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At least 397 records · Page 22

Solution-Based Synthesis of Ultrathin Quasi-2D Amorphous Carbon for Nanoelectronics

The synthesis of ultrathin 2D amorphous dielectric film represents a major challenge due to the metastable nature of amorphous phases. We describe a scalable and solution-based strategy to prepare wafer-scale 2D amorphous carbon with thickness down to 1–2 atomic layers from coal-derived carbon quantum dots as precursors. The prepared atomically thin 2D amorphous carbon can be suspended over cavities as freestanding membranes with high modulus of 400±100 GPa and demonstrate robust dielectric properties with dielectric strength above 20 MV·cm-1 and leakage current density below 10-4 A·cm-2 through a scaled thickness of three-atomic layers. When implemented as ultrathin gate dielectrics in 2D transistors or ion-transport media in memristors, they enable exceptional device performance and spatiotemporal uniformity, resulting from their amorphous form, intrinsic ultrathinness, and 2D atomic structures.

Pham, Viet Hung [NETL Site Support Contractor, Nat↗

Optical Properties of Non-stoichiometric Amorphous Silicates with Application to Circumstellar Dust Extinction

We determine the optical constants of non-stoichiometric amorphous magnesium-iron silicates and demonstrate that they can well reproduce the observed mid-infrared emission spectra of evolved stars. Stoichiometric and non-stoichiometric amorphous magnesium-iron silicate films are fabricated by pulsed laser deposition. Transmittance and ellipsometry measurements are performed in the wavelength range between 2 and 200 μm and 1.7 and 33 μm, respectively. Optical constants are derived from transmittance and ellipsometric Ψ and Δ spectra by means of oscillator models. These newly obtained optical constants are applied in radiative transfer models for examining reproducibility of the observed spectral features of circumstellar dust shells around supergiants. The spectra of four selected supergiants are dominated by amorphous silicate dust emission in the wavelength range between 9 and 25 μm. To obtain a good fit to the observed spectra, we take into account amorphous corundum and metallic iron particles as additional dust components to the model calculations to rationalize the dust emission at λ<8 μm. For each of the objects, a set of model parameters (dust mass and condensation temperature) is derived by an automated optimization procedure that reproduces the observation well. Consequently, our model spectra using new optical data reveal that the silicate bands at ∼10 and ∼18 μm depend on the magnesium and iron ratio in the silicate system, and that a good fit requires a significant iron content of the amorphous silicate dust component to reproduce the observed peak positions and shape of the silicate bands.

79 ASTRONOMY AND ASTROPHYSICS↗

A kinetic study of hydrous alteration of amorphous MgSiO smokes - Implications for cometary particles and chondrite matrix

Measurements of the rate of hydrous alteration of amorphous Mg-SiO smokes are reported as a function of temperature, as inferred by observing changes in the infrared spectra of these materials. It is shown that under the conditions reported for the nucleus of Comet Halley, based on measurements made by the Vega and Giotto missions, amorphous, anhydrous Mg-SiO smokes would become hydrated within several weeks in the dusty regolith observed on the surface. However, if such grains were released in 'jets' or from loose ice fragments, then previously amorphous grains would retain their anhydrous nature. Similarly, brief periods of aqueous activity on meteorite parent bodies would convert amorphous, fine-grained material to hydrated phyllosilicates much more rapidly than coarse mineral grains. A kinetic model might therefore be developed to explain the observed textural relationships in the matrices of carbonaceous chondrites such as Mokoia, where amorphous phyllosilicates are intimately associated with coarse anhydrous grains.

