plane conductivity, suppressed out-of-plane light absorption, and a chain-length-dependent blue shift of a near-infrared absorption feature. These results demonstrate topochemical surface modification as a direct handle for engineering MXenes as surface-programmable optical media.

Hybrid materials↗

Deep-blue emitting 9,10-bis(perfluorobenzyl)anthracene

A new deep-blue emitting and highly fluorescent anthracene (ANTH) derivative containing perfluorobenzyl (Bn F ) groups, 9,10-ANTH(Bn F ) 2 , was synthesized in a single step reaction of ANTH or ANTH(Br) 2 with Bn F I, using either a high-temperature Cu-/Na 2 S 2 O 3 -promoted reaction or via a room-temperature photochemical reaction. Its structure was elucidated by NMR spectroscopy and single crystal X-ray diffractometry. The latter revealed no π–π interaction between neighboring ANTH cores. A combination of high photoluminescence quantum yield (PLQY) of 0.85 for 9,10-ANTH(Bn F ) 2 , its significantly improved photostability compared to ANTH and 9,10-ANTH derivatives, and a simple synthetic access makes it an attractive material as a deep-blue OLED emitter and an efficient fluorescent probe.

Chemistry↗

Titanium carbide and titania phases on Antarctic ice particles of probable extraterrrestrial origin

Two unique titania-rich particles, found within ancient Antarctic ice have been discovered and characterized, and are believed to be of extraterrestrial origin. Both particles contain abundant submicron-sized crystals of Magneli phases (Ti(n)O(2n-1). In addition, one particle contains a core of TiC. Whereas the Magneli phases would have been stable in the early solar nebula, and so probably formed there, the TiC is more likely to have condensed in the cool, dusty, carbon-rich outer shell of a red giant star. It is suggested that both particles are interplanetary dust particles whose Magneli phases carry a record of the PO2-T conditions of the early solar nebula. It is further suggested that the TiC grain in particle 705 is remnant interstellar dust.

Zolensky, M. E.↗

New Ultrafast Scintillators with Core Valence Luminescence: Cs 2 MgCl 4 and Cs 3 MgCl 5

Future experiments in high energy physics and medical imaging require radiation detectors having properties which are not presently available. The main limitations arise from lack of suitable scintillation crystals. This dilemma prompts the need for research leading to the discovery of new fast and bright scintillator materials that combine unique properties to fulfil modern experiment requirements without compromises. In this work, single crystals of Cs 2 MgCl 4 and Cs 3 MgCl 5 up to 12 mm in diameter are grown via the vertical Bridgman method. Scintillation properties are reported for the first time, and core valence luminescence is observed for both compounds. X-ray excited radioluminescence emission of Cs 2 MgCl 4 is centered at 295 nm, with a scintillation decay time of 2.25 ± 0.05 ns and relatively high core-valence light yield of 2,200 ± 110 ph/MeV. Cs 3 MgCl 5 has two main emission peaks centered at 242 nm and 302 nm, decay time of 1.46 ± 0.05 ns, and light yield of 1,340 ± 70 ph/MeV. The better coincidence time resolution (CTR) is obtained with Cs 2 MgCl 4 , which is measured to be 129 ± 4 ps FWHM. Density functional theory (DFT) calculations are also performed and provide supporting evidence that the observed scintillation originates from core valence luminescence. Furthermore, the combination of speed and brightness of these new scintillators could be useful for fast timing applications in which moderately dense materials are required.

36 MATERIALS SCIENCE↗

Small‐Molecule Mixed Ionic‐Electronic Conductors for Efficient N‐Type Electrochemical Transistors: Structure‐Function Correlations

Abstract The fundamental challenge in electron‐transporting organic mixed ionic‐electronic conductors (OMIECs) is simultaneous optimization of electron and ion transport. Beginning from Y6‐type/U‐shaped non‐fullerene solar cell acceptors, we systematically synthesize and characterize molecular structures that address the aforementioned challenge, progressively introducing increasing numbers of oligoethyleneglycol (OEG; g) sidechains from 1 g to 3 g, affording OMIECs 1gY, 2gY, and 3gY, respectively. The crystal structure of 1gY preserves key structural features of the Y n series: a U‐shaped/planar core, close π–π molecular stacking, and interlocked acceptor groups. Versus inactive Y6 and Y11, all of the new glycolated compounds exhibit mixed ion‐electron transport in both conventional organic electrochemical transistor (cOECT) and vertical OECT (vOECT) architectures. Notably, 3gY with the highest OEG density achieves a high transconductance of 16.5 mS, an on/off current ratio of ~10 6 , and a turn‐on/off response time of 94.7/5.7 ms in vOECTs. Systematic optoelectronic, electrochemical, architectural, and crystallographic analysis explains the superior 3gY‐based OECT performance in terms of denser n gY OEG content, increased crystallite dimensions with decreased long‐range crystalline order, and enhanced film hydrophilicity which facilitates ion transport and efficient redox processes. Finally, we demonstrate an efficient small‐molecule‐based complementary inverter using 3gY vOECTs, showcasing the bioelectronic applicability of these new small‐molecule OMIECs.

