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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Atomistic understanding of interdependence of crystal growth of two seeds embedded in glass

Recent results showed that during growth, a crystal seed embedded in glass experiences nonuniform forces from the host matrix. This result raised the possibility that during devitrification of glass, the growth of a crystal can be affected by the presence of neighboring crystals. To investigate the nature of any such interdependence of growth of neighboring crystals, atomic scale morphology of two seeds growing in a glass matrix was simulated as a function of their separation and relative misorientation. The results show a coupled rotation of seeds driven by (1) non-uniform forces from the surrounding glass, and (2) mutual interactions between the seeds. At small separations and low misorientation, each seed rotates toward perfect alignment, ultimately forming a single crystal. The onset and rate of alignment, as well as subsequent crystal growth, are strongly dependent on the growth temperature. In contrast, at larger separations and higher misorientation, the seeds cannot achieve full alignment before coalescing, resulting in polycrystalline structures.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Sensitivity of pore collapse heating to the melting temperature and shear viscosity of HMX

A multiscale modeling strategy is used to quantify factors governing the temperature rise in hot spots formed by pore collapse from supported and unsupported shock waves in the high explosive HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine). Two physical aspects are examined in detail, namely the melting temperature and liquid shear viscosity. All-atom molecular dynamics simulations of phase coexistence are used to predict the pressure-dependent melting temperature up to 5 GPa. Equilibrium simulations and the Green–Kubo formalism are used to obtain the temperature- and pressure-dependent liquid shear viscosity. Starting from a simplified continuum-based grain-scale model of HMX, in this study we systematically increase the complexity of treatments for the solid–liquid phase transition and liquid shear viscosity in simulations of pore collapse. Using a realistic pressure-dependent melting temperature completely suppresses melting for supported shocks, which is otherwise predicted when treating it as a constant determined at atmospheric pressure. Alternatively, melt pools form around collapsed pores when the pressure (and melting temperature) are reduced during the release stage of unsupported shocks. Capturing the pressure dependence of the shear viscosity increases the peak temperature of melt pools by hundreds of Kelvin through viscous work. The complicated interplay of the solid-phase plastic work, solid–liquid phase transition, and liquid-phase viscous work identified here motivate taking a systematic approach to building increasingly complex grain-scale models.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Selective Photodimerization in a Cyclodextrin Metal–Organic Framework

For the most part, enzymes contain one active site wherein they catalyze in a serial manner chemical reactions between substrates both efficiently and rapidly. Imagine if a situation could be created within a chiral porous crystal containing trillions of active sites where substrates can reside in vast numbers before being converted in parallel into products. Here, we report how it is possible to incorporate 1-anthracenecarboxylate (1-AC – ) as a substrate into a γ-cyclodextrin-containing metal–organic framework (CD-MOF-1), where the metals are K + cations, prior to carrying out [4+4] photodimerizations between pairs of substrate molecules, affording selectively one of four possible regioisomers. One of the high-yielding regioisomers exhibits optical activity as a result of the presence of an 8:1 ratio of the two enantiomers following separation by high-performance liquid chromatography. The solid-state superstructure of 1-anthracenecarboxylate potassium salt (1-ACK), which is co-crystallized with γ-cyclodextrin, reveals that pairs of substrate molecules are not only packed inside tunnels between spherical cavities present in CD-MOF-1, but also stabilized—in addition to hydrogen-bonding to the C-2 and C-3 hydroxyl groups on the d-glucopyranosyl residues present in the γ-cyclodextrin tori—by combinations of hydrophobic and electrostatic interactions between the carboxyl groups in 1-AC– and four K + cations on the waistline between the two γ-cyclodextrin tori in the tunnels. Here, these non-covalent bonding interactions result in preferred co-conformations that account for the highly regio- and enantioselective [4+4] cycloaddition during photoirradiation. Theoretical calculations, in conjunction with crystallography, support the regio- and stereochemical outcome of the photodimerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Nanoconfinement and mass transport in metal–organic frameworks

The ubiquity of metal–organic frameworks in recent scientific literature underscores their highly versatile nature. MOFs have been developed for use in a wide array of applications, including: sensors, catalysis, separations, drug delivery, and electrochemical processes. Often overlooked in the discussion of MOF-based materials is the mass transport of guest molecules within the pores and channels. Given the wide distribution of pore sizes, linker functionalization, and crystal sizes, molecular diffusion within MOFs can be highly dependent on the MOF-guest system. In this paper, we discuss the major factors that govern the mass transport of molecules through MOFs at both the intracrystalline and intercrystalline scale; provide an overview of the experimental and computational methods used to measure guest diffusivity within MOFs; and highlight the relevance of mass transfer in the applications of MOFs in electrochemical systems, separations, and heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