Nelson, Robert↗

Direct measurement of free-energy barrier to nucleation of crystallites in amorphous silicon thin films

A method is introduced to measure the free-energy barrier W(sup *), the activation energy, and activation entropy to nucleation of crystallites in amorphous solids, independent of the energy barrier to growth. The method allows one to determine the temperature dependence of W(sup *), and the effect of the preparation conditions of the initial amorphous phase, the dopants, and the crystallization methds on W(sup *). The method is applied to determine the free-energy barrier to nucleation of crystallites in amorphous silicon (a-Si) thin films. For thermally induced nucleation in a-Si thin films with annealing temperatures in the range of from 824 to 983 K, the free-energy barrier W(sup *) to nucleation of silicon crystals is about 2.0 - 2.1 eV regardless of the preparation conditions of the films. The observation supports the idea that a-Si transforms into an intermediate amorphous state through the structural relaxation prior to the onset of nucleation of crystallites in a-Si. The observation also indicates that the activation entropy may be an insignificant part of the free-energy barrier for the nucleation of crystallites in a-Si. Compared with the free-energy barrier to nucleation of crystallites in undoped a-Si films, a significant reduction is observed in the free-energy barrier to nucleation in Cu-doped a-Si films. For a-Si under irradiation of Xe(2+) at 10(exp 5) eV, the free-energy barrier to ion-induced nucleation of crystallites is shown to be about half of the value associated with thermal-induced nucleation of crystallites in a-Si under the otherwise same conditions, which is much more significant than previously expected. The present method has a general kinetic basis; it thus should be equally applicable to nucleation of crystallites in any amorphous elemental semiconductors and semiconductor alloys, metallic and polymeric glasses, and to nucleation of crystallites in melts and solutions.

Shi, Frank G.↗

Crystallization of amorphous water ice in the solar system

Electron diffraction studies of vapor-deposited water ice have characterized the dynamical structural changes during crystallization that affect volatile retention in cometary materials. Crystallization is found to occur by nucleation of small domains, while leaving a significant part of the amorphous material in a slightly more relaxed amorphous state that coexists metastably with cubic crystalline ice. The onset of the amorphous relaxation is prior to crystallization and coincides with the glass transition. Above the glass transition temperature, the crystallization kinetics are consistent with the amorphous solid becoming a "strong" viscous liquid. The amorphous component can effectively retain volatiles during crystallization if the volatile concentration is approximately 10% or less. For higher initial impurity concentrations, a significant amount of impurities is released during crystallization, probably because the impurities are trapped on the surfaces of micropores. A model for crystallization over long timescales is described that can be applied to a wide range of impure water ices under typical astrophysical conditions if the fragility factor D, which describes the viscosity behavior, can be estimated.

NASA Center ARC↗

Amorphous Rover

A proposed mobile robot, denoted the amorphous rover, would vary its own size and shape in order to traverse terrain by means of rolling and/or slithering action. The amorphous rover was conceived as a robust, lightweight alternative to the wheeled rover-class robotic vehicle heretofore used in exploration of Mars. Unlike a wheeled rover, the amorphous rover would not have a predefined front, back, top, bottom, or sides. Hence, maneuvering of the amorphous rover would be more robust: the amorphous rover would not be vulnerable to overturning, could move backward or sideways as well as forward, and could even narrow itself to squeeze through small openings.

Curtis, Steven A.↗

Transmission X-ray Diffraction (XRD) Patterns Relevant to the MSL Chemin Amorphous Component: Sulfates And Silicates

