Electrochemical Leaching of Cobalt from Cobaltite: Box-Behnken Design and Optimization with Response Surface Methodology
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Sm2Fe17C3 phase (2:17) is metastable and exhibits excellent intrinsic hard magnetic properties. Doping elements such as Ga facilitate the formation of a single-phase 2:17 structure in arc-melted Sm2Fe17Cx alloys, which opens a promising route for fabricating fully dense bulk Sm2Fe17Cx magnets via high-temperature techniques such as melting and sintering. First-principles electronic structure calculation indicates that Ga prefers to partially replace Fe at the 9d and 18h crystallographic sites in Sm2Fe17C3 and Sm2Fe17, respectively. This difference in site preference is attributed to the distinct chemical environments surrounding the Fe atoms in the two compounds. Ga substitution favors the Sm–Ga bonding formation while avoiding Ga–C interactions. Doped Ga atoms result in more negative formation energy in Sm2(Fe, Ga)17C3, indicating improved structural stability. Crystal Orbital Hamilton Population analysis reveals that carbon insertion weakens the bonding of Sm-Fe (18h) and Sm-Fe (18f) in Sm2Fe17C3. Ga doping facilitates electron redistribution across chemical bonds, thereby reinforcing Fe(18h)–Sm and Fe(18f)–Sm interactions and stabilizing the carbon-centered octahedral local structure. This synergistic effect contributes significantly to the observed enhancement in phase stability of Sm2(Fe, Ga)17Cx. These findings suggest that chemical bond engineering through the selective doping of Ga can enhance phase stability and facilitate the synthesis of Sm2Fe17C3, providing a viable strategy for developing advanced magnets.
Identification of innovative solutions to unique materials problems is an every-day quest for members of the aerospace community. Finding a technique that will minimize costs, maximize throughput, and generate quality results is always the target. United Space Alliance Materials Engineers recently conducted such a search in their drive to return the Space Shuttle fleet to operational status. The removal of high performance thermal coatings from solid rocket motors represents a formidable task during post flight disassembly on reusable expended hardware. The removal of these coatings from unfired motors increases the complexity and safety requirements while reducing the available facilities and approved processes. A temporary solution to this problem was identified, tested and approved during the Solid Rocket Booster (SRB) return to flight activities. Utilization of ultra high-pressure liquid nitrogen (LN2) to strip the protective coating from assembled space shuttle hardware marked the first such use of the technology in the aerospace industry. This process provides a configurable stream of liquid nitrogen (LN2) at pressures of up to 55,000 psig. The performance of a one-time certification for the removal of thermal ablatives from SRB hardware involved extensive testing to ensure adequate material removal without causing undesirable damage to the residual materials or aluminum substrates. Testing to establish appropriate process parameters such as flow, temperature and pressures of the liquid nitrogen stream provided an initial benchmark for process testing. Equipped with these initial parameters engineers were then able to establish more detailed test criteria that set the process limits. Quantifying the potential for aluminum hardware damage represented the greatest hurdle for satisfying engineers as to the safety of this process. Extensive testing for aluminum erosion, surface profiling, and substrate weight loss was performed. This successful project clearly demonstrated that the liquid nitrogen jet possesses unique strengths that align remarkably well with the unusual challenges that space hardware and missile manufacturers face on a regular basis. Performance of this task within the confines of a critical manufacturing facility marks a milestone in advanced processing.
The innovative process of Friction Stir Welding (FSW) has generated tremendous interest since its inception about a decade or so ago since the first patent in 1991 by TWI of Cambridge, England. This interest has been seen in many recent international conferences and publications on the subject and relevant published literature. Still the process needs both intensive basic study of deformation mechanisms during this FSW process and analysis and feasibility study to evaluate production methods that will yield high quality strong welds from the stirring action of the appropriate pin tool into the weld plate materials. Development of production processes is a complex task that involves effects of material thickness, materials weldability, pin tool design, pin height, and pin shoulder diameter and related control conditions. The frictional heating with rotational speeds of the pin tool as it plunges into the material and the ensuing plastic flow arising during the traverse of the welding faying surfaces provide the known special advantages of the FSW process in the area of this new advanced joining technology.