A High-Speed Rotational Diamond Anvil Cell for In Situ Analysis of Hierarchical Microstructural Evolution of Metallic Alloys during Extreme Shear Deformation

High speed shear deformation is ubiquitous in engineering applications, ranging from material processing methods such as friction stir processing/extrusion and in tribological contacts. However, analyzing the microstructural evolution of materials while they are undergoing high speed shear deformation have been a long-standing challenge. This led to predominant reliance on ex situ microscopy before and after shear deformation. But ex situ microscopy lacks the ability to analyze dynamic and transient hierarchical microstructural evolution mechanisms that could occur during shear deformation of materials. Therefore, to better understand the dynamic mechanisms of mass and energy transfer in materials under shear deformation, we developed a first of its kind high-speed rotational diamond anvil cell (HS-RDAC) for synchrotron-based in situ high-energy x-ray diffraction (XRD). We studied the time resolved lattice strain evolution, XRD peak broadening and changes in spatial variation of shear deformation induced alloying in pure metal and metal alloy sheets and powder mixture using the HS-RDAC. These in situ results were combined with detailed ex situ microstructural characterization before and after the shear deformation using transmission electron microscopy and atom probe tomography, which revealed the different stages of evolution of a shear deformation induced hierarchical nanostructure. Multiscale computational simulations including computational fluid dynamics, crystal plasticity, molecular dynamic simulation and density functional theory uncovered the mechanisms behind morphological changes, evolution of defect structures and changes in driving force for shear deformation induced intermixing. In conclusion, this in situ HS-RDAC capability, in combination with ex situ microstructural characterization and computational simulations, can provide new insights into the hierarchical microstructural evolution pathway during shear deformation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Electronic band gaps from quantum Monte Carlo methods

We develop a method for calculating the fundamental electronic gap of semiconductors and insulators using grand canonical quantum Monte Carlo simulations. Further, we discuss the origin of the bias introduced by supercell calculations of finite size and show how to correct the leading and subleading finite size errors either based on observables accessible in the finite-sized simulations or from density-functional theory calculations. Our procedure is applied to carbon, silicon, and molecular hydrogen crystals, and compared to experiment for carbon and silicon.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Nuclear Theory (Final Technical Report)

This Grant spans a period of 29 years. Achievements of the principal investigator for Task A (F. Iachello), and of the principal investigator for Task B (Y. Alhassid) during this period. Because of the large span in years, the achievements of the P.I. are many, both within the realm of Nuclear Physics and in Interdisciplinary subjects (Hadronic Physics, Molecular Physics, Crystal Physics and Mathematical Physics).

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Organic Multiferroics (Final Technical Report)

The research objective of this project is to explore the unusual physical properties of molecular electronic crystal materials, comprised of two chemically and electronically distinct donor and acceptor molecules, which combine two or more properties in the same crystal lattice in a manner that is difficult or impossible to achieve in continuous inorganic crystalline solids.

36 MATERIALS SCIENCE↗
DOE OSTI2022

End-to-end optimization for battery materials and molecules by combining graph neural networks and reinforcement learning

The National Renewable Energy Laboratory (NREL), together with the Colorado School of Mines (CSM) and Colorado State University (CSU), has developed a machine learning-enhanced approach to design new battery materials. Currently, such materials are designed in part via numerous expensive high-fidelity computational simulations that predict the performance of a given composition. Even with computational screening tools, the vast landscape of possible molecular or crystal structures exceeds current and future computational capacity. Improving the efficiency by which new materials can be optimized will therefore disrupt the cost, risk, and time required to bring new energy solutions to the marketplace. Predicting the properties of an organic molecule or periodic crystalline material given its structure has grown increasingly common. These approaches leverage large-scale computational and experimental databases and ML approaches such as graph neural networks. The inverse design problem of finding a material that possesses desired properties is substantially more challenging, since enumerating all valid material structures is not feasible. In this project, we leveraged recent success in reinforcement learning to efficiently navigate this high-dimensional search space. Just as algorithms can find the optimal chess moves from nearly limitless options, we train an approach to evolve a simple starting structure into a complex structure that possess the desired properties. Our solution has been demonstrated by applying it to two related design application tasks for short- and long-term energy storage, respectively: (1) the design of solid-state ion conductors and (2) the design of organic redox-active materials. The project has resulted an open-source software library for material design, documented examples of applying the library to both organic and inorganic material optimization, and peer-reviewed publications detailing the data, computational models, and resulting candidate materials.