The Mars Science Laboratory (MSL) CheMin instrument on the Curiosity rover is a transmission X-ray diffractometer (Co-Kalpha radiation source and a approx.5deg to approx.52deg 2theta range) where the analyzed powder samples are constrained to have discrete particle diameters <150 microns by a sieve. To date, diffraction patterns have been obtained for one basaltic soil (Rocknest (RN)) and four drill fines of coherent rock (John Klein (JK), Cumberland (CB), Windjana (WJ), and Confidence Hills (CH)). The CheMin instrument has detected and quantified the abundance of both primary igneous (e.g., feldspar, olivine, and pyroxene) and secondary (e.g., Ca-sulfates, hematite, akaganeite, and Fe-saponite) minerals. The diffraction patterns of all CheMin samples are also characterized by a broad diffraction band centered near 30deg 2theta and by increasing diffraction intensity (scattering continuum) from approx.15deg to approx.5deg, the 2theta minimum. Both the broad band and the scattering continuum are attributed to the presence of an XRD amorphous component. Estimates of amorphous component abundance, based on the XRD data itself and on mass-balance calculations using APXS data crystalline component chemistry derived from XRD data, martian meteorites, and/or stoichiometry [e.g., 6-9], range from approx.20 wt.% to approx.50 wt.% of bulk sample. The APXSbased calculations show that the amorphous component is rich in volatile elements (esp. SO3) and is not simply primary basaltic glass, which was used as a surrogate to model the broad band in the RN CheMin pattern. For RN, the entire volatile inventory (except minor anhydrite) is assigned to the amorphous component because no volatile-bearing crystalline phases were reported within detection limits [2]. For JK and CB, Fesaponite, basanite, and akaganeite are volatile-bearing crystalline components. Here we report transmission XRD patterns for sulfate and silicate phases relevant to interpretation of MSL-CheMin XRD amorphous components.

Morris, R. V.↗

Infrared Spectra and Optical Constants of Elusive Amorphous Methane

New and accurate laboratory results are reported for amorphous methane (CH4) ice near 10 K for the study of the interstellar medium (ISM) and the outer Solar System. Near- and mid-infrared (IR) data, including spectra, band strengths, absorption coefficients, and optical constants, are presented for the first time for this seldom-studied amorphous solid. The apparent IR band strength near 1300 cm(exp −1) (7.69 micrometer) for amorphous CH4 is found to be about 33% higher than the value long used by IR astronomers to convert spectral observations of interstellar CH4 into CH4 abundances. Although CH4 is most likely to be found in an amorphous phase in the ISM, a comparison of results from various laboratory groups shows that the earlier CH4 band strength at 1300 cm(exp −1) (7.69 micrometer) was derived from IR spectra of ices that were either partially or entirely crystalline CH4 Applications of the new amorphous-CH4 results are discussed, and all optical constants are made available in electronic form.

ISM: abundances↗

Cold Conditions Promote Mg and Si Incorporation in Fe/Si-Rich and Al-Poor X-Ray Amorphous Material in Mars-Relevant Field Environments

X-ray amorphous material that is variably Fe/Si-rich, Al-poor, and volatile containing is prevalent (~15-73 wt.%) within ancient fluvial-lacustrine and eolian sediments examined by the CheMin instrument in Gale crater. Al-rich X-ray amorphous material within Mars-analog environments on Earth has previously been proposed to result from aqueous alteration under cold and icy conditions. However, to the best of our knowledge, no work to date has examined the effects of climate upon the formation of Al-poor and Fe/Si-rich X-ray amorphous material. This study therefore investigates the production of Al-poor and Fe-containing X-ray amorphous material and the chemical heterogeneity within that material under varying temperature conditions to better interpret the formation of Fe-containing X-ray amorphous material detected on Mars.

A D Feldman↗

Amorphous metal formulations and structured coatings for corrosion and wear resistance

A system for coating a surface comprising providing a source of amorphous metal that contains more than 11 elements and applying the amorphous metal that contains more than 11 elements to the surface by a spray. Also a coating comprising a composite material made of amorphous metal that contains more than 11 elements. An apparatus for producing a corrosion-resistant amorphous-metal coating on a structure comprises a deposition chamber, a deposition source in the deposition chamber that produces a deposition spray, the deposition source containing a composite material made of amorphous metal that contains more than 11 elements, and a system that directs the deposition spray onto the structure.

36 MATERIALS SCIENCE↗

Amorphous metal formulations and structured coatings for corrosion and wear resistance

A system for coating a surface comprising providing a source of amorphous metal that contains more than 11 elements and applying the amorphous metal that contains more than 11 elements to the surface by a spray. Also a coating comprising a composite material made of amorphous metal that contains more than 11 elements. An apparatus for producing a corrosion-resistant amorphous-metal coating on a structure comprises a deposition chamber, a deposition source in the deposition chamber that produces a deposition spray, the deposition source containing a composite material made of amorphous metal that contains more than 11 elements, and a system that directs the deposition spray onto the structure.

