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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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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Interactions of VO x Species with Amorphous TiO 2 Domains on ALD-Derived Alumina-Supported Materials

We report that alumina-supported VO x –TiO 2 materials are synthesized by atomic layer deposition (ALD) and characterized by diffuse reflectance UV–vis (DRUV–vis) spectroscopy, Raman spectroscopy, and density functional theory (DFT) calculations in order to identify the metal oxide structures present on the surface of the support. Preferential binding of VO x to TiO 2 domains is demonstrated by Raman spectroscopy studies and confirmed by DFT. Varying distributions of V–O–Ti, V–O–V, and V–O–Al bonds are present in the examined materials. The interactions of VO x and TiO 2 are elucidated further under a reducing, H 2 environment at elevated temperatures. An enhancement in reducibility of VOx species is expected and observed upon the modification of alumina with TiO 2 above monolayer coverages, but also when a single ALD cycle of TiO 2 is deposited following the deposition of VO x on the support. X-ray photoelectron spectroscopy (XPS) detects changes in the oxidation state of vanadium, but not titanium during reduction. Lastly, reversible migration and aggregation of V and Ti atoms is also detected upon heating in H 2 .

36 MATERIALS SCIENCE↗
DOE OSTI2025

Impact of amorphous pockets on displacement damage evolution in silicon

Silicon has long been known to exhibit amorphization in response to heavy particle bombardment. For doses below the total amorphization threshold, partial amorphization is observed in the form of scattered amorphous pockets. While extensive research has gone into modeling the formation and evolution of amorphous pockets in response to irradiation, no studies yet investigate their impact on the evolution of other damage such as interstitial supersaturation and clustering. In this study, we survey the impact of amorphous pockets on defect evolution in silicon when treated as static sinks. MD is first used to show that amorphous pockets provide energetically favorable sites for point defects relative to the crystalline bulk, supporting the hypothesis that they act as sinks. A 0-D cluster dynamics model is then constructed, taking an interstitial clustering model from the literature and including amorphous pockets as a sink species. We conduct our survey for temperatures between 30 and 400 °C and sink strengths between 1 to 6 x 10 10 cm −2 . Both implantation- and radiation-induced damage states are investigated using interstitial and vacancy concentrations as initial condition variables. We find that, due to the differing migration rates of the interstitial and the vacancy, amorphous pockets have a non-monotonic impact on the final damage state depending on the effective sink strength of the amorphous pockets, resulting in increased damage formation in regimes of intermediate amorphization. In conclusion, this result emphasizes the important role of amorphous pockets in governing the evolution of damage in partially amorphized crystalline materials.

36 MATERIALS SCIENCE↗
NASA NTRS2014

Amorphous Phases on the Surface of Mars

Both primary (volcanic/impact glasses) and secondary (opal/silica, allophane, hisingerite, npOx, S-bearing) amorphous phases appear to be major components of martian surface materials based on orbital and in-situ measurements. A key observation is that whereas regional/global scale amorphous components include altered glass and npOx, local scale amorphous phases include hydrated silica/opal. This suggests widespread alteration at low water-to-rock ratios, perhaps due to snow/ice melt with variable pH, and localized alteration at high water-to-rock ratios. Orbital and in-situ measurements of the regional/global amorphous component on Mars suggests that it is made up of at least three phases: npOx, amorphous silicate (likely altered glass), and an amorphous S-bearing phase. Fundamental questions regarding the composition and the formation of the regional/global amorphous component(s) still remain: Do the phases form locally or have they been homogenized through aeolian activity and derived from the global dust? Is the parent glass volcanic, impact, or both? Are the phases separate or intimately mixed (e.g., as in palagonite)? When did the amorphous phases form? To address the question of source (local and/or global), we need to look for variations in the different phases within the amorphous component through continued modeling of the chemical composition of the amorphous phases in samples from Gale using CheMin and APXS data. If we find variations (e.g., a lack of or enrichment in amorphous silicate in some samples), this may imply a local source for some phases. Furthermore, the chemical composition of the weathering products may give insight into the formation mechanisms of the parent glass (e.g., impact glasses contain higher Al and lower Si [30], so we might expect allophane as a weathering product of impact glass). To address the question of whether these phases are separate or intimately mixed, we need to do laboratory studies of naturally altered samples made up of mixed phases (e.g., palagonite) and synthetic single phases to determine their short-range order structures and calculate their XRD patterns to use in models of CheMin data. Finally, to address the timing of the alteration, we need to study rocks on the martian surface of different ages that may contain glass (volcanic or impact) with MSL and future rovers to better understand how glass alters on the martian surface, if that alteration mechanism is universal, and if alteration spans across long periods of time or if there is a time past which unaltered glass remains.

Rampe, E. B.↗
NASA NTRS2015

X-Ray Amorphous Phases in Antarctica Dry Valley Soils: Insight into Aqueous Alteration Processes on Mars?