Cho, Yongjoon↗

Small‐Molecule Mixed Ionic‐Electronic Conductors for Efficient N‐Type Electrochemical Transistors: Structure‐Function Correlations

Abstract The fundamental challenge in electron‐transporting organic mixed ionic‐electronic conductors (OMIECs) is simultaneous optimization of electron and ion transport. Beginning from Y6‐type/U‐shaped non‐fullerene solar cell acceptors, we systematically synthesize and characterize molecular structures that address the aforementioned challenge, progressively introducing increasing numbers of oligoethyleneglycol (OEG; g) sidechains from 1 g to 3 g, affording OMIECs 1gY, 2gY, and 3gY, respectively. The crystal structure of 1gY preserves key structural features of the Y n series: a U‐shaped/planar core, close π–π molecular stacking, and interlocked acceptor groups. Versus inactive Y6 and Y11, all of the new glycolated compounds exhibit mixed ion‐electron transport in both conventional organic electrochemical transistor (cOECT) and vertical OECT (vOECT) architectures. Notably, 3gY with the highest OEG density achieves a high transconductance of 16.5 mS, an on/off current ratio of ~10 6 , and a turn‐on/off response time of 94.7/5.7 ms in vOECTs. Systematic optoelectronic, electrochemical, architectural, and crystallographic analysis explains the superior 3gY‐based OECT performance in terms of denser n gY OEG content, increased crystallite dimensions with decreased long‐range crystalline order, and enhanced film hydrophilicity which facilitates ion transport and efficient redox processes. Finally, we demonstrate an efficient small‐molecule‐based complementary inverter using 3gY vOECTs, showcasing the bioelectronic applicability of these new small‐molecule OMIECs.

Cho, Yongjoon↗

Impact of acid site speciation and spatial gradients on zeolite catalysis

This mini-review provides an overview of the current state of acid site control in zeolite catalysts, including methods of synthesis, advanced characterization, and measured effects of acid properties (speciation, concentration, proximity, siting, and spatial distribution) on a variety of commerciallyrelevant reactions. The diversity of aluminum species is described with respect to their location at specific sites in zeolite crystals as well as mesoscopic gradients in elemental composition that give rise to zoned or core-shell architectures. Challenges in the identification of acid siting are highlighted within the context of trial-and-error synthesis methods for a range of aluminosilicate frameworks, which hinder a priori design of catalysts, and limitations in techniques to suitably characterize active sites. Emphasis is also placed on knowledge gaps in zeolite catalysis wherein broad development of structure-performance relationships relies on future advancement of synthesis and analytical methods in parallel with atomistic modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evidence of a glassy magnetic transition driven by structural disorder in BiFeO 3 nanoparticles

Important effects appear in low and high temperature magnetometry of multiferroic BiFeO 3 (BFO) nanoparticles as sizes are reduced from 105 nm to 18 nm. In these particles, a magnetic transition appears close to 200 K probably associated with a spin reorientation which is absent in bigger particles. At higher temperatures and up to the bulk ferroelectric Curie temperature (1000 K), two additional magnetic transitions can be identified. Around T N 600 K, a size-dependent magnetic transition appears, associated with an antiferromagnetic transition. A model based on atomic vibration instability can describe the variation of T N with nanoparticle size. Furthermore, for certain sizes, the properties are dominated by the glassy state arising from the disorder produced by the formation of a core-shell structure. This implies that the magnetic behavior of nanoparticles is strongly affected by their crystal structure close to the transition temperature. Finally, the structural disorder which couples to the magnetic properties add control to the magnetic and ferroelectric properties of BFO nanoparticles.

36 MATERIALS SCIENCE↗

Structural organization of space polymers

Extraterrestrial polymers of glycine with iron have been characterized by mass spectrometry to have a core mass of 1494 Da with dominant rod-like variants at mass to charge ratios of 1567 and 1639 [McGeoch et al., “Meteoritic proteins with glycine, iron and lithium,” arXiv:2102.10700 (2021)]. Several principal macro-structural morphologies are observed in solvent extracts from a chondritic Vigarano class alteration type 3 meteoritic material. The first is an extended sheet of linked (three-legged) triskelia containing the 1494 Da core entity that encloses gas bubbles in the solvent. A second is of fiber-like crystals found here, via x-ray diffraction, to be multiple-walled nanotubes made from a square lattice of the 1494 Da polymer. A third is a dispersion of floating phantom-like short tubes of up to 100 μm length with characteristic angled bends that suggest the influence of a specific underlying protein structure. Here, it is proposed that the angled tubes are the observable result of a space-filling superpolymerization of 1638 Da polymer subunits guided by the tetragonal symmetry of linking silicon bonds. Distorted hexagonal sheets are linked by perpendicular subunits in a three-dimensional hexagonal diamond structure to fill the largest possible volume. This extended very low-density structure is conjectured to have dominated in a process of chemical selection because it captured a maximum amount of molecular raw material in the ultra-low density of molecular clouds or of the proto-solar nebula. This could have led ultimately to the accretion of the earliest planetary bodies.

59 BASIC BIOLOGICAL SCIENCES↗