Autocatalysis and Oriented Attachment Direct the Synthesis of a Metal–Organic Framework
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
SEARCH · Engineering Papers
Results for “in situ crystallization”
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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Fused-ring isomerism modulates molecular packing and device performance in non-halogenated organic solar cells
Subtle changes in molecular backbone geometry impact intermolecular interactions and performance of organic solar cells. Here, three isomeric small-molecule acceptors (NaO1, NaO2, and NaO3) are investigated to reveal how different fused-ring configurations control molecular packing, electronic coupling, and film formation. Structural and spectroscopic analyses show that the linearly fused NaO1 forms a compact three-dimensional packing network with large and balanced electronic couplings (>24 meV) across multiple directions, while the more curved analogues exhibit excessive crystallization and phase segregation. In-situ optical measurements demonstrate that NaO1 promotes fast and continuous structural evolution during film formation, resulting in smooth morphology and homogeneous phase distribution. These structural and dynamic advantages facilitate efficient charge generation and transport, accompanied by reduced non-radiative energy loss, ultimately achieving an efficiency of 20.07% for non-halogenated ternary devices. Our findings highlight how fused-ring isomerism decisively governs structure–packing–performance relationships in organic solar cells.
36 MATERIALS SCIENCE↗
Structural response of α-quartz under plate-impact shock compression
Because of its far-reaching applications in geophysics and materials science, quartz has been one of the most extensively examined materials under dynamic compression. Despite 50 years of active research, questions remain concerning the structure and transformation of SiO 2 under shock compression. Continuum gas-gun studies have established that under shock loading quartz transforms through an assumed mixed-phase region to a dense high-pressure phase. While it has often been assumed that this high-pressure phase corresponds to the stishovite structure observed in static experiments, there have been no crystal structure data confirming this. In this study, we use gas-gun shock compression coupled with in situ synchrotron x-ray diffraction to interrogate the crystal structure of shock-compressed α-quartz up to 65 GPa. Our results reveal that α-quartz undergoes a phase transformation to a disordered metastable phase as opposed to crystalline stishovite or an amorphous structure, challenging long-standing assumptions about the dynamic response of this fundamental material.
58 GEOSCIENCES↗
Cirrus radiative characteristics and the radiative impact of small particles
An understanding of the way radiation interacts with clouds is vital for understanding the sensitivity of the earth's climate to both natural and anthropogenic changes in the atmosphere. Cirrus clouds are thought to be an important modulator of climate sensitivity. The feedback effect of cirrus on climate can be positive or negative depending upon the microphysics and scattering properties of the cloud. These properties of cirrus clouds are not well understood partly because of their thin tenuous nature and partly because of their microphysical properties. The high altitude and cold temperatures within these clouds along with their transparency greatly increase the difficulty in which accurate measurements can be obtained and interpreted both by aircraft and remote sensing. Therefore, the understanding of the interaction of radiation in cirrus clouds is crucial to determining the ways in which these clouds interact with climate forcings. The sensitivity of the radiative budgets of cirrus cloudiness to their microphysical composition and the environments in which they occur is examined. Especially important is the impact of small particles on the radiative properties of cirrus. Remote sensing estimates of the effective crystal size of cirrus and in situ measurements show large differences up to 100 microns. Thus it becomes important to identify the sources of these differences. For this reason, simulations of actual FIRE cases are compared with the in situ radiative observations and inferences are made concerning the cause of the discrepancies.
Stackhouse, Paul W., Jr.↗
Ureilite smelting
Ureilites containing homogeneous Fo76 olivine cores in intimate co-existence with graphite must have recrystallized at pressures of at least approximately 100 bars to suppress smelting of the fayalite component of the olivine to Fe metal. Smelting of olivine and pyroxene-saturated magmatic liquids produces orthopyroxene-without-olivine crystalline derivatives unlike those in ureilites. Thus the Mg# compositional variation within the ureilite suite, which is commonly attributed to partial smelting, cannot plausibly be produced by assemblages rich in liquid. In situ smelting of graphitic olivine + pigeonite crystal mushes can produce the correct crystal assemblage, but fails to provide a plausible account for the removal of metal from ureilites or for the correlation of Mg# with Delta O-17. Even if Mg# and Delta O-17 variations are established in the nebula, ureilite recrystallization with graphite must have occurred at pressures greater than the minima we have experimentally established, corresponding to parent objects not less than approximately 100 km in radius.
