DEVELOPMENT OF HIGH SATURATION INDUCTION FE-NI BASED METAL AMORPHOUS NANOCOMPOSITE BY OPTIMIZATION OF GLASS FORMING ABILITY
PhD Thesis
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PhD Thesis
The operations of solar cell manufacture are briefly examined. The formation of reliable, ohmic, low-loss, and low-cost metal contacts on solar cells is a critical process step in cell manufacturing. In a commonly used process, low-cost metallization is achieved by screen printing a metal powder-glass frit ink on the surface of the Si surface and the conductive metal powder. A technique utilizing a molybdenum-tin alloy for the metal contacts appears to lower the cost of materials and to reduce process complexity. The ink used in this system is formulated from MoO3 with Sn powder and a trace amount of titanium resonate. Resistive losses of the resulting contacts are low because the ink contains no frit. The MoO3 is finally melted and reduced in forming gas (N2+H2) to Mo metal. The resulting Mo is highly reactive which facilitates the Mo-Si bonding.
We report on the solubility of (Li 2 S) 60 (SiS 2 ) x (P 2 S 5 ) 40–x , (0 ≤ x ≤ 40) sulfide glass solid-state electrolytes in the 1:1 (v/v) DME:DOL solvent mixture, a popular choice for lithium metal battery liquid electrolytes. SiS 2 -rich glasses within the compositional range of (Li 2 S) 60 (SiS 2 ) x (P 2 S 5 ) 40–x (28 ≤ x ≤ 40) were found to be functionally insoluble in DME:DOL. Hybrid symmetric test cells with a thin liquid electrolyte layer (0.6 M LiTFSI + 0.4 M LiNO 3 in 1:1 (v/v) DME:DOL) at the interface between lithium metal electrodes and an insoluble (Li 2 S) 60 (SiS 2 ) 28 (P 2 S 5 ) 12 glass wafer were tested. Hybrid test cells delivered a critical current density of 3.0 mA cm –2 at 25 °C and 0.1 MPa, which is nearly double the CCD of comparable dry symmetric test cells cycled at 10× higher stack pressure.
The research described in this progress report involved the study of petrological, geochemical, and volcanic processes that occur on the Moon and the SNC meteorite parent body, generally accepted to be Mars. The link between these studies is that they focus on two terrestrial-type parent bodies somewhat smaller than earth, and the fact that they focus on the types of magmas (magma compositions) present, the role of volatiles in magmatic processes, and on processes of magma evolution on these planets. We are also interested in how these processes and magma types varied over time.In earlier work on the A15 green and A17 orange lunar glasses, we discovered a variety of metal blebs. Some of these Fe-Ni metal blebs occur in the glass; others (in A17) were found in olivine phenocrysts that we find make up about 2 vol 96 of the orange glass magma. The importance of these metal spheres is that they fix the oxidation state of the parent magma during the eruption, and also indicate changes during the eruption . They also yield important information about the composition of the gas phase present, the gas that drove the lunar fire-fountaining. During the tenure of this grant, we have continued to work on the remaining questions regarding the origin and evolution of the gas phase in lunar basaltic magmas, what they indicate about the lunar interior, and how the gas affects volcanic eruptions. Work on Martian magmas petrogenesis questions during the tenure of this grant has resulted in advances in our methods of evaluating magmatic oxidation state variations in Mars and some new insights into the compositional variations that existed in the SNC magmas over time . Additionally, Minitti has continued to work on the problem of possible shock effects on the abundance and distribution of water in Mars minerals.
