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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

New Solids in As-O-Mo, As(P)-O-Mo(W) and As(P)-O-Nb(W) Systems That Exhibit Nonlinear Optical Properties

Interactions between well-mixed fine powders of As 2 O 3 , P 2 O 5 , MoO 3 , WO 3 and Nb 2 O 5 at different stoichiometry in quartz ampoules under vacuum at ~1000 °C in the presence of metallic molybdenum (or niobium), over several weeks, led to shiny dichroic crystalline materials being formed in cooler parts of the reaction vessel. An addition of small quantities of metals-Mo or Nb-was made with the aim of partially reducing their highly oxidized Mo(VI), W(VI) or Nb(V) species to corresponding Mo(V), W(V) and Nb(IV) centers, in order to form mixed valence solids. Sublimed crystals of four new compounds were investigated using a variety of techniques, with prime emphasis on the X-ray analysis, followed by spectroscopy (diffusion reflectance, IR, Raman and EPR), second harmonic generation (SHG), thermal analysis under N 2 and air atmosphere, and single crystals electrical conductivity studies. The results evidenced the formation of new complex solids of previously unknown compositions and structures. Three out of four compounds crystallized in non-centrosymmetric space groups and represent layered 2D polymeric puckered structures that being stacked on each other form 3D lattices. All new solids exhibit strong second-harmonic-generation (SHG effect; based on YAG 1064 nm tests with detection of 532 nm photons), and a rare photosalient effect when crystals physically move in the laser beam. Single crystals’ electrical conductivity of the four new synthesized compounds was measured, and the results showed their semiconductor behavior. Values of band gaps of these new solids were determined using diffusion reflectance spectroscopy in the visible region. Aspects of new solids’ practical usefulness are discussed.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Luminescent and Magnetic Tb-MOF Flakes Deposited on Silicon

The synthesis of a terbium-based 2D metal–organic framework (MOF), of formula [Tb(MeCOO)(PhCOO) 2 ] (1), a crystalline material formed by neutral nanosheets held together by Van der Waals interactions, is presented. The material can be easily exfoliated by sonication and deposited onto different substrates. Uniform distributions of Tb-2D MOF flakes onto silicon were obtained by spin-coating. We report the luminescent and magnetic properties of the deposited flakes compared with those of the bulk. Complex 1 is luminescent in the visible and has a sizeable quantum yield of QY = 61% upon excitation at 280 nm. Photoluminescence measurements performed using a micro-Raman set up allowed us to characterize the luminescent spectra of individual flakes on silicon. Magnetization measurements of flakes-on-silicon with the applied magnetic field in-plane and out-of-plane display anisotropy. Ac susceptibility measurements show that 1 in bulk exhibits field-induced slow relaxation of the magnetization through two relaxation paths and the slowest one, with a relaxation time of τ lf ≈ 0.5 s, is assigned to a direct process mechanism. The reported exfoliation of lanthanide 2D-MOFs onto substrates is an attractive approach for the development of multifunctional materials and devices for different applications.

2D MOFs↗
DOE OSTI2020

Violation of the T –1 Relationship in the Lattice Thermal Conductivity of Mg 3 Sb 2 with Locally Asymmetric Vibrations

Most crystalline materials follow the guidelines of T –1 temperature-dependent lattice thermal conductivity (κ L ) at elevated temperatures. Here, we observe a weak temperature dependence of κ L in Mg 3 Sb 2 , T –0.48 from theory and T –0.57 from measurements, based on a comprehensive study combining ab initio molecular dynamics calculations and experimental measurements on single crystal Mg 3 Sb 2 . These results can be understood in terms of the so-called “phonon renormalization” effects due to the strong temperature dependence of the interatomic force constants (IFCs). The increasing temperature leads to the frequency upshifting for those low-frequency phonons dominating heat transport, and more importantly, the phonon-phonon interactions are weakened. In-depth analysis reveals that the phenomenon is closely related to the temperature-induced asymmetric movements of Mg atoms within MgSb 4 tetrahedron. With increasing temperature, these Mg atoms tend to locate at the areas with relatively low force in the force profile, leading to reduced effective 3 rd -order IFCs. The locally asymmetrical atomic movements at elevated temperatures can be further treated as an indicator of temperature-induced variations of IFCs and thus relatively strong phonon renormalization. The present work sheds light on the fundamental origins of anomalous temperature dependence of κ L in thermoelectrics.