25 ENERGY STORAGE↗
NASA NTRS1967

High-temperature thermodynamics.

High temperature thermodynamics requiring species and phases identification, crystal structures, molecular geometries and vibrational, rotational and electronic energy levels and equilibrium constants

Margrave, J. L.↗
NASA NTRS1972

Electron paramagnetic resonance study of two smectic A liquid crystals.

Study of the molecular ordering in two smectic A liquid crystals using vanadyl acetylacetonate as a paramagnetic probe. The average hyperfine splitting of the spectrum in the smectic A mesophase is measured as a function of the orientation relative to the dc magnetic field of the spectrometer after alignment of the molecules of the liquid crystal.

Fryburg, G. C.↗
NASA NTRS1986

Recent developments in materials and detectors for the infrared; Proceedings of the Meeting, Cannes, France, November 25, 26, 1985

The present conference on advancements in IR-sensitive materials and detector technologies employing them gives attention to thermal detectors, focal plane array processing detectors, novel detector designs, general properties of IR optics materials, and preparation methods for such materials. Specific topics encompass the fabrication of InSb MIS structures prepared by photochemical vapor deposition, IR heterodyne detectors employing cadmium mercury telluride, low microphony pyroelectric arrays, IR detection based on minority carrier extrusion, longwave reststrahl in IR crystals, and molecular beam techniques for optical thin film fabrication.

Morten, F. D.↗
NASA NTRS1999

Crystallization and preliminary X-ray diffraction analysis of restriction endonuclease EcoRII

Crystals of the restriction endonuclease EcoRII have been obtained by the vapor-diffusion technique in the presence of ammonium sulfate or polyethylene glycol. The best crystals were grown with ammonium sulfate as a precipitant. Crystals with dimensions of up to 0.6 x 0. 6 x 0.6 mm have been observed. The crystals diffract to about 4.0 A resolution at a cryo-temperature of 100 K using a rotating-anode X-ray source and a Rigaku R-AXIS IV imaging-plate detector. The space group has been determined to be either I23 or I2(1)3, with unit-cell parameters a = b = c = 160.3 A, alpha = beta = gamma = 90 degrees. The crystal asymmetric unit contains two protein molecules, and self-rotation function analysis shows a pseudo-twofold symmetry relating the two monomers. Attempts to improve the resolution of crystal diffraction and to search for heavy-atom derivatives are under way.

Deoxyribonucleases, Type II Site-Specific/chemistr↗
DOE OSTI2020

Reactor for hydrothermal growth of structured materials

Design, fabrication, and usage of a reactor are presented for synthesis of structured materials from a liquid-phase precursor by heating. The structured materials are particles, membranes or films of micro-porous molecular sieve crystals such as zeolite and meso-porous materials. The precursor solution and structured materials in the reactor are uniformly heated by a planar heater with characteristic heat transfer dimension in the range of 3 mm to 10 cm. A planar heater having width and length at least three times of the characteristic heat transfer dimension provides at least one surface of uniform temperature distribution for heating purposes. Heating is conducted over a temperature range of 20 to 300° C. The planar heater can be heated by electrical power of by thermal fluid.

36 MATERIALS SCIENCE↗
NASA NTRS2004

Kinetic Roughening and Energetics of Tetragonal Lysozyme Crystal Growth: A Preliminary Atomic Force Microscopy Investigation

We examined particulars of crystal growth from measurements obtained at both microscopic and molecular levels. The crystal growth measurements performed at the microscopic level are well characterized by a model that balances the flux of macromolecules towards the crystal surface with the flux of the crystal surface. Numerical evaluation of model with measurements of crystal growth, in time, provided accurate estimates for the average growth velocities. Growth velocities thus obtained were also interpreted using well-established phenomenological theories. Moreover, we find that microscopic measurements of growth velocity measurements obtained as a function of temperature best characterizes changes in crystal growth modes, when present. We also examined the possibility of detecting a change in crystal growth modes at the molecular level using atomic force microscopy, AFM. From preliminary AFM measurements performed at various supersaturations, we find that magnitude of surface height fluctuations, h(x), increases with supersaturation. Further examination of surface height fluctuations using methods established for fluctuation spectroscopy also enabled the discovery of the existence of a characteristic length, c, which may possibly determine the mode of crystal growth. Although the results are preliminary, we establish the non- critical divergence of 5 and the root-mean-square (rms) magnitude of height-height fluctuations as the kinetic roughening transition temperatures are approached. Moreover, we also examine approximate models for interpreting the non-critical behavior of both 6 and rms magnitude of height-height fluctuations, as the solution supersaturation is increased towards the kinetic roughening supersaturation.

Gorti, Sridhar↗