Walker, David↗
Climate Impacts of Ice Nucleation
Several different ice nucleation parameterizations in two different General Circulation Models (GCMs) are used to understand the effects of ice nucleation on the mean climate state, and the Aerosol Indirect Effects (AIE) of cirrus clouds on climate. Simulations have a range of ice microphysical states that are consistent with the spread of observations, but many simulations have higher present-day ice crystal number concentrations than in-situ observations. These different states result from different parameterizations of ice cloud nucleation processes, and feature different balances of homogeneous and heterogeneous nucleation. Black carbon aerosols have a small (0.06 Wm(exp-2) and not statistically significant AIE when included as ice nuclei, for nucleation efficiencies within the range of laboratory measurements. Indirect effects of anthropogenic aerosols on cirrus clouds occur as a consequence of increasing anthropogenic sulfur emissions with different mechanisms important in different models. In one model this is due to increases in homogeneous nucleation fraction, and in the other due to increases in heterogeneous nucleation with coated dust. The magnitude of the effect is the same however. The resulting ice AIE does not seem strongly dependent on the balance between homogeneous and heterogeneous ice nucleation. Regional effects can reach several Wm2. Indirect effects are slightly larger for those states with less homogeneous nucleation and lower ice number concentration in the base state. The total ice AIE is estimated at 0.27 +/- 0.10 Wm(exp-2) (1 sigma uncertainty). This represents a 20% offset of the simulated total shortwave AIE for ice and liquid clouds of 1.6 Wm(sup-2).
Gettelman, Andrew↗
Basaltic Shergottite NWA 856: Differentiation of a Martian Magma
NWA 856 or Djel Ibone, is a basaltic shergottite discovered as a single stone of 320 g in South Morocco in April, 2001. This meteorite is fresh, i.e. shows minimal terrestrial weathering for a desert find. No shergottite discovered in North Africa can be paired with NWA 856. The purpose of this study is to constrain its crystallization history using textural observations, crystallization sequence modeling and in-situ trace element analysis in order to understand differentiation in shergottite magmatic systems.
Ferdous, J.↗
Uniaxial compression of [001]-oriented CaFe 2 As 2 single crystals:the effects of microstructure and temperature on superelasticity Part I: Experimental observations
Micropillar compression experiments on [001]-oriented CaFe 2 As 2 single crystals have recently revealed the existence of superelasticity with a remarkably high elastic limit of over 10%. The collapsed tetragonal phase transition, which is a uni-axial contraction process in which As-As bonds are formed across an intervening Ca-plane, is the main mechanism of superelasticity. Usually, superelasticity and the related structural transitions are affected strongly by both the microstructure and the temperature. As such, in this study, we investigated how the microstructure and temperature affect the superelasticity of [001]-oriented CaFe 2 As 2 micropillars cut from solution-grown single crystals, by performing a combination of in-situ cryogenic micromechanical testing and transmission electron microscopy studies. Our results show that the microstructure of CaFe 2 As 2 is influenced strongly by the crystal growth conditions and by subsequent heat treatment. The presence of Ca and As vacancies and FeAs nanoprecipitates affect the mechanical behavior significantly. In addition, the onset stress for the collapsed tetragonal transition decreases gradually as the temperature decreases. These experimental results are discussed primarily in terms of the formation of As-As bonds, which is the essential feature of this mechanism for superelasticity. Our research outcomes provide a more fundamental understanding of the superelasticity exhibited by CaFe 2 As 2 under uni-axial compression.
36 MATERIALS SCIENCE↗
Detached Growth of Germanium and Germaniumsilicon
Up to now, detached growth was observed mainly under microgravity, i.e. under the absence of hydrostatic pressure that hinders the formation of a free melt meniscus. the detached growth of germanium doped with gallium was obtained under 1 g conditions, the growth was performed in quartz-glass ampoule. Part of the crystal grew without wall contact, the detached growth was observed in-situ with a CCD-camera as well as after the growth process in form of growth lines and the formation of <111> facets on the crystal surface. GeSi crystal (oriientation: <111>, maximum silicon content: 4 at%, seed material: Ge) was grown in a pBN crucible (excluding the possibility of in-situ monitoring of the growth process). The grown crystal exhibits three growth facets, indicating also wall free growth. Surface analysis of the crystals (NDIC, SEM) and characterization of crystal segregation (EDAX, resistivity measurement) and defect structure (EPD, x-ray diffraction measurements) will be presented.