36 MATERIALS SCIENCE↗

In situ observation of medium range ordering and crystallization of amorphous TiO 2 ultrathin films grown by atomic layer deposition

The evolution of medium range ordering (MRO) and crystallization behavior of amorphous TiO 2 films grown by atomic layer deposition (ALD) were studied using in situ four-dimensional scanning transmission electron microscopy. The films remain fully amorphous when grown at 120 °C or below, but they start showing crystallization of anatase phases when grown at 140 °C or above. The degree of MRO increases as a function of temperature and maximizes at 140 °C when crystallization starts to occur, which suggests that crystallization prerequires the development of nanoscale MRO that serves as the site of nucleation. In situ annealing of amorphous TiO 2 films grown at 80 °C shows enhancement of MRO but limited number of nucleation, which suggests that post-annealing develops only a small portion of MRO into crystal nuclei. The MRO regions that do not develop into crystals undergo structural relaxation instead, which provides insights into the critical size and degree of ordering and the stability of certain MRO types at different temperatures. In addition, crystallographic defects were observed within crystal phases, which likely negate corrosion resistance of the film. Our result highlights the importance of understanding and controlling MRO for optimizing ALD-grown amorphous films for next-generation functional devices and renewable energy applications.

36 MATERIALS SCIENCE↗

Enhanced Drug Delivery by Dissolution of Amorphous Drug Encapsulated in a Water Unstable Metal–Organic Framework (MOF)

Encapsulating a drug molecule into a water-reactive metal–organic framework (MOF) leads to amorphous drug confined within the nanoscale pores. Rapid release of drug occurs upon hydrolytic decomposition of MOF in dissolution media. Application to improve dissolution and solubility for the hydrophobic small drug molecules curcumin, sulindac, and triamterene is demonstrated. The drug@MOF composites exhibit significantly enhanced dissolution and achieves high supersaturation in simulated gastric and/or phosphate buffer saline media. This combination strategy where MOF inhibits crystallization of the amorphous phase and then releases drug upon MOF irreversible structural collapse represents a novel and generalizable approach for drug delivery of poorly soluble compounds while overcoming the traditional weakness of amorphous drug delivery: physical instability of the amorphous form.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of the Boron Content on the Amorphization Process and Magnetic Properties of the Mechanically Alloyed Fe{sub 92−x}Nb{sub 8}B{sub x} Powders

The effect of the B content on the microstructural, structural, and magnetic properties of partially amorphous Fe{sub 92−x}Nb{sub 8}B{sub x} (x = 5, 10, 15, and 20) alloys has been investigated by means of scanning electron microscopy, X-ray diffraction, high and low-temperature extraction-type magnetometers. The XRD results reveal the formation of a nanocomposite structure where nanocrystalline bcc α-Fe and Fe{sub 2}B phases are embedded into an amorphous matrix. The FeB boride is observed for higher boron contents (x = 15 and 20), and the crystallite sizes are in the range of 7–24 nm. As the B content increases, the amorphous phase-relative proportion and coercivity increase, whereas the saturation magnetization decreases. An important magnetic hardening occurs by lowering the temperature from 400 to 5 K for x = 20% B. The variation of the Curie temperature can be attributed to the heterogeneity of the amorphous matrix.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Magnetic Spectra of Soft Magnetic Composites Based on Fe-Si-Cr-B Amorphous and Carbonyl-Iron Powders

