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At least 1,567 records · Page 87

Recent Advances in the Chemistry of Hydrometallurgical Methods

Producing pure substances has been the obsession of scientists for centuries and has defined chemistry as we know it. Nowadays, most of our economy still relies on the chemist ability to extract and purify metallic elements from raw or recycled materials, which, in most cases, is done partly or entirely via hydrometallurgical methods. In this work, the authors present the critical aspects of this relatively overlooked, yet critical, chemistry discipline. This review article highlights the importance of hydrometallurgical processes for strategic industrial sectors, put in perspective traditional separation methods with emerging ones (new metal-binding chelators, ionic liquids, deep eutectic solvents, microfluidic devices, biomaterials, etc.), critically reviews progress made on separation methods over the past two decades, and highlights the challenges lying ahead for the hydrometallurgists in academia and the industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental determination of systems suitable for study as monotectic binary metallic alloy solidification models

Transparent binary metallic alloy solidification models are important in attempts to understand the processes causing liquid-liquid and solid-liquid phase transformations in metallic alloy systems. These models permit visual observation of the phase transformation and the processes proceding solidification. The number of these transparent monotectic binary models needs to be expanded to distinguish between the unique and general phenomena observed. The expansion of the number of accurately determined monotectic phase diagrams of model systems, and contribution to a data base for eventual use with UNIFAC group contribution methods is examined.

Smith, J. E., Jr.↗

Synthesis and Compatibility of Ionic Liquid Containing Rod-Coil Polyimide Gel Electrolytes with Lithium Metal Electrodes

A highly cross-linked polyimide-polyethylene oxide copolymer has been synthesized that is capable of holding large volumes of liquid component, simultaneously maintaining good dimensional stability. An amine end capped oligomer was made that was imidized in solution, followed by reaction with a triisocyanate in the presence of desired additives at ambient temperature. Polymer films are able to hold over 4 times their weight in room temperature ionic liquid RTIL or carbonate solvent. Electrolytes were studied that contained varying amounts of RTIL, lithium trifluoromethanesulfonimide LiTFSi, and alumina nanoparticles. Electrochemical stability of these electrolytes with lithium metal electrodes was studied by galvanic cycling and impedance spectroscopy. Improved cycling stability and decreased interfacial resistance were observed when increasing amounts of RTIL and LiTFSi were added. The addition of small amounts of alumina further decreased interfacial resistance by nearly an order of magnitude. During the course of the study, cycling stability increased from less than 3 to greater than 1000 h at 60 C and 0.25 mA/cm2 current density.

Tigelaar, Dean M.↗

Selective sulfidation of metal compounds

There is urgent, unprecedented demand for critical by-product and co-product metallic elements for the infrastructure (magnets, batteries, catalysts and electronics) needed to power society with renewable electricity1,2,3. However, the extraction of d-block and f-block metals from mineral and recycled streams is thermodynamically difficult, typically requiring complete dissolution of the materials, followed by liquid–liquid separation using metal-ion complexing or chelating behaviour4,5. The similar electronic structure of these metals results in poor separation factors, necessitating immense energy, water and chemicals consumption6,7,8. Here a metal-processing approach based on selective anion exchange is proposed. Several simple process levers (gas partial pressure, gas flowrate and carbon addition) are demonstrated to selectively sulfidize a target metal from a mixed metal-oxide feed. The physical and chemical differences between the sulfide and oxide compounds (for example, density, magnetic susceptibility and surface chemistry) can then be exploited for vastly improved separation compared with liquid–liquid methods9. The process conditions of sulfidation are provided for 56 elements and demonstrated for 15 of them. An assessment of the environmental and economic impacts suggests a path towards 60–90% reductions in greenhouse gas emissions while offering substantial capital cost savings compared with liquid–liquid hydrometallurgy.