36 MATERIALS SCIENCE↗
NASA NTRS1973

New techniques for far-infrared filters.

The techniques considered make it possible to construct high performance low-pass wide-band, and medium-band filters at wavelengths in the range from 25 to 300 micrometers. Short wavelength rejection without appreciable loss at long wavelengths is achieved by means of small particle scattering. Spectral definition in the far infrared is obtained by cooling one or more crystalline materials to liquid-He or liquid-nitrogen temperatures. The problem of reflection losses at the various surfaces is solved by a new antireflection coating technique.

Armstrong, K. R.↗
NASA NTRS1975

Evaluation of semiconductor specimens by X-ray analysis

Germanium and GaAs crystals were investigated for studies on photovoltaic effects, chemical etching and epitaxial growth according to the overall objective to assess the defect structure of single crystalline materials. A brief survey of basic theory and topographical techniques is provided; examples of topographs are presented.

Walter, H. U.↗
NASA NTRS1979

Precision cleaver for "soft" crystals

"Soft" crystals are cleaved as thin 0.005 inch with special cleaver. Thin slices of soft crystalline materials are used in X-ray spectrometers. Slices are usually cut by hand with wire or blade. Wire tends to scratch surface and to produce slices of nonuniform thickness. Device will rapidly cut soft crystals in smooth, thin, uniform slices.

Benedicto, J. S. J.↗
NASA NTRS1978

Strain-rate/temperature behavior of high density polyethylene in compression

The compressive strain rate/temperature behavior of highly linear, high density polyethylene was analyzed in terms of the predictive relations developed for metals and other crystalline materials. For strains of 5 percent and above, the relationship between applied strain rate, dotted epsilon, and resulting flow stress, sigma, was found to be: dotted epsilon exp times (Q sub f/RT) = k'(sigma/sigma sub c) to the nth power; the left-hand side is the activation-energy-compensated strain rate, where Q sub f is activation energy for flow, R is gas constant, and T is temperature; k is a constant, n is temperature-independent stress exponent, and sigma/sigma sub c is structure-compensated stress. A master curve resulted from a logarithmic plot of activation-energy-compensated strain rate versus structure-compensated stress.

Clements, L. L.↗
NASA NTRS1981

Cleaving machine for hard crystals

Hard crystalline materials such as lithium fluoride (LiF) are cleaved in thin sections by semiautomatic machine. Yield of undistorted LiF crystals is almost 100 percent, even when cleaved section is only 1/32 inch thick. Machine contains spring-activated hammer that limits penetration of blade and controls shock that cleaves crystal. Fixture with spring-loaded clamps precisely locates and holds crystal, restraining it in ideal position for cleaving. Crystal then splays apart.

Benedicto, J. S. J.↗
NASA NTRS1979

Trace element release from estuarine sediments of South Mosquito Lagoon near Kennedy Space Center

Analytical partitioning of four trace metals in estuarine sediments collected from eight sites in South Mosquito Lagoon near Kennedy Space Center, in terms of four different categories was accomplished using four different extraction techniques. The concentrations of the four trace metals, Zn, Mn, Cd, and Cu, released in interstitial water extract, 1 N ammonium acetate extract, conc. HCl extract and fusion extract of sediments as well as their concentrations in water samples collected from the same location were determined using flame atomic absorption technique. From the analytical results the percentages of total amount of each metal distributed among four different categories, interstitial water phase, acetate extractable, acid extractable and detrital crystalline material, were determined. Our results suggest that analytical partitioning of trace metals in estuarine sediments may be used to study the mechanism of incorporation of trace metals with sediments from natural waters. A correlation between the seasonal variation in the concentration of acetate extractable trace metals in the sediment and similar variation in their concentration in water was observed. A mechanism for the release of trace metals from estuarine sediments to natural water is also suggested.