Metal direlectric surface interactions and dielectric films on metal substrates were investigated. Since interfacial interaction depends so heavily on the nature of the surfaces, analytical surface tools such as Auger emission spectroscopy, X-ray photoelectron spectroscopy and field ion microscopy were used to assist in surface and interfacial characterization. The results indicate that with metals contacting certain glasses in the clean state interfacial, bonding produces fractures in the glasses while when a film such as water is present, fractures occur in the metal near the interface. Friction forces were used to measure the interfacial bond strengths. Studies with metals contacting polymers using field ion microscopy revealed that strong bonding forces could develop being between a metal and polymer surface with polymer transferring to the metal surface in various ways depending upon the forces applied to the surface in contact. With the deposition of refractory carbides, silicides and borides onto metal and alloy substrates the presence of oxides at the interface or active gases in the deposition plasma were shown to alter interfacial properties and chemistry. Auger ion depth profile analysis indicated the chemical composition at the interface and this could be related to the mechanical, friction, and wear behavior of the coating.
Non ]oxide fiber optics such as heavy metal fluoride and chalcogenide glasses are extensively used in infrared transmitting applications such as communication systems, chemical sensors, and laser fiber guides for cutting, welding and medical surgery. The addition of rare earths such as erbium, enable these materials to be used as fiber laser and amplifiers. Some of these glasses however are very susceptible to crystallization. Even small crystals can lead to light scatter and a high attenuation coefficient, limiting their usefulness. Previously two research teams found that microgravity suppressed crystallization in heavy metal fluoride glasses. Looking for a less expensive method to suppress crystallization, ground based research was performed utilizing an axial magnetic field. The experiments revealed identical results to those obtained via microgravity processing. This research then led to a patented process for eliminating crystals in optical fiber preforms and the resulting optical fibers. In this paper, the microgravity results will be reviewed as well as patents and papers relating to the use of magnetic fields in various material and glass processing applications. Finally our patent to eliminate crystals in non ]oxide glasses utilizing a magnetic field will be detailed.
Electron probe microanalysis and analytical electron microscopy techniques were employed to obtain structural and chemical analyses of metal particles in the size range of less than 1000 A and greater than 5 microns from the glassy constituents of 3 lunar highland samples 65315, 67435 and 78235. Most of the micron size metal particles in the glass coatings of the three samples are of meteoritic Co-Ni content. The Ni content of submicron metal often differs significantly from the micron size metal in the same glass. This difference can be explained by one of 3 reasons: (a) the presence of metal of different sizes and Ni contents in the rock prior to the shock event, (b) the presence of metal particles in the lunar soil of meteoritic or variable Ni content which were incorporated when the glass formed and (c) the production of submicroscopic Fe metal from the reduction of Fe(+2) in the shock produced melt.
The purposes of our ongoing investigations of Apollo 15 green and Apollo 17 orange and black volcanic glasses are threefold: first, to increase our understanding of the volcanic origin of the glasses; second, to determine the nature of the coating materials deposited on the glasses during their cooling in the volcanic environment; and, third, to help determine the nature of the gases involved in the volcanic fire-fountaining that occurred at approximately 3.5 Ga on the moon. We are continuing studies of coatings on volcanic glasses using analytical techniques not available when these glasses were originally studied; these include high-resolution FE-TEM and X-ray mapping, along with other highly detailed methods including TEM electron diffraction analysis. Initial studies of Apollo 15 green volcanic glasses using the techniques described above revealed for the first time the presence of areas containing distinct layering of volcanic surface deposits. S was associated with some of the inner layer of metallic Fe but was absent from the outer layer. Zn was associated with S in some places in the inner layer. An example of a typical spherule used for this study is shown in Fig. 1. It is a black (quench-crystallized) bead from near the bottom of the 74001/2 double drive tube; black beads such as this one are essentially identical in composition to the orange (uncrystallized) beads of the 74001/2 core.
Experiments at the NASA Lewis Research Center's Microgravity Material Science Laboratory using physical and mathematical models to delineate the effects of gravity on processes of scientific and commercial interest are discussed. Where possible, transparent model systems are used to visually track convection, settling, crystal growth, phase separation, agglomeration, vapor transport, diffusive flow, and polymer reactions. Materials studied include metals, alloys, salts, glasses, ceramics, and polymers. Specific technologies discussed include the General Purpose furnace used in the study of metals and crystal growth, the isothermal dendrite growth apparatus, the electromagnetic levitator/instrumented drop tube, the high temperature directional solidification furnace, the ceramics and polymer laboratories and the center's computing facilities.
