Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “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.

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

At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS2006

In-Situ Crystallization of a Lithium Disilicate Glass--Effect of Pressure on Crystal Growth Rate

Crystallization of a Li2O.2SiO2 (LS2) glass subjected to a uniform hydrostatic pressure of 4.5 GPa and 6 GPa was investigated up to a temperature of 750 C. The density of the compressed glass is about 2% greater at 4.5 GPa than at 1 atm and, depending upon the processing temperature, up to 10% greater at 6 GPa. Crystal growth rates investigated as a function of temperature and pressure show that lithium disilicate crystal growth is an order of magnitude slower at 4.5 GPa than 1 atm resulting in a shift of +45 C (plus or minus 10 C) in the growth rate curve at high pressure compared to 1 atm condition. At 6 GPa lithium disilicate crystallization is suppressed entirely, while a new high pressure lithium metasilicate crystallizes at temperatures 95 C (plus or minus 10 C) higher than those reported for lithium disilicate crystallization at 1 atm. The decrease in crystal growth rate with increasing pressure for lithium disilicate glass up to 750 C is related to an increase in viscosity with pressure associated with fundamental changes in glass structure accommodating densification.

Fuss, T.↗
DOE OSTI2020

Large Single Crystals of V 1– x Mo x O 2 from a Two-Step Chemical Vapor Transport Synthesis

This article details the synthesis of single crystals with the chemical formulas V 1-x Mo x O 2 ( 0 ≤ x ≤ 0.6) using the chemical vapor transport method at high temperatures (850 to 950 °C). These compounds are of interest due to the special relationship between their structure and electronic properties. Understanding this relationship will help guide future efforts in designing energy-saving devices. While some of these compounds have been synthesized before, this is the first time their synthesis has been reported for such a wide range of compounds in the form of bulk single crystals. The single crystal form is required for detailed characterization of the compounds. The materials were characterized chemically and structurally in order to validate the precise chemical compositions that were reported. Characterization methods included x-ray diffraction, inductively-coupled plasma atomic emission spectroscopy, and electron dispersive spectroscopy. The synthesis method is tunable, and the introduction of multiple steps both overcome the previous chemical challenges precluding synthesis of high molybdenum content crystals and allow for the creation of larger single crystals that were otherwise possible. The crystals synthesized this way are suitable for specialized measurements for determining the precise physical properties and atomic structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Measuring the diffraction properties of an imaging quartz(211) crystal

A dual goniometer X-ray system was used to measure the reflectivity curve for a spherically bent quartz(211) crystal. An analysis of the dual goniometer instrument response function for the rocking curve width measurement was developed and tested against the actual measurements. The rocking curve was measured at 4510.8 eV using the Ti Kα1 characteristic spectral line. The crystal is the dispersion element for a high resolution spectrometer used for plasma studies. It was expected to have a very narrow rocking curve width. The analysis showed that we could measure the upper bound for the rocking curve width of the Qz(211) crystal. The upper bound was 58 μrad giving a lower bound for the instrument resolving power E/ΔE = 34 000. Greatly improved insight into the dual goniometer operation and its limitations was achieved.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2016

Determination of crystal growth rates during rapid solidification of polycrystalline aluminum by nano-scale spatio-temporal resolution in situ transmission electron microscopy

In situ investigations of rapid solidification in polycrystalline Al thin films were conducted using nano-scale spatio-temporal resolution dynamic transmission electron microscopy. Differences in crystal growth rates and asymmetries in melt pool development were observed as the heat extraction geometry was varied by controlling the proximity of the laser-pulse irradiation and the associated induced melt pools to the edge of the transmission electron microscopy support grid, which acts as a large heat sink. Experimental parameters have been established to maximize the reproducibility of the material response to the laser-pulse-related heating and to ensure that observations of the dynamical behavior of the metal are free from artifacts, leading to accurate interpretations and quantifiable measurements with improved precision. Interface migration rate measurements revealed solidification velocities that increased consistently from ∼1.3 m s{sup −1} to ∼2.5 m s{sup −1} during the rapid solidification process of the Al thin films. Under the influence of an additional large heat sink, increased crystal growth rates as high as 3.3 m s{sup −1} have been measured. The in situ experiments also provided evidence for development of a partially melted, two-phase region prior to the onset of rapid solidification facilitated crystal growth. Using the experimental observations and associated measurements as benchmarks, finite-element modeling based calculations of the melt pool evolution after pulsed laser irradiation have been performed to obtain estimates of the temperature evolution in the thin films.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