Menon, M. P.↗
NASA NTRS1980

Structure and optical properties of evaporated films of the Cr- and V-group metals

Thin films of Cr, Mo, and W rapidly evaporated in high vacuum (5 x 10 to the -7th torr) onto room-temperature substrates show anomalously low reflectance (compared to bulk samples). From electron and X-ray diffraction and electron microscopy, the normal bcc crystal structure is found, but with very fine grains. Columnar grains about 100 A in diameter were separated by a less dense grain-boundary network about 10-A wide. The measured optical conductivity agrees with an inhomogeneous-medium model that assumes the normal crystalline conductivity for the grain interiors, with model parameters that correlate to the observed columnar grain size. In contrast, V and Nb films rapidly evaporated onto room-temperature substrates have the reflectance of bulk crystalline material. On liquid-nitrogen temperature substrates, however, V and Nb have normal bcc crystal structure but with small flat-plate grains, and the same model, with appropriate parameters, accounts for the optical conductivity. The difference between these two groups apparently depends on residual gases segregated at the grain boundaries in the Cr-group films.

Nestell, J. E., Jr.↗
NASA NTRS1980

Variations in interior morphology of 15-20 km lunar craters - Implications for a major subsurface discontinuity

Craters vary in morphology as a function of crater diameter, age, and mode of origin. This study concentrates on the morphology of young lunar impact craters within a limited size range. Elimination of morphologic variations generally attributed to crater size or age leaves a small population which should nearly reflect the varying properties of the lunar substrate. The sample consists of 17 craters 15-20 km in diameter with both simple and complex morphologies. While depth/diameter ratios do not obviously differ between mare and highland subsets, apparent depth, rim height, and profile data do differ distinctly. Highland craters tend to be deep, simple, and bowl-shaped. Mare craters tend to be shallow and flat-floored. Rim heights of complex mare craters are typically greater than those of simple craters. Differences of highland and mare crater morphologies are attributed to variations in the thickness of the lunar megaregolith. Highland craters in this size range do not penetrate the megaregolith. The depth and morphology of complex craters are controlled by the discontinuity at the transition from highly brecciated megaregolith to more coherent crystalline material of the upper crust.

De Hon, R. A.↗
NASA NTRS1981

Dehydration-induced luminescence in clay minerals

Reports of triboluminescent phenomena in organic crystalline materials prompted a search for related processes in clay minerals. The reported extensive mechanical distortion produced on freezing and drying of montmorillonite was particularly interesting because of studies of condensation reactions in a wet/dry cycled reaction sequence. The discovery of an unusual luminescent process in several clay minerals is reported and its characteristics are described.

Coyne, L. M.↗
NASA NTRS1984

Finite-difference fluid dynamics computer mathematical models for the design and interpretation of experiments for space flight

Numerical methods are used to design a spherical baroclinic flow model experiment of the large scale atmosphere flow for Spacelab. The dielectric simulation of radial gravity is only dominant in a low gravity environment. Computer codes are developed to study the processes at work in crystal growing systems which are also candidates for space flight. Crystalline materials rarely achieve their potential properties because of imperfections and component concentration variations. Thermosolutal convection in the liquid melt can be the cause of these imperfections. Such convection is suppressed in a low gravity environment. Two and three dimensional finite difference codes are being used for this work. Nonuniform meshes and implicit iterative methods are used. The iterative method for steady solutions is based on time stepping but has the options of different time steps for velocity and temperature and of a time step varying smoothly with position according to specified powers of the mesh spacings. This allows for more rapid convergence. The code being developed for the crystal growth studies allows for growth of the crystal as the solid-liquid interface. The moving interface is followed using finite differences; shape variations are permitted. For convenience in applying finite differences in the solid and liquid, a time dependent coordinate transformation is used to make this interface a coordinate surface.

Roberts, G. O.↗
NASA NTRS1983

Surfaces

Techniques for the characterization of surface cleanliness and roughness for predicting the quality of an adhesive bond are outlined. Generally, smooth surfaces are only available from cleavage of crystalline materials along a natural cleavage plane. Films must be deposited on metal surfaces to achieve the same smoothness. Once the surfaces are clean, however, reaction with the ambient atmosphere becomes likely through diffusive and absorption processes, producing asperities. Electron diffraction, Auger electron, and X ray emission spectroscopy are used to characterize surface condition. Once the surface is observed to be clean, the application of an adhesive will usually prohibit separation along the adhesive; separation is then confined to the weaker of the two materials. Finally, the use of polytetrafluorothylene adhesive to test the adhesion between polymers and metal surfaces is described.