Noncrystalline oxides under pressure undergo gradual structural modifications, highlighted by the formation of a dense noncrystalline network topology. The nature of the densified networks and their electronic structures at high pressures may account for the mechanical hardening and the anomalous changes in electromagnetic properties. Despite its importance, direct probing of the electronic structures in amorphous oxides under compression above the Mbar pressure (>100 GPa) is currently lacking. Here, we report the observation of pressure-driven changes in electronic configurations and their delocalization around oxygen in glasses using inelastic X-ray scattering spectroscopy (IXS). In particular, the first O K-edge IXS spectra for compressed GeO 2 glass up to 148 GPa, the highest pressure ever reached in an experimental study of GeO 2 glass, reveal that the glass densification results from a progressive increase of oxygen proximity. While the triply coordinated oxygen [3] O is dominant below ~50 GPa, the IXS spectra resolve multiple edge features that are unique to topologically disordered [4] O upon densification above 55 GPa. Topological compaction in GeO 2 glass above 100 GPa results in pronounced electronic delocalization, revealing the contribution from Ge d-orbitals to oxide densification. Strong correlations between the glass density and the electronic configurations beyond the Mbar conditions highlight the electronic origins of densification of heavy-metal-bearing oxide glasses. Furthermore, current experimental breakthroughs shed light on the direct probing of the electronic density of states in high-Z oxides above 1 Mbar, offering prospects for studies on the pressure-driven changes in magnetism, superconductivity, and electronic transport properties in heavy-metal-bearing oxides under compression.
This is the final report discussing the work done for the Space Environments and Effects (SEE) Program. It discusses test chamber design, coating research, and test results on electrically thermal control coatings. These thermal control coatings are being developed to have several orders of magnitude higher electrical conductivity than most available thermal control coatings. Most current coatings tend to have a range in surface resistivity from 1,011 to 1,013 ohms/sq. Historically, spacecraft have had thermal control surfaces composed of dielectric materials of either polymers (paints and metalized films) or glasses (ceramic paints and optical solar reflectors). Very seldom has the thermal control surface of a spacecraft been a metal where the surface would be intrinsically electrically conductive. The poor thermal optical properties of most metals have, in most cases, stopped them from being used as a thermal control surface. Metals low infrared emittance (generally considered poor for thermal control surfaces) and/or solar absorptance, have resulted in the use of various dielectric coatings or films being applied over the substrate materials in order to obtain the required optical properties.
Nucleation rates in condensed systems are frequently not at their steady state values. Such time dependent (or transient) nucleation is most clearly observed in devitrification studies of metallic and silicate glasses. The origin of transient nucleation and its role in the formation and stability of desired phases and microstructures are discussed. Numerical models of nucleation in isothermal and nonisothermal situations, based on the coupled differential equations describing cluster evolution within the classical theory, are presented. The importance of transient nucleation in glass formation and crystallization is discussed.
Polyimides widely used as high-performance polymers because of their excellent thermal stability and toughness. However, their coefficients of thermal expansion (CTE's) greater than those of metals, ceramics, and glasses. Decreasing CTE's of polyimides increase usefulness for aerospace and electronics applications in which dimensional stability required. Additives containing metal ions reduce coefficients of thermal expansion of polyimides. Reductions range from 11 to over 100 percent.
Since 1997, Marshall Space Flight Center s Electrostatic Levitator (ESL) facility has been used to study the characteristics of new metals, ceramics, and glass compounds - in both their hot molten states and as they are cooled to form solid materials. The ESL provides a unique way to test such substances without having to make contact with a container or crucible that would contaminate the sample. Simply put, objects analyzed in the levitator's chamber float in mid-air with no visible means of support or containment, suspended only by static electricity. While a sample object is levitated, a laser beam heats it until it melts so that scientists can measure its physical properties without interference from a container.