36 MATERIALS SCIENCE↗

Improved Stability and Cyclability of Ceramic Solid Electrolyte by Coating Polymer

Rechargeable all-solid-state lithium (Li) metal batteries show better safety and energy density compared to commercial Li-ion batteries using liquid electrolyte. As the key component of Li metal batteries, ceramic solid-state electrolyte has attracted great interest because of its high ion conductivity and great potential in interfacing with Li metal. Ceramic electrolyte has a more stable interface with Li metal than liquid electrolyte, but chemical reaction and Li dendrite growth at the electrolyte/Li interface are still significant, which causes device degradation and failure by cycling of Li plating and stripping. Unlike ceramic electrolyte, polymer electrolyte has a relatively stable interface with Li metal and better mechanical flexibility. Therefore, we introduced a polymer electrolyte coating to protect the ceramic electrolyte from direct contact with Li metal. The galvanotactic cycling Li plating/striping data on the devices with (without) the coating illustrates increased (decreased) overall conductivity and cyclability of the test cell by the cycling. Nanometer-scale ionic-transport imaging, based on atomic force microscopy, shows that cycling degrades the ceramic-only electrolyte by partially blocking ionic transport in areas; in contrast, cycling on the polymer-coated electrolyte improves ionic conductivity. Compared with the ceramic-only electrolyte, this novel polymer electrolyte coating on ceramic electrolyte shows less degradation when in contact with Li metal.

25 ENERGY STORAGE↗

Metal-carbon composites and methods for their production

A method for producing a carbon nanotube-metal composite in which carbon nanotubes are layered on a metal substrate, the method comprising: (i) depositing a liquid, in which carbon nanotubes are suspended, onto said metal substrate; (ii) during or after step (i), subjecting said liquid to a shearing force sufficient to spatially confine the liquid to induce at least partial alignment of said carbon nanotubes on said metal substrate; and (iii) removing said liquid to produce said carbon nanotube-metal composite; wherein, after step (iii), the lengthwise dimensions of said carbon nanotubes are adhered to and oriented parallel with said metal surface, and said carbon nanotubes are at least partially aligned with each other. In some embodiments, the liquid is deposited in the form of droplets, and the droplets are subjected to a shearing force to cause them to elongate, which induces at least partial alignment of the carbon nanotubes.

Aytug, Tolga↗

Platinum liquid-vapor phase boundary mapped by fluid flyer experiments

We report a direct measurement of the temperature and density of a metal along its liquid-vapor coexistence (L-V) curve. By shocking platinum to a high-pressure liquid, we imparted sufficient heat for subsequent isentropic release to place it in a state on the boundary between the liquid and vapor phases. Released material in the liquid phase acted as a high velocity flyer pinned to the L-V curve. We measured velocity and radiant emission of the flyer as well as the interface motion and transiting shock states induced in a downstream window material by its impact. We used these measurements to calculate temperature and density of the L-V curve state which we compare to density functional theory predictions.

Equations of state↗

Friction and wear of selected metals and alloys in sliding contact with AISI 440 C stainless steel in liquid methane and in liquid natural gas

Aluminum, titanium, beryllium, nickel, iron, copper, and several copper alloys were run in sliding contact with AISI 440C in liquid methane and natural gas. All of the metals run except copper and the copper alloys of tin and tin-lead showed severely galled wear scars. Friction coefficients varied from 0.2 to 1.0, the lowest being for copper, copper-17 wt. % tin, and copper-8 wt. % tin-22 wt. % lead. The wear rate for copper was two orders of magnitude lower than that of the other metals run. An additional order of magnitude of wear reduction was achieved by the addition of tin and/or lead to copper.

Wisander, D. W.↗

X Ray Measurement of Tank Liquid Level

Liquid surface observed through metal container wall, allowing direct determination of quantities and changes. X-ray measurement of liquid level produces photograph in which liquid appears as solid dark mass. Commercially-available portable X-ray machine is used.