On Change in the Silicon Crystal Structure Implanted with Hydrogen Ions during Annealing Based on Three-Crystal X-Ray Diffractometry Data

In this paper, we present the results of a three-crystal X-ray diffractometry (XRD) study of the state of a disturbed layer formed in silicon crystals by implantation of hydrogen ions with energies of 100 + 200 + 300 keV and a total dose of 2 × 10{sup 16} cm{sup –2} during the subsequent heat exposure in the temperature range from 200 to 1100°C. Here, X-ray studies were performed in the three-crystal XRD scheme when the sample under consideration operates as a second stationary crystal with various fixed angular detuning α from the Bragg position while the third (perfect) crystal-analyzer sweeps the angular distribution of radiation diffracted by the second crystal. Based on a comparison of the shape of diffraction and diffuse maxima for the samples under study, a qualitative conclusion about a significant transformation of radiation defects at post-implantation annealing was derived.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

How Accurate Can Crystal Structure Predictions Be for High-Energy Molecular Crystals?

Molecular crystals have shallow potential energy landscapes, with multiple local minima separated by very small differences in total energy. Predicting molecular packing and molecular conformation in the crystal generally requires ab initio methods of high accuracy, especially when polymorphs are involved. We used dispersion-corrected density functional theory (DFT-D) to assess the capabilities of an evolutionary algorithm (EA) for the crystal structure prediction (CSP) of well-known but challenging high-energy molecular crystals (HMX, RDX, CL-20, and FOX-7). While providing the EA with the experimental conformation of the molecule quickly re-discovers the experimental packing, it is more realistic to start instead from a naïve, flat, or neutral initial conformation, which reflects the limited experimental knowledge we generally have in the computational design of molecular crystals. By doing so, and using fully flexible molecules in fully variable unit cells, we show that the experimental structures can be predicted in fewer than 20 generations. Nonetheless, one must be aware that some molecular crystals have naturally hindered evolutions, requiring as many attempts as there are space groups of interest to predict their structures, and some may require the accuracy of all-electron calculations to discriminate between closely ranked structures. To save resources in this computationally demanding process, we showed that a hybrid xTB/DFT-D approach could be considered in a subsequent study to push the limits of CSP beyond 200+ atoms and for cocrystals.

42 ENGINEERING↗
DOE OSTI2017

Crystal structure of Mdm12 and combinatorial reconstitution of Mdm12/Mmm1 ERMES complexes for structural studies

Membrane contact sites between organelles serve as molecular hubs for the exchange of metabolites and signals. In yeast, the Endoplasmic Reticulum – Mitochondrion Encounter Structure (ERMES) tethers these two organelles likely to facilitate the non-vesicular exchange of essential phospholipids. Present in Fungi and Amoebas but not in Metazoans, ERMES is composed of five distinct subunits; among those, Mdm12, Mmm1 and Mdm34 each contain an SMP domain functioning as a lipid transfer module. We previously showed that the SMP domains of Mdm12 and Mmm1 form a hetero-tetramer. Here we describe our strategy to diversify the number of Mdm12/Mmm1 complexes suited for structural studies. We use sequence analysis of orthologues combined to protein engineering of disordered regions to guide the design of protein constructs and expand the repertoire of Mdm12/Mmm1 complexes more likely to crystallize. Using this combinatorial approach we report crystals of Mdm12/Mmm1 ERMES complexes currently diffracting to 4.5 Å resolution and a new structure of Mdm12 solved at 4.1 Å resolution. Our structure reveals a monomeric form of Mdm12 with a conformationally dynamic N-terminal β-strand; it differs from a previously reported homodimeric structure where the N-terminal β strands where swapped to promote dimerization. Based on our electron microscopy data, we propose a refined pseudo-atomic model of the Mdm12/Mmm1 complex that agrees with our crystallographic and small-angle X-ray scattering (SAXS) solution data. - Highlights: • We solved a 4.1 Å resolution crystal structure of Mdm12, the soluble subunit of ERMES. • The two Mdm12 apo monomers differ in the conformation of their N-terminal β-strands. • We reconstituted and crystallized two distinct Mdm12/Mmm1 complexes. • SAXS analysis of the complexes agrees with our previous electron microscopy data. • The structure suggests a head-to-tail association in the Mdm12/Mmm1 complex.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