Fe–Si–Cr–B amorphous and carbonyl-iron powders insulated with phosphoric acid solution were used to prepare soft magnetic composites. The mass ratios of phosphoric acid insulation solution and the carbonyl-iron powder dependences of the magnetic spectrum, the density, and the resistivity were studied. Both the real part and the imaginary part of the core’s complex permeability increased after an initial decrease with the acid mass ratio increasing. This is similar to the variation tendency of the core’s density and opposite to the variation tendency of the core’s resistivity. The amount of the air gap, reflected by the density, was proposed to be the most important factor that has a great influence on the composite’s magnetic properties. The increase of the air gap reduced the effective demagnetizing field and the resistivity. This improved the permeability and the hysteresis loss and deteriorated the eddy-current loss. Carbonyl-iron powder addition was found to improve the moldability and the permeability of the composite based on the Fe-Si-Cr-B amorphous powder, although its loss was higher than that of the amorphous powder. All these findings can be referenced when designing an amorphous-based soft magnetic composite (SMC) core with balanced permeability, loss, and cost for high-frequency inductor within a MHz band.

36 MATERIALS SCIENCE↗

Sliding Wear Behavior of Spark-Plasma-Sintered Fe-Based Amorphous Alloy Coatings on Cu-Ni Alloy

This paper reports on the processing of Fe{sub 48}Cr{sub 15}Mo{sub 14}Y{sub 2}C{sub 15}B{sub 6} amorphous alloy coatings on Cu-10%Ni (wt.%) alloy using spark plasma sintering. The amorphous alloy coatings were sintered at temperatures ranging from 575 to 675 °C at a pressure of 50 MPa. The development of microstructure, phases, and wear properties with sintering temperature of the coatings is investigated. The sintered coatings were found to be near fully dense with hardness close to that of the sintered bulk amorphous alloy. X-ray analysis indicated increasing degree of devitrification of the amorphous coatings with increasing sintering temperature. The wear behavior of the coatings is significantly influenced by the sintering temperature with volume wear rate first decreasing in the temperature range of 575-650 °C and then increasing above 650 °C. The variation in wear behavior is explained based on relative stability of the protective surface layer and embrittlement of the surface with the sintering temperature.

36 MATERIALS SCIENCE↗

Amorphization due to electronic energy deposition in defective strontium titanate

The synergistic interaction of electronic energy loss by ions with ion-induced defects created by elastic nuclear scattering processes has been investigated for single crystal SrTiO 3 . An initial pre-damaged defect state corresponding to a relative disorder level of 0.10–0.15 sensitizes the SrTiO 3 to amorphous track formation along the ion path of 12 and 20 MeV Ti, 21 MeV Cl and 21 MeV Ni ions, where Ti, Cl and Ni ions otherwise do not produce amorphous or damage tracks in pristine SrTiO 3 . The electronic stopping power threshold for amorphous ion track formation is found to be 6.7 keV/nm for the pre-damaged defect state studied in this work. Lastly, these results suggest the possibility of selectively producing nanometer scale, amorphous ion tracks in thin films of epitaxial SrTiO 3 .

36 MATERIALS SCIENCE↗

First-principles study of surface properties of crystalline and amorphous uranium aluminides

Surface energy is a crucial material property required for the modeling of fission gas bubble behavior in nuclear materials. However, there is no information available regarding the surface properties of uranium aluminides. In this work we systematically investigate the surface properties of uranium aluminides (UAl 3 and UAl 4 ) by first-principles density functional theory (DFT) calculations. Specifically, a total of 13 surface orientations with a maximum Miller index (MMI) up to 3 are studied for cubic UAl 3 , while 19 surfaces with a MMI of 2 for orthorhombic UAl 4 . Using the surface energies predicted by DFT, the surface properties of equilibrium single crystal UAl 3 and UAl 4 , including surface area weighted surface energy, dominant surface orientations and surface anisotropy, are obtained from Wulff construction. To understand gas bubble behaviors in amorphous uranium aluminides under irradiation, we study the surface properties of amorphous UAl 3 and UAl 4 . Compared to the crystalline phases, the amorphous phases are found to have lower surface energies due to the reduced number of breaking U-Al bonds close to the surface. The currently obtained surface properties of UAl 3 and UAl 4 can be used for the future modeling of gas bubble behaviors in both crystalline and amorphous uranium aluminide fuels.

36 MATERIALS SCIENCE↗