Critical minerals lists have flourished in the past decade, in particular linked to the importance of critical minerals for low-carbon transitions. We identified 27 critical minerals or materials lists across 15 countries and the European Union (EU). These lists are designed to attract public and private attention and investments to secure both domestic and foreign supplies. This review article fills a gap in the existing literature by analyzing the ways in which these lists are defined and utilized by countries engaged in a mineral rush. We focus our attention on three categories of minerals – battery minerals, platinum-group metals (PGMs), and rare earth elements (REEs) that are particularly important to energy transitions. We situate this research in the broader legal and administrative developments that have driven critical minerals policies in the past decade. We provide an in-depth analysis of the commonalities and variations in the raw materials included in these lists, and identify six core limitations of critical minerals lists: (1) unclear links between criticality assessments and mineral prioritization (2) failure to account for the full mineral value-chain; (3) limited strategic alignment between allied nations; (4) limited flexibility in dynamic environments (5) limited consideration for recycling and by-product sourcing; and (6) reliance on incomplete reserve and resource data.
HgZnSe and HgZnTe are electronic materials of interest for potential IR detector and focal plane array applications due to their improved strength and compositional stability over HgCdTe, but they are difficult to grow on Earth and to fully characterize. Conventional contact methods of characterization, such as Hall and van der Paw, although adequate for many situations are typically labor intensive and not entirely suitable where only very small samples are available. To adequately characterize and compare properties of electronic materials grown in low earth orbit with those grown on Earth, innovative techniques are needed that complement existing methods. This paper describes the implementation and test results of a unique non-contact method of characterizing uniformity, mobility, and carrier concentration together with results from conventional methods applied to HgZnSe and HgZnTe. The innovative method has advantages over conventional contact methods since it circumvents problems of possible contamination from alloying electrical contacts to a sample and also has the capability to map a sample. Non- destructive mapping, the determination of the carrier concentration and mobility at each place on a sample, provides a means to quantitatively compare, at high spatial resolution, effects of microgravity on electronic properties and uniformity of electronic materials grown in low-Earth orbit with Earth grown materials. The mapping technique described here uses a 1mm diameter polarized beam of radiation to probe the sample. Activation of a magnetic field, in which the sample is placed, causes the plane of polarization of the probe beam to rotate. This Faraday rotation is a function of the free carrier concentration and the band parameters of the material. Maps of carrier concentration, mobility, and transmission generated from measurements of the Faraday rotation angles over the temperature range from 300K to 77K will be presented. New information on band parameters, obtained by combining results from conventional Hall measurements of the free carrier concentration with Faraday rotation measurements, will also be presented. One example of how this type of information was derived is illustrated in the following figure which shows Faraday rotation vs wavelength modeled for Hg(l-x)ZnxSe at a temperature of 300K and x=0.07. The plasma contribution, total Faraday rotation, and interband contribution to the Faraday rotation, are designated in the Figure as del(p), FR tot, and del(i) respectively. Experimentally measured values of FR tot, each indicated by + , agree acceptably well with the model at the probe wavelength of 10.6 microns. The model shows that at the probe wavelength, practically all the rotation is due to the plasma component, which can be expressed as delta(sub p)= 2pi(e(sup 3))NBL/c(sup 2)nm*(sup 2) omega(sup 2). In this equation, delta(sub p) is the rotation angle due to the free carrier plasma, N is the free carrier concentration, B the magnetic field strength, L the thickness of the sample, n the index of refraction, omega the probe radiation frequency, c the speed of light, e the electron charge, and m* the effective mass. A measurement of N by conventional techniques, combined with a measurement of the Faraday rotation angle allows m* to be accurately determined since it is an inverse square function.