Macias, R. G.↗

Assessment of Materials-Based Options for On-Board Hydrogen Storage for Rail Applications

The objective of this project was to evaluate material- and chemical-based solutions for hydrogen storage in rail applications as an alternative to high-pressure hydrogen gas and liquid hydrogen. Three use cases were assessed: yard switchers, long-haul locomotives, and tenders. Four storage options were considered: metal hydrides, nanoporous sorbents, liquid organic hydrogen carriers, and ammonia, using 700 bar compressed hydrogen as a benchmark. The results suggest that metal hydrides, currently the most mature of these options, have the highest potential. Storage in tenders is the most likely use case to be successful, with long-haul locomotives the least likely due to the required storage capacities and weight and volume constraints. Overall, the results are relevant for high-impact regions, such as the South Coast Air Quality Management District, for which an economical vehicular hydrogen storage system with minimal impact on cargo capacity could accelerate adoption of fuel cell electric locomotives. The results obtained here will contribute to the development of technical storage targets for rail applications that can guide future research. Moreover, the knowledge generated by this project will assist in development of material-based storage for stationary applications such as microgrids and backup power for data centers.

08 HYDROGEN↗

Apollo 14 composite casting demonstration

The purpose of the demonstration was to show that mixtures of materials of different specific gravities would remain stable in the liquid state and during freezing in low g and not segregate as they do on earth. An inflight demonstration was performed on the Apollo 14 mission during the translunar and and transearth coast periods. The apparatus consisted of an electrical heater, a heat sink device for cooling, and sealed metal capsules containing matrix materials having a low-melting point and dispersants. The evaluation of the demonstration samples was accomplished by comparing space processed (flight) samples with (control) samples processed on the ground under otherwise similar conditions. In the low q environment of space flight the dispersions of particles, fibers, and gases in a liquid metal matrix were maintained during solidification. Dispersions of normally immiscible liquids were also maintained during solidification.

Yates, I. C., Jr.↗

Fracture and crack growth resistance studies of 304 stainless steel weldments relating to retesting of cryogenic vessels

Fracture and crack growth resistance characteristics of 304 stainless steel alloy weldments as relating to retesting of cryogenic vessels were examined. Welding procedures were typical of those used in full scale vessel fabrication. Fracture resistance survey tests were conducted in room temperature air, liquid nitrogen and liquid hydrogen. In air, both surface-flawed and center-cracked panels containing cracks in weld metal, fusion line, heat-affected zone, or parent metal were tested. In liquid nitrogen and liquid hydrogen, tests were conducted using center-cracked panels containing weld centerline cracks. Load-unload, sustained load, and cyclic load tests were performed in air or hydrogen gas, liquid nitrogen, and liquid hydrogen using surface-flawed specimens containing weld centerline cracks. Results were used to evaluate the effectiveness of periodic proof overloads in assuring safe and reliable operation of over-the-road cryogenic dewars.

Hall, L. R.↗

Formation of Metal and Silicate Globules in Gujba: A New Bencubbin-like Meteorite Fall

Gujba is a coarse-grained meteorite fall composed of 41 vol% large kamacite globules, 20 vol% large light-colored silicate globules with cryptocrystalline, barred pyroxene and barred olivine textures, 39 vol% dark-colored, silicate-rich matrix, and rare refractory inclusions. Gujba resembles Bencubbin and Weatherford in texture, oxygen-isotopic composition and in having high bulk delta N-15 values (approximately +685%0). The He-3 cosmic-ray exposure age of Gujba (26 +/- 7 Ma) is essentially identical to that of Bencubbin, suggesting that they were both reduced to meter-size fragments in the same parent-body collision. The Gujba metal globules exhibit metal-troilite quench textures and vary in their abundances of troilite and volatile siderophile elements. We suggest that the metal globules formed as liquid droplets either via condensation in an impact-generated vapor plume or by evaporation of preexisting metal particles in a plume. The lower the abundance of volatile elements in the metal globules, the higher the globule quench temperature. We infer that the large silicate globules also formed from completely molten droplets; their low volatile-element abundances indicate that they also formed at high temperatures, probably by processes analogous to those that formed the metal globules. The coarse-grained Bencubbin-Weatherford-Gujba meteorites may represent a depositional component from the vapor cloud enriched in coarse and dense particles. A second class of Bencubbin-like meteorites (represented by Hammadah a1 Hamra 237 and QUE 94411) may be a finer fraction derived from the same vapor cloud