Chromium represents a significant challenge for the vitrification of high-level nuclear waste into silicate and borosilicate glasses due to its low solubility and variable oxidation states, which can limit the waste loading due to promotion of crystallization or phase separation during processing. In this study, we modeled chromium containing silicate glasses using molecular dynamics simulations with three machine learning interatomic potentials (MLIPs), MACE, CHGNet, and PFP were employed, to gain insights on glass composition and oxidation states on the structures of these glasses. One of the goals is to evaluate their ability of these MLIPs to accurately represent the general structure of silicate glasses and chromium local environments as a function of chromium oxidation states. Density Functional Theory (DFT) based calculations and experimental data such as neutron structure factors were used to validate the structural models. It was found that the foundation models of all three MLIPs are able to reproduce general structural features of the sodium silicate glass structure consistent with experimental and DFT data, but only CHGNet and PFP can accurately capture the oxidation states and local environment of chromium: tetrahedral for Cr6+ and octahedral for Cr3+. Furthermore, we studied the effect of varying Cr3+/ Cr6+ (Cr3+/Crtotal) ratio and total chromium content using PFP. Our results show that Cr6+ enhances network polymerization by reducing non-bridging oxygens through Na? charge compensation required due to the formation of chromate (CrO42-) species, while Cr³? acts as a network modifier that disrupts connectivity. System size effects on the structural characteristics and chromium environments were also tested using the PFP potential. This work highlights the importance of careful validation on the precision, transferability, and potential of MLIPs for modeling glasses containing transition metal elements that can exist in multiple oxidation states. It is also encouraging to see the foundational models are all three MLFFs are able to reproduce the basic sodium silicate glass structures, while suggesting additional training or refining is needed to improve the description of more complex systems containing transition metals.
Upon reheating, most glassy metal alloys crystallize at a temperature not far removed from the glass temperature Tg and far below the liquidus temperature T1. It has been reported by Kui et al. (1984) that the alloy Ni40Pd40P20, which exhibits a scaled glass temperature of about 0.68, has been melt quenched, under a flux of dehydrated B2O3, to a glass at rates as low as 1 deg/s. Here some specimens of this alloy, when similarly fluxed during reheating, have been reheated to temperatures within 50 deg of T1 and 280 deg above Tg at rates of about 2.5 deg/s, and then cooled again to Tg, without crystallization. From this behavior it is inferred that the steady frequency of homogeneous nucleation of crystals in the alloy is less than 0.1/cu cm s.
Using available data from the literature, an outline is formulated for the major physical and chemical effects expected during solar-wind bombardment of the lunar regolith. In agreement with results of Auger and other analyses of the composition of lunar grain surfaces, this outline predicts that solar-wind sputtering will tend to clean exposed grain surfaces by ejecting material at velocities exceeding lunar escape velocity. Results are also discussed which show that Fe is partially reduced in the outer few 10 nm of grain surfaces and that this reduced Fe forms 10-nm-diameter metal spheres throughout the glass during agglutinate formation by micrometeorite impacts. These metal spheres give the agglutinates their distinctive optical and magnetic properties and are partially responsible for the decreasing albedo of the lunar surface with exposure age.
A charge-coupled device with a low-emissivity metal layer located between a sensing layer and a substrate provides reduction in ghost images. In a typical charge-coupled device of a silicon sensing layer, a silicon dioxide insulating layer, with a glass substrate and a metal carrier layer, a near-infrared photon, not absorbed in the first pass, enters the glass substrate, reflects from the metal carrier, thereby returning far from the original pixel in its entry path. The placement of a low-emissivity metal layer between the glass substrate and the sensing layer reflects near infrared photons before they reach the substrate so that they may be absorbed in the silicon nearer the pixel of their points of entry so that the reflected ghost image is coincident with the primary image for a sharper, brighter image.