Dold, P.↗
In Situ Scattering Studies of Superconducting Vacancy‐Ordered Monoclinic TiO Thin Films
Abstract The structural and transport properties of vacancy‐ordered monoclinic superconducting titanium oxide (TiO) thin films grown by molecular beam epitaxy are investigated. The evolution of the crystal structure during growth is monitored by in situ synchrotron X‐ray diffraction. Long‐range ordering of Ti and O vacancies in the disordered cubic phase stabilizes the vacancy‐ordered monoclinic TiO phase. The reduced structural disorder arising from vacancy‐ordering is correlated with a superconductor‐metal transition (SMT) in contrast to the superconductor‐insulator transition (SIT) observed in cubic TiO, orthorhombic Ti 2 O 3 , and the Magneli γ − Ti 3 O 5 and γ − Ti 4 O 7 phase. Magnetoresistance measurements for the SIT phases indicate superconducting fluctuations persisting in the normal phase. These results confirm the role of disorder related to Ti and O vacancies and structural inhomogeneity in determining the electronic properties of the normal state of titanium oxide‐based superconductors.
Baksi, Merve↗
In situ high-temperature X-ray diffraction study of Sc-doped titanium oxide nanocrystallites
Titanium dioxide is an inexpensive wide-gap highly ionic semiconductor with striking photocatalytic capabilities in several heterogeneous photoredox reactions. A small crystal size is desirable to maximize the surface area, since photocatalytic reactions occur at the surface of a photocatalyst. Presented in this work are the synthesis and microstructural characterization of 4 at.% Sc-doped TiO 2 (4SDT) prepared by water-based co-precipitation. The crystal structure of 4SDT was examined via in situ high-temperature powder X-ray diffraction experiments from 25 to 1200°C. Rietveld analysis revealed single-phase anatase up to 875°C, while at 900°C the anatase-to-rutile phase transformation occurred and at higher temperatures additional reflections of Sc-rich phases (Sc 2 TiO 5 from 975°C and Ti 3 Sc 4 O 12 or Sc 2 O 3 at 1200°C) were observed. Debye function analysis (DFA) was applied to model the total scattering pattern directly in reciprocal space, allowing the reconstruction of Ti vacancies. Both Rietveld and DFA methods were applied to estimate the nanocrystallite size and shape with consistent growth in crystallite size with temperature: an ellipsoid shape with equatorial ~4.7 nm / axial (001) ~6.9 nm at 25°C to equatorial ~27.9 nm / axial (001) ~39.6 nm at 900°C refined by Rietveld analysis, versus a cylinder shape with D a , b = 4.3 nm and size dispersion σ ab = 1.5 nm, L c = 4.9 nm and σ c = 2.3 nm at 25°C to D a , b = 21.4 nm, σ ab = 8.3 nm, L c = 23.9 and σ c = 10.9 nm at 900°C estimated by DFA. The microstructural changes obtained by Rietveld and DFA methods were supported by high-resolution transmission electron microscopy image analysis, as well as by the less direct nitrogen sorption techniques that provide information on the size of non-agglomerated and dense particles. The Ti site-occupancy factor showed a linear increase from 0.6–0.8 at 25°C to unity at 900°C for anatase, and from ~0.7 at 900°C to unity at 1200°C for rutile, via Rietveld analysis and DFA.
36 MATERIALS SCIENCE↗
In situ temperature profile measurements with high-energy X-rays as a probe of optical floating zone crystal growth environment
The ability of optical floating zone (OFZ) furnaces to rapidly produce large single crystals of complex emerging materials has had a transformative effect on many scientific fields that require samples of this type. However, the crystal growth process within the OFZ furnace is not well understood owing to the challenges involved in monitoring the high-temperature crystal growth process. Novel beamline-compatible optical furnaces that approximate the inhomogeneous growth environment within an OFZ furnace have been fabricated and tested in high-energy synchrotron beamlines. In this paper, it is demonstrated that temperature profiles can be effectively extracted from powder diffraction data collected on polycrystalline ceramic rods heated at their tip. Furthermore, these measured temperature profiles can be accurately reproduced using a heat-transfer model that accounts for solid-state thermal conduction, partial sample lamp power absorption, convective air cooling and radiative cooling, allowing key thermal parameters such as thermal conductivity to be extracted from experimental data.