The Chemistry and Mineralogy (CheMin) instrument onboard the Mars Curiosity rover has detected abundant amounts (approx. 25-30 weight percentage) of X-ray amorphous materials in a windblown deposit (Rocknest) and in a sedimentary mudstone (Cumberland and John Klein) in Gale crater, Mars. On Earth, X-ray amorphous components are common in soils and sediments, but usually not as abundant as detected in Gale crater. One hypothesis for the abundant X-ray amorphous materials on Mars is limited interaction of liquid water with surface materials, kinetically inhibiting maturation to more crystalline phases. The objective of this study was to characterize the chemistry and mineralogy of soils formed in the Antarctica Dry Valleys, one of the driest locations on Earth. Two soils were characterized from different elevations, including a low elevation, coastal, subxerous soil in Taylor Valley and a high elevation, ultraxerous soil in University Valley. A variety of techniques were used to characterize materials from each soil horizon, including Rietveld analysis of X-ray diffraction data. For Taylor Valley soil, the X-ray amorphous component ranged from about 4 weight percentage in the upper horizon to as high as 15 weight percentage in the lowest horizon just above the permafrost layer. Transmission electron microscopy indicated that the presence of short-range ordered (SRO) smectite was the most likely candidate for the X-ray amorphous materials in the Taylor Valley soils. The SRO smectite is likely an aqueous alteration product of mica inherited from granitic materials during glaciation of Taylor Valley. The drier University Valley soils had lower X-ray amorphous contents of about 5 weight percentage in the lowest horizon. The X-ray amorphous materials in University Valley are attributed to nanoparticles of TiO2 and possibly amorphous SiO2. The high abundance of X-ray amorphous materials in Taylor Valley is surprising for one of the driest places on Earth. These materials may have been physically and chemical altered during soil formation, however, the limited interaction with water and low temperatures may result in the formation of "immature" X-ray amorphous or SRO materials. Perhaps, a similar process contributes to the formation of the high content of X-ray amorphous materials detected on Mars.

Ming, D. W.↗
DOE OSTI2018

Potential benefit of amorphization in the retention of gaseous species in irradiated pyrochlores

Understanding the structure-property relationship for materials destined for irradiation extremes is a key step in developing materials with reliable, long-term performance. One crucial relationship is the ability of a material to withstand or accommodate amorphization, as this dictates its potential use as a nuclear waste form. Pyrochlores are one such class of materials for consideration as waste forms and there has been significant work examining how both the crystal structure and chemistry impacts amorphization resistance, leading to the important conclusion that the amorphization resistance of pyrochlores (A 2 B 2 O 7 ) is very sensitive to the nature of the B cations. For example, pyrochlores with B=Ti amorphize much more readily than B=Zr compounds. However, there are still questions regarding how these types of materials respond to prolonged or high-dose irradiation conditions. Gd 2 Ti 2 O 7 (GTO) and Gd 2 Zr 2 O 7 (GZO) pyrochlores were implanted with 400 keV Kr++ ions at room temperature to calculated peak damages of 119 and 135 displacements per atom (dpa), respectively. As expected, GTO amorphized completely under irradiation. However, discrete bubbles of Kr coalesced within the amorphous matrix without micro-cracking or spallation. In contrast, GZO transforms to a disordered fluorite structure under irradiation with no indications of localized amorphization. But, the accumulation of Kr within the host material leads to sub-grain structures, extended defects, and the development of micro-cracks. Thus, while GTO readily amorphizes even under low dose irradiations, the resistance of the amorphous GTO matrix to micro cracking and gas release, even in the presence of large bubble formation, suggests an enhanced propensity to retain gaseous species. Finally, consideration of long-term dose accumulation effects in nuclear waste forms would suggest reconsideration of amorphization processes in pyrochlores and related materials as a potential beneficial effect for immobilization and long-term storage of actinide materials.

36 MATERIALS SCIENCE↗
NASA NTRS1995

High-Density Amorphous Ice, the Frost on Interstellar Grains

Most water ice in the universe is in a form which does not occur naturally on Earth and of which only minimal amounts have been made in the laboratory. We have encountered this 'high-density amorphous ice' in electron diffraction experiments of low-temperature (T less than 30 K) vapor-deposited water and have subsequently modeled its structure using molecular dynamics simulations. The characteristic feature of high-density amorphous ice is the presence of 'interstitial' oxygen pair distances between 3 and 4 A. However, we find that the structure is best described as a collapsed lattice of the more familiar low-density amorphous form. These distortions are frozen in at temperatures below 38 K because, we propose, it requires the breaking of one hydrogen bond, on average, per molecule to relieve the strain and to restructure the lattice to that of low-density amorphous ice. Several features of astrophysical ice analogs studied in laboratory experiments are readily explained by the structural transition from high-density amorphous ice into low-density amorphous ice. Changes in the shape of the 3.07 gm water band, trapping efficiency of CO, CO loss, changes in the CO band structure, and the recombination of radicals induced by low-temperature UV photolysis all covary with structural changes that occur in the ice during this amorphous to amorphous transition. While the 3.07 micrometers ice band in various astronomical environments can be modeled with spectra of simple mixtures of amorphous and crystalline forms, the contribution of the high-density amorphous form nearly always dominates.

Jenniskens, P.↗