Structural evolution and thermophysical properties of ZrxNi100−x metallic liquids and glasses
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Nitrogen content of metallic spherules in tektite and impactite glasses
The role of Al in aluminosilicate glasses remains somewhat a mystery: at low concentrations, it increases the resistance to hydrolysis of the glass, whereas at high concentrations an opposite effect is observed. To understand the origin of the phenomenon on a fundamental atomistic scale, we performed 577 MD simulations and applied potential mean force (PMF) calculations to estimate the activation barriers for hydrolysis and to statistically correlate them with local structural features of the glass. Models of pure silicate and aluminosilicate glasses are constructed and investigated. PMF simulation results are further validated by the experimental measurements and revealed that Al is very easy to dissociate, but it also increases the glass chemical durability through significantly increasing both the strength of Si and network connectivity of the glass. In contrast, at high Al concentration, preferential dissolution of Al weakens the silicate network, which it supposes to strengthen, and so the glass resistance becomes poor. Through PMF calculations, we evaluated the activation barriers for dissociating bonds around Al as 0.49 eV, which is less than a half of the energy to dissociate bonds around Si in pure silicate (1.22 eV) and around Si in aluminosilicate glass (1.34 eV), all these energy differences being statistically significant. Molecular structural level investigation revealed that Si with Al as a second neighbor in the glass network has a significantly higher activation energy for dissociation than Si in pure silicate glass. Furthermore, the proposed approach opens the way to the development of quantitative predictive models of glass durability.
Maturity, which is a measure of the time lunar soils have been in the upper approximately 1 mm of the surface, is correlated with changes in the soils' optical properties. Mature soil is darker and somewhat redder than immature soil of the same composition, and features in the reflectance spectrum become more subdued with increasing maturity. The maturation process also involves accumulation of agglutinitic glass and submicroscopic metallic iron particles. We have produced submicrometer iron metal blebs on the surface and within glass and mineral grains by the method of high-temperature reduction. This technique has permitted the determination of optical changes in samples much simpler than lunar soil, and offers a useful tool with which to investigate the maturation process.
Advantages and disadvantages of glass components in ultrahigh vacuum systems
New series of high expansion coefficient glasses can be sealed by fusion onto hot surfaces of metals and alloys. Glasses have relatively low working temperatures, good chemical durability, and can be used in electrical insulators and feedthroughs to fluid or vacuum systems.
Crystal nucleation behavior in metallic alloys known to form glasses in melt quenching was characterized and from this characterization the possibility that massive amounts of certain alloys could be slow cooled to the glass state was assessed. Crystal nucleation behavior of pure liquid metals was examined experimentally, under containerless conditions, and theoretically.
Filter disks made of glass frit have been found to be effective as means of high-throughput collection of metal oxide particles, ranging in size from a few to a few hundred nanometers, produced in gas-phase condensation reactors. In a typical application, a filter is placed downstream of the reactor and a valve is used to regulate the flow of reactor exhaust through the filter. The exhaust stream includes a carrier gas, particles, byproducts, and unreacted particle-precursor gas. The filter selectively traps the particles while allowing the carrier gas, the byproducts, and, in some cases, the unreacted precursor, to flow through unaffected. Although the pores in the filters are much larger than the particles, the particles are nevertheless trapped to a high degree: Anecdotal information from an experiment indicates that 6-nm-diameter particles of MnO2 were trapped with greater than 99-percent effectiveness by a filtering device comprising a glass-frit disk having pores 70 to 100 micrometer wide immobilized in an 8-cm-diameter glass tube equipped with a simple twist valve at its downstream end.
A method for making a glass-to-metal seal is described. A domed metal enclosure having a machined seal ring is fitted to a glass post machined to a slight taper and to a desired surface finish. The metal part is then heated by induction in a vacuum. As the metal part heats and expands relative to the glass post, the metal seal ring, possessing a higher coefficient of expansion than the glass post, slides down the tapered post. Upon cooling, the seal ring crushes against the glass post forming the seal. The method results in a glass-to-metal seal possessing extremely good leak resistance, while the parts are kept clean and free of the contaminants.