36 MATERIALS SCIENCE↗
Vapor Growth of ZnSe-based Compound Semiconductors in Low Gravity environment on International Space Station
Six low-gravity experiments of crystal growth of ZnSe-based compound semiconductors by physical vapor transport (PVT) are scheduled to be processed inside Low Gradient Furnace (LGF) on Materials Science Research Rack (MSRR) in Material Science Laboratory (MSL) on International Space Station (ISS) starting from February 27th, 2023. The flight samples consist of three unseeded growths of ZnSe, Cr-doped ZnSe and ZnSeTe as well as growth of ZnSe on top of three single crystal ZnSe seeds with orientation of (100), (110) and (111). The main scientific objective of the flight experiments is to establish the effects of gravity-driven fluid flows on Earth to (i) the non-uniform incorporation of impurities and defects and (ii) the deviation from stoichiometry observed in the grown crystals caused by growth interface fluctuations and evolution as the results of buoyancy-driven convection and irregular fluid-flows. The investigation will also evaluate the effects of gravity on the PVT process by examining (i) the growth kinetics on various seed orientations, (ii) the dopant segregation and distribution in the Cr doped ZnSe, and (iii) the compositional segregation and distribution in the ternary ZnSeTe crystal grown by PVT. Additionally, from X-ray diffraction/topography and by measuring the density and distribution of various crystalline defects it will assess the self-induced strain effects developed during processing at elevated temperatures caused by the weight of the crystals. During the ground-based preparations, the following tasks have been accomplished: • Establish the thermodynamic properties of the ZnSe binary and related ternary systems by measuring the partial pressures of the vapor phase coexisting with the condensed phases and perform phase diagram calculations for comparison. • Evaluate the effects of gravity-driven convection in the growth process by performing experiments under various vapor transport orientations relative to gravity vector, i.e., horizontal, vertically stabilized and destabilized configurations. • Establish a quantitative correlation between growth parameters and the characteristics and properties of the grown crystals by characterizing the crystals using a variety of techniques. • Evaluate the fundamentals of the current theories on vapor transport and crystal growth kinetics by performing in-situ and real-time monitoring techniques during growth. • Develop a one-dimensional diffusion limited theory of mass transport and two- and three-dimensional numerical simulations of both mass transport and heat transfer and thus establish the microgravity requirements for the flight experiments and to predict the characteristics of the grown crystals such as the solid-vapor interface shapes… etc. and establish a fundamental understanding of the crystal growth process from the comparison with experimental results.
ZnSe↗
The CRYSTAL-FACE Mission
The Cirrus Regional Study of Tropical Anvils and Cirrus Layers - Florida Area Cirrus Experiment (CRYSTAL-FACE) was a measurement campaign designed to investigate tropical cirrus cloud physical properties and formation processes. Understanding the production of upper tropospheric cirrus clouds is essential for the successful modeling of the Earth's climate. The mission was staged in July 2002 with flights of 6 aircraft from Key West, Florida. Several aircraft were used for in situ and remote sensing of aerosols, ice crystals, meteorological fields, radiative fluxes, and gas concentrations. The NASA ER-2 and WB-57, the Proteus aircraft, owned by Northrop Grumman and operated by Scaled Composites, CIRPAS provided the DeHavilland UV-l8A, "Twin Otter" aircraft, the University of North Dakota provided a Cessna Citation II aircraft , and NSF supported the ELDORA radar onboard the Naval Research Laboratory P-3 aircraft. In this presentation, I will describe some of the flights, the conditions, and some of the results from the mission.