Predictive modeling of crystal accumulation in high-level waste glass melters processing radioactive waste

The effectiveness of HLW vitrification is limited by precipitation/accumulation of spinel crystals [(Fe, Ni, Mn, Zn)(Fe, Cr)2O4] in the glass discharge riser of Joule-heated ceramic melters during idling. These crystals do not affect glass durability; however, if accumulated in thick layer, they can clog the melter and prevent discharge of molten glass into canisters. To address this problem, an empirical model was developed that can predict thicknesses of accumulated layers as a function of glass composition. This model predicts well the accumulation of single crystals and/or small-scale agglomerates, but, excessive agglomeration observed in high-Ni-Fe glass resulted in an under-prediction of accumulated layers, which gradually worsen over time as an increased number of agglomerates formed. Accumulation rate of ~53.8 ± 3.7 µm/h determined for this glass will result in ~26 mm thick layer in 20 days of melter idling.

Crystal accumulation↗
DOE OSTI2016

Measurement and models of bent KAP(001) crystal integrated reflectivity and resolution (invited)

The Advanced Light Source beamline-9.3.1 x-rays are used to calibrate the rocking curve of bent potassium acid phthalate (KAP) crystals in the 2.3-4.5 keV photon-energy range. Crystals are bent on a cylindrically convex substrate with a radius of curvature ranging from 2 to 9 in. and also including the flat case to observe the effect of bending on the KAP spectrometric properties. As the bending radius increases, the crystal reflectivity converges to the mosaic crystal response. The X-ray Oriented Programs (XOP) multi-lamellar model of bent crystals is used to model the rocking curve of these crystals and the calibration data confirm that a single model is adequate to reproduce simultaneously all measured integrated reflectivities and rocking-curve FWHM for multiple radii of curvature in both 1st and 2nd order of diffraction.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2026

Orientation-tunable local crystallization of Si films enabled by atomic imprint crystallization

Here, in this paper, we demonstrate area-selective crystallization of amorphous Si into tunable crystal orientations enabled by atomic imprint crystallization (AIC), where an amorphous Si layer is crystallized by solid phase epitaxy (SPE) from an externally impressed single-crystalline Si template. Using micro-patterned single-crystalline Si templates, a limited area of an amorphous Si film, where the film surface and patterned template surface are in contact, is crystallized via SPE to create an array of crystallographically aligned dots embedded in amorphous matrix. Combining AIC from the top surface and conventional SPE from the substrate, we demonstrate the fabrication of an array of crystalline dots embedded in single-crystalline matrix with tunable in-plane rotation angle. The results indicate the high tunability of the crystallization process enabled by AIC, allowing precise control of crystallographic properties of thin films with area-selectivity; such capability opens opportunities for the design of new materials for a wide range of applications in materials science.

Amorphous↗
DOE OSTI2016

Crystallization of Sodium Phosphate Dodecahydrate and Re-crystallization to Natrophosphate in Simulated Hanford Nuclear Waste - 16188