The American Society of Mechanical Engineers AG-1 Code on Nuclear Air and Gas Treatment is updated every two years. This paper provides an overview of issues being discussed within AG-1 committee meetings and revisions that will be included in the next version of the code. Additional information is provided on issues being discussed ranging from media velocity limits, control of airflow using actual versus and standard cubic feet per minute. Navigation and identification of applicable high-efficiency particulate air (HEPA) filter code sections can be confusing for those unfamiliar with AG-1. A general reorganization of filtration code sections clarifies geometry, flow, and performance envelopes for nuclear grade HEPA filters. The initial step consists of establishment of Section FN covering qualification of conventional, ceramic, metal, and high strength fibrous glass media. Future filter sections are currently expected to be characterized by geometry and flow direction (axial vs. radial). The Department of Energy's (DOE) Nuclear Air Cleaning Handbook (NACH) is also undergoing revision. An update on the status of that effort, along with issues and changes being considered. The original charter of the AG-1 Code was specific to commercial nuclear power plants, and to safety-related air cleaning systems. This has evolved over the years to include normal non-safety ventilation systems and process gas systems. Corollary guidance for DOE facilities has been available in several editions of the Nuclear Air Cleaning Handbook, starting with ORNL-NSIC 65. The latest edition of the Handbook, 2003, is undergoing revision and modifications. (authors)
The surface of a glassy material exhibits enhanced mobility compared to the bulk counterpart, however the underlying mechanism for this remains elusive. Herein, we present studies of the dynamical properties of a prototypical glass-forming metallic liquid Zr 50 Cu 50 as a function of the distance from both the free surface and pinned surface using molecular dynamics simulations. We found that the surface mobility increases gradually on approaching the free surface, with a concomitant increase of the non-Gaussianity. The phonon density of states at the free surface exhibits lower characteristic frequencies than in the bulk and pinned surface. These findings suggest phonon softening caused by anisotropic fluctuations at free surfaces as an alternative physical mechanism leading to the enhanced dynamics at free glassy surfaces from the perspective of collective excitations.
Metal pattern bonding technique for cover glass attachment to silicon solar cells for space applications
We propose that Kuiper Belt samples (in this case comet coma grains from the Jupiter family comet Wild 2) are recognizably different from the bulk of materials in outer belt asteroids, because of their different formation positions and times in the early solar system. We believe this despite similarities found between some Wild 2 grains and components of carbonaceous chondrites (i.e. some CAI and chondrules). Kuiper Belt samples must preserve measurable mineralogical and compositional evidence of formation at unique positions and times in the early solar nebula, and these formational differences must have imparted recognizable special characteristics. We hypothesize that these characteristics include: (1) Unique major element compositional ranges of common astromaterial minerals, especially olivine and pyroxene; (2) Unique minor element compositions of major silicate phases, especially olivine and low-Ca pyroxene; (3) Degree and effects of radiation processing -- including amorphous rims, metal coatings, and Glass with Embedded Metal and Sulfides (GEMS); (4) Presence of abundant presolar silicate grains as recognized by anomalous oxygen in silicates; (5) Oxidation state of the mineral assemblage. We are working our way through all available Wild 2 samples, selecting 1-2 non-consecutive viable TEM grids from each possible extracted Wild 2 grain. We especially prefer TEM grids from grains for which complete mineralogical details have not been published (which is to say the majority of the extracted grains). We are performing a basic mineralogic survey by E-beam techniques, to establish the essential features of the extracted Wild 2 grains. We are making a particular effort to carefully and accurately measure minor elements of olivine and pyroxene, as these minerals are widespread in astromaterials, and comparisons of their compositions will serve to place the Wild 2 silicates in contact with asteroids, meteorites and chondritic interplanetary dust particles processing. We are also making a special effort to search for mineralogical products of aqueous alteration, since their presence would reveal that Wild 2 was once internally heated, a result with dramatic implications for models of early solar system primitive bodies. Thus far carbonates are the only potential evidence for aqueous alteration for Wild 2.