Rubin, Alan E.↗

Detecting Conductive Liquid Leaking from Nonconductive Pipe

A method that can be implemented with relatively simple electronic circuitry provides a capability for detecting leakage of an electrically conductive liquid from an electrically nonconductive underground pipe. Alternatively or in addition, the method can be applied to locate the pipe, whether or not there is a leak. Although the method is subject to limitations (some of which are described below), it is still attractive as an additional option for detecting leaks and locating pipes without need for extensive digging. The method is based on capacitive coupling of an alternating electrical signal from the liquid to a portable electronic unit that resembles a metal detector. A signal voltage is applied to the liquid at some convenient point along the pipe: for example, the signal could be coupled into the liquid via an aboveground metal pipe fitting, the interior surface of which is in contact with the liquid. The signal is conducted through the liquid in the pipe; in the case of diffusive leak of liquid into the surrounding ground, the signal is conducted through the leak, into the portion of the adjacent ground that has become soaked with the liquid. (A drip leak cannot be detected by this method because there is no conductive path between the liquid inside and the liquid outside the pipe.) The portable unit includes an electrically conductive plate connected to the input terminal of an amplifier. When the plate is brought near the pipe or the leaked liquid, a small portion of the signal power is coupled capacitively from the liquid to the plate. The user scans the plate near the ground surface to find the locus of maximum signal strength. The leak can be identified as a relatively wide area, contiguous with the location of the pipe, over which the signal is detectable.

Youngquist, Robert C.↗

Galvanic Liquid Applied Coating Development for Protection of Steel in Concrete

Corrosion of reinforcing steel in concrete is a major problem affecting NASA facilities at Kennedy Space Center (KSC), other government agencies, and the general public. Problems include damage to KSC launch support structures, transportation and marine infrastructures, as well as building structures. A galvanic liquid applied coating was developed at KSC in order to address this problem. The coating is a non-epoxy metal rich ethyl silicate liquid coating. The coating is applied as a liquid from initial stage to final stage. Preliminary data shows that this coating system exceeds the NACE 100 millivolt shift criterion. The remainder of the paper details the development of the coating system through the following phases: Phase I: Development of multiple formulations of the coating to achieve easy application characteristics, predictable galvanic activity, long-term protection, and minimum environmental impact. Phase II: Improvement of the formulations tested in Phase I including optimization of metallic loading as well as incorporation of humectants for continuous activation. Phase III: Application and testing of improved formulations on the test blocks. Phase IV: Incorporation of the final formulation upgrades onto large instrumented structures (slabs).

Curran, Joseph John↗

Crossover from two-dimensional to three-dimensional superconducting states in bismuth-based cuprate superconductor

To decipher the mechanism of high-temperature superconductivity, it is important to know how the superconducting pairing emerges from the unusual normal states of cuprate superconductors, including the pseudogap, strange metal and anomalous Fermi liquid phases. A long-standing issue is how the superconducting pairing is formed and condensed in the strange metal phase, because this is where the superconducting transition temperature is highest. In this work, we use state-of-the-art high-pressure measurements to report the experimental observation of a pressure-induced crossover from two- to three-dimensional (2D to 3D) superconducting states in optimally doped Bi 2 Sr 2 CaCu 2 O 8+δ bulk superconductor. By analysing the temperature dependence of the resistance, we find that the 2D superconducting transition exhibits a Berezinskii–Kosterlitz–Thouless-like behaviour. The emergence of this 2D superconducting transition provides direct evidence that the strange metal state is predominantly 2D-like. Lastly, this is important for a thorough understanding of the phase diagram of cuprate superconductors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Current evaluation of the tripropellant concept

An analytical study was conducted to determine the specific-impulse advantages of adding metals to conventional liquid-bipropellant systems. These tripropellant systems theoretically offer higher specific impulse and increased propellant density compared with bipropellant systems. Metals considered were Be, Li, and Al. Bipropellant systems were H2/O2, N2H4/N2O4, RP-1/O2, and H2/F2. Thermochemical calculations were performed for sea-level expansion from 6.895-MN/sq. m. (1000-psia) chamber pressure over a wide range of mixture ratios and propellant compositions. Three-dimensional plots characterize the specific impulse of each tripropellant system. Technology issues pertinent to metallized propellant systems are discussed.

Zurawski, R. L.↗