Buckley, D. H.↗
NASA NTRS1984

Fracto-emission - The role of charge separation

Fracto-emission is the emission of particles (e.g., electrons, ions, ground state and excited neutrals, and photons) during and following fracture. It is found that during fracture in vacuum of adhesive bonds and crystalline materials involving large amounts of charge separation on the surface the emission of charged particles, excited neutrals, light, and radio waves occurs with unique and revealing time dependencies. Simultaneous fracto-emission measurements on several systems are reported. The results are interpreted in terms of a conceptual model involving the following steps: (1) charge separation due to fracture, (2) desorption of gases from the material into the crack tip, (3) a gas discharge in the crack, (4) energetic bombardment of the freshly created crack walls, and (5) thermally stimulated electron emission, accompanied by electron stimulated desorption of ions and excited neutrals. In addition to evidence from fracture experiments, results from studies of electron bombardment of a polymer surface are presented.

Dickinson, J. T.↗
NASA NTRS1986

Growth of crystals of several boron-carbon compositions by chemical vapor deposition

Boron-carbon compounds have been deposited by the flow of carbon tetrachloride and boron trichloride, in the presence of a large excess of hydrogen, over a graphite surface maintained at 1000-1300 C. Deposits were formed on either an RF-heated disc or a tube or insert heated by a resistance furnace. Crystalline materials ranging in composition from B2C to B17C have been obtained.

Kevill, D. N.↗
NASA NTRS1986

Thermoluminescence and the shock and reheating history of meteorites. III - The shergottites

Thermoluminescence (TL) measurements on Shergotty, ALHA 77005, Zagami, and EETA 79001 (lithology A) have been used to obtain further information on the shock history of these meteorites. The level of TL sensitivity in the shergottites varied by a factor of 10, but was always low, probably reflecting the amount of crystalline material in the maskelynite. There are trends in the TL peak temperature, peak width, and TL sensitivity which are believed to be associated with different proportions of feldspar in high- and low-temperature forms. This interpretation is consistent with the observed changes induced in the TL properties by annealing shergottites at 400-900 C. It is suggested that the observed trends were produced during postshock crystallization at a variety of cooling rates, the increasing order of cooling rate being EETA 79001, Zagami, ALHA 77005, and Shergotty, and that there is high-temperature feldspar present in all the samples. This implies a postshock temperature above 600 C, and a small (less than 10 m) size of the ejecta. Current theories are well able to explain how objects of this size could have been ejected from Mars.

Hasan, F. A.↗
NASA NTRS1988

K-T impact(s): Continental, oceanic or both

Although geochemical and mineralogical evidence indicate that a major accretionary event occurred at the K-T boundary, no impact crater of suitable size and age was recognized. The 35 km Manson Structure, Iowa, was suggested recently as a possibility and Ar-40/Ar-39 determinations indicate that its formation age is indistinguishable from that of the K-T boundary. In order to test a possible association between Manson and the K-T boundary clay, the geochemistry and mineralogy of the K-T boundary clays at the Scollard Canyon section, Alberta and the Starkville South section, Colorado are compared with three dominant lithologies affected by the Manson impact: Proterozoic red clastics, underlying late-state granites, and gneisses. The chemical and mineralogical makeup of the Scollard Canyon boundary clay and its clastic constituents are presented, commenting on the implications for impact models. An impact into crystalline material of continental affinity appears to be required to explain the mineralogy and chemistry of the Scollard Canyon (and other Western N. American K-T sections). The low REE abundances of some K-T boundary layers are unusual but perhaps attempts should be made to understand the contributions of individual crustal components (e.g., carbonates, arkoses) as well as the potential for alteration involving these and other elements during and after impact-induced vaporization, before mantle excavation is invoked. If further studies confirm the results of published studies of marine boundary clays that indicate an oceanic target, attention must be paid to the possibility that multiple impacts occurred at the K-T boundary - one or more on the continents and one or more in the ocean.

Sharpton, V. L.↗