The objective of this ground based study is to test the hypothesis that shear thinning (the non-Newtonian response of viscosity to shear rate) is a viable mechanism to explain the observation of enhanced glass formation in numerous low-g experiments. In 1-g, fluid motion results from buoyancy forces and surface tension driven convection. This fluid flow will introduce shear in undercooled liquids in 1-g. In low-g it is known that fluid flows are greatly reduced so that the shear rate in fluids can be extremely low. It is believed that some fluids may have weak structure in the absence of flow. Very small shear rates could cause this structure to collapse in response to shear resulting in a lowering of the viscosity of the fluid. The hypothesis of this research is that: Shear thinning in undercooled liquids decreases the viscosity, increasing the rate of nucleation and crystallization of glass forming melts. Shear in the melt can be reduced in low-g, thus enhancing undercooling and glass formation. The viscosity of a model glass (lithium di-silicate, L2S) often used for crystallization studies has been measured at very low shear rates using a dynamic mechanical thermal analyzer. Our results are consistent with increasing viscosity with a lowering of shear rates. The viscosity of L2S may vary as much as an order of magnitude depending on the shear rate in the temperature region of maximum nucleation and crystal growth. Classical equations for nucleation and crystal growth rates, are inversely related to the viscosity and viscosity to the third power respectively. An order of magnitude variation in viscosity (with shear) at a given temperature would have dramatic effects on glass crystallization Crystallization studies with the heavy metal fluoride glass ZBLAN (ZrF2-BaF2-LaF3-AlF3-NaF) to examine the effect of shear on crystallization are being initiated. Samples are to be melted and quenched under quiescent conditions at different shear rates to determine the effect on crystallization. The results from this study are expected to advance the current scientific understanding of glass formation in low-g and glass crystallization under glass molding conditions and will improve the scientific understanding of technological processes such as fiber pulling, bulk amorphous alloys, and glass fabrication processes.
A novel method to produce thin films spatially disposed on desired areas of workpieces is disclosed. Examples of include the formation of a yttria stabilized zirconia (YSZ) film formed on a desired portion of a stainless steel interconnect for solid oxide fuel cells by Atomic Layer Deposition (ALD). A number of methods to produce the spatially disposed YSZ film structures are described including polymeric and silicone rubber masks. The thin film structures have utility for preventing the reaction of glasses with metals, in particular alkali-earth containing glasses with ferritic stainless steels, allowing high temperature bonding of these materials.
Poly-silicon thin films on glass substrates are synthesized using laser initiated metal induced crystallization of hydrogenated amorphous silicon films. These films can be used to fabricate solar cells on low cost glass and flexible substrates. The process starts by depositing 200 nm amorphous silicon films on the glass substrates. Following this, 200 nm of sputtered aluminum films were deposited on top of the silicon layers. The samples are irradiated with an argon ion cw laser beam for annealing. Laser power densities ranging from 4 to 9 W/cm2 were used in the annealing process. Each area on the sample is irradiated for a different exposure time. Optical microscopy was used to examine any cracks in the films and loss of adhesion to the substrates. X-Ray diffraction patterns from the initial results indicated the crystallization in the films. Scanning electron microscopy shows dendritic growth. The composition analysis of the crystallized films was conducted using Energy Dispersive x-ray Spectroscopy. The results of poly-silicon films synthesis on space qualified flexible substrates such as Kapton are also presented.
Neutron and gamma-ray imaging systems are deployed within the field of nuclear safeguards for the detection and localization of special nuclear materials and other materials of interest. 237 Np is one of these materials of interest due its presence in spent nuclear fuel and potential for use in nuclear weapons when purified. Here, for the first time, a 6 kg neptunium sphere (98.8 wt% 237 Np) was measured using a dual-particle imager, from the University of Michigan, consisting of organic glass and inorganic scintillators. The novel composition of organic glass scintillator was recently developed at Sandia National Labs and has been used in particle imaging systems due to its time resolution and particle discrimination capabilities. Gamma-ray energy spectra from single and coincident events were extracted and the sequencing of Compton scatter and photoelectric absorption gamma-ray events was used to generate images using simple backprojection. The emissions of interest in this work are the 312 keV and 416 keV gamma rays from 233 Pa, a daughter isotope from the neptunium decay series. The results of this work show that there is close agreement between the true source location in angular space and the converged location from the gamma ray images created using the system. The gamma spectroscopy from single and coincident events also identified the characteristic emission from the daughter isotope and could be used to assist with the identification of 237 Np. Furthermore, successful localization of the source with 5 s of data demonstrates the practical application of the imaging system for imaging and detection of material in weapons-useable quantities.
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