Newman, P.↗
The Potassium-Argon Laser Experiment (KARLE): In Situ Geochronology for Planetary Robotic Missions
Isotopic dating is an essential tool to establish an absolute chronology for geological events, including crystallization history, magmatic evolution, and alteration events. The capability for in situ geochronology will open up the ability for geochronology to be accomplished as part of lander or rover complement, on multiple samples rather than just those returned. An in situ geochronology package can also complement sample return missions by identifying the most interesting rocks to cache or return to Earth. The K-Ar Laser Experiment (KArLE) brings together a novel combination of several flight-proven components to provide precise measurements of potassium (K) and argon (Ar) that will enable accurate isochron dating of planetary rocks. KArLE will ablate a rock sample, measure the K in the plasma state using laser-induced breakdown spectroscopy (LIBS), measure the liberated Ar using mass spectrometry (MS), and relate the two by measuring the volume of the ablated pit by optical imaging. Our work indicates that the KArLE instrument is capable of determining the age of planetary samples with sufficient accuracy to address a wide range of geochronology problems in planetary science. Additional benefits derive from the fact that each KArLE component achieves analyses useful for most planetary surface missions.
Cohen, B. A.↗
In-Situ Pressure Measurements During the Detached Growth of Germanium
Crystal growth by the vertical Bridgman method in which there is little or no contact between the wall and the crystal has been termed detached solidification. Detachment has been observed frequently in previous microgravity experiments, and has been reported under some terrestrial conditions as well. It is expected that detachment can be conditioned by establishing an appropriate pressure difference below and above the melt. To test this hypothesis, an experimental technique has been developed to measure this pressure difference during the growth of germanium by the vertical Bridgman method. The apparatus allows for both monitoring the pressures and actively controlling them during growth. For a given melt height, there is a maximum pressure difference attainable before gas bubbles up through the melt. This maximum pressure increases with increasing melt height. As the melt height approaches zero, the maximum pressure difference, about 20 mbar in these experiments, is determined by the surface tension and gap width of the meniscus at the bottom of the melt.
Volz, M. P.↗
Impact of high-power impulse magnetron sputtering pulse width on the nucleation, crystallization, microstructure, and ferroelectric properties of hafnium oxide thin films
The impact of the high-power impulse magnetron sputtering (HiPIMS) pulse width on the crystallization, microstructure, and ferroelectric properties of undoped HfO 2 films is investigated. HfO 2 films were sputtered from a hafnium metal target in an Ar/O 2 atmosphere, varying the instantaneous power density by changing the HiPIMS pulse width with fixed time-averaged power and pulse frequency. The pulse width is shown to affect the ion-to-neutral ratio in the depositing species with the shortest pulse durations leading to the highest ion fraction. In situ x-ray diffraction measurements during crystallization demonstrate that the HiPIMS pulse width impacts nucleation and phase formation, with an intermediate pulse width of 110 μ s stabilizing the ferroelectric phase over the widest temperature range. Although the pulse width impacts the grain size with the lowest pulse width resulting in the largest grain size, the grain size does not strongly correlate with the phase content or ferroelectric behavior in these films. In conclusion, these results suggest that precise control over the energetics of the depositing species may be beneficial for forming the ferroelectric phase in this material.
36 MATERIALS SCIENCE↗
Dynamic processes in transient phases during self-assembly of organic semiconductor thin films
Understanding and manipulating crystallization processes has been an important challenge for solution-processed organic thin films, both for fundamental studies and for fabricating thin films with near-intrinsic charge transport properties. We report an in situ X-ray scattering study of the crystallization of 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-C 10 ) during its deposition from solution. At temperatures modestly below the smectic-E/crystalline phase boundary, the crystallization goes through a transient liquid crystal state before reaching the final stable crystalline phase. Significant dynamics occur in the first few seconds of the transition, which are observed through fluctuations in the X-ray scattering intensity, and are correlated with the time interval that the transient thin film coexists with the evaporating solvent. The transition to the stable crystalline phase takes minutes or even hours under these conditions, which may be a result of the asymmetry of the molecule. Transient phases are of potential interest for applications, since they can act as a route to self-assembly of organic thin films. However, our observations show that the long-lived monolayer-stacked intermediate state does not act as a template for the bilayer-stacked crystalline phase. Rather, the grain structure is replaced through nucleation, where the nucleation free-energy barrier is related to a potential barrier that prevents molecules to flip their long axis by 180°.
36 MATERIALS SCIENCE↗