The nuclear waste at the Hanford site near Richland, WA, has large concentrations of phosphate in the form of the phosphate ion, sodium phosphate dodecahydrate (Na{sub 3}PO{sub 4}.12H{sub 2}O.(1/4)NaOH) and natrophosphate (Na{sub 7}F(PO{sub 4}){sub 3}.19H{sub 2}O). Sodium phosphate dodecahydrate can form a gel and natrophosphate can crystallize large particles, complicating the processing of slurries of both salts. The gel is regarded as more problematic, so natrophosphate has historically been crystallized to prevent phosphate gelling. This study determined if natrophosphate crystals can grow to large size in short time periods (a few weeks), time periods relevant to short process shutdowns. Solutions of NaOH and NaAl(OH){sub 4} were blended at different ratios with stock solutions containing NaOH, NaF, and Na{sub 3}PO{sub 4} at 50 deg. C. The mixtures were allowed to cool to 22 deg. C, and the crystal growth was monitored by Polarized Light Microscopy (PLM) for 17 days. Four of the six blends investigated gelled rapidly due to Na{sub 3}PO{sub 4}.12H{sub 2}O.(1/4)NaOH precipitation. The gel slowly dissipated over time as the solids recrystallized into natrophosphate. In one case, the natrophosphate reached sizes of greater than 1000 microns in diameter in just 4 days. This rapid gelling and crystallization kinetics is important to engineers trying to manage nuclear wastes high in phosphates. Hanford tank farm engineers are developing sampling plans to support temperature and process control strategies for preventing the formation of solid phosphates. They are also developing methods of suspending large natrophosphate crystals. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Syntheses, crystal structures, and optical properties of CsBa{sub 5}Ti{sub 2}Se{sub 9}Cl and CsBa{sub 2}Cl{sub 5}

The mixed-cation compounds CsBa{sub 5}Ti{sub 2}Se{sub 9}Cl and CsBa{sub 2}Cl{sub 5} were synthesized in the same solid-state reaction at 1173 K. CsBa{sub 5}Ti{sub 2}Se{sub 9}Cl adopts the Cs{sub 3}CoCl{sub 5} structure type in the tetragonal crystal system whereas CsBa{sub 2}Cl{sub 5} crystallizes in the PbU{sub 2}Se{sub 5} structure type in the monoclinic crystal system. The CsBa{sub 5}Ti{sub 2}Se{sub 9}Cl structure displays both Cs/Ba and Se/Cl disorder. From optical absorption measurements CsBa{sub 5}Ti{sub 2}Se{sub 9}Cl is an indirect wide-gap semiconductor. From theoretical calculations CsBa{sub 2}Cl{sub 5} has a large band gap of 6.4 eV. - Graphical abstract: General view of the crystal structure of CsBa{sub 5}Ti{sub 2}Se{sub 9}Cl. Display Omitted - Highlights: • CsBa{sub 5}Ti{sub 2}Se{sub 9}Cl is an indirect wide-gap semiconductor. • Red crystals of CsBa{sub 5}Ti{sub 2}Se{sub 9}Cl show an absorption transition at 2.00(2) eV. • As expected, DFT calculations indicate CsBa{sub 2}Cl{sub 5} has a large band gap of 6.4 eV. • Unexpectedly, crystals of CsBa{sub 2}Cl{sub 5} are pink, perhaps from minimal Ti impurities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Ternary molecular switching in a single-crystal optical actuator with correlated crystal strain

A growing portfolio of single-crystal optical actuators is forging a new class of photonic materials that hold prospects for quantum technologies. Ruthenium-based complexes that exhibit this phenomenon via SO 2 -linkage photoisomerisation are of particular interest since they display multiple metastable states, once induced by green light; yet, complete photoconversion into each SO 2 -isomeric state is rarely achieved. We discover a new complex, trans-[Ru(SO 2 )(NH 3 ) 4 (4-bromopyridine)]tosylate 2 , that produces 100% photoconverted η 1 -OSO isomeric crystal structures at 90 K, which fully transition into η 2 -(OS)O photoisomers upon warming to 100 K, while the dark-state η 1 -SO 2 structure is wholly recovered by heating the crystal to room temperature. Crystal structures and optical-absorption profiles of each state are captured via in-situ light-induced single-crystal X-ray diffraction and optical-absorption spectroscopy. Results show that both photoisomeric species behave as optical switches, but with distinct optical properties. The photoisomerisation process causes thermally-reversible micro- and nanoscopic crystal strain, as characterised by optical microscopy and in-situ light-induced atomic-force microscopy.

actuators↗