Critical raw materials (CRMs) and/or critical minerals and materials (CMMs) are metals, metal groups, and non-metallic minerals essential for the many modern technologies, including wind turbine, electric vehicles and energy storage systems. Different countries have slightly different metrics for determining criticality. However, broadly speaking, the European Union (EU) and United States (US)both define them as materials that reach or exceed thresholds for both economic importance and supply risk. Furthermore, both organizations have implemented instruments, such as the EU's 2024 Critical Raw Materials Act and the US Department of Energy's (DOE) Critical Minerals and Materials Strategy, to facilitate research and development of CRM/CMM ranging from mineral deposit development to geometallurgy to separations to advanced manufacturing. This talk is aimed at an EU audience to explain the DOE CMM strategy and how it compares to the steps taken by the EU to facilitate progress. Furthermore, this talk takes a geology-centric approach on the challenges geoscientists face and how their roles may change in the future.
Abstract Additive manufacturing promises a major transformation of the production of high economic value metallic materials, enabling innovative, geometrically complex designs with minimal material waste. The overarching challenge is to design alloys that are compatible with the unique additive processing conditions while maintaining material properties sufficient for the challenging environments encountered in energy, space, and nuclear applications. Here we describe a class of high strength, defect-resistant 3D printable superalloys containing approximately equal parts of Co and Ni along with Al, Cr, Ta and W that possess strengths in excess of 1.1 GPa in as-printed and post-processed forms and tensile ductilities of greater than 13% at room temperature. These alloys are amenable to crack-free 3D printing via electron beam melting (EBM) with preheat as well as selective laser melting (SLM) with limited preheat. Alloy design principles are described along with the structure and properties of EBM and SLM CoNi-base materials.
This Technical Memorandum briefly covers various innovations in materials science and development throughout the course of the American Space program. It details each innovation s discovery and development, explains its significance, and describes the applications of this material either in the time period discovered or today. Topics of research include silazane polymers, solvent-resistant elastomeric polymers (polyurethanes and polyisocyanurates), siloxanes, the Space Shuttle thermal protection system, phenolic-impregnated carbon ablator, and carbon nanotubes. Significance of these developments includes the Space Shuttle, Apollo programs, and the Constellation program.
Holistic and intentional training prepares next-generation materials informatics leaders and workforce for expedited materials discovery and design.
The pursuit for higher-coherence superconducting qubits has led to the adoption of new materials and innovative fabrication techniques. Among the commonly used superconducting materials, tantalum-based or tantalum-capped superconducting qubits have demonstrated the longest lifetimes, outperforming niobium devices even in the presence of their native oxides. Given the losses introduced by the surface oxide, one method to further improve performance is to reduce or eliminate the native oxide on tantalum through UHV annealing. In this work, we examine the effect of dissolved oxygen as a function of annealing temperature on the superconducting properties of tantalum thin films. Dissolved oxygen is quantified using atom probe tomography (APT) and secondary ion mass spectrometry (TOF-SIMS) and correlated with electromagnetic transport measurements performed using a Physical Property Measurement System (PPMS). This study observes that annealing decomposes the native oxide and drives oxygen diffusion into the film matrix. Increasing oxygen content decreases the superconducting transition temperature (Tc) and the residual resistivity ratio (RRR). The critical field decreases with the incorporation of oxygen, while the film’s coherence length decreases relatively by 5%. These results, as well as findings from ongoing studies linking fabrication processes to the structural and chemical properties of the superconducting film and Josephson junction, provide insight into effective strategies for improving the performance of superconducting devices.
One of the main sources of clean electricity in the civilian power grid comes from light water reactors (LWRs). Some of these LWRs are being decommissioned prematurely because they may not be economically sustainable. It is proposed that the use of accident-tolerant fuel concepts may enable for LWR plant operation extension by making them safer and more economically competitive to operate. For example, the use of iron-chromium-aluminum (FeCrAl) alloys for the cladding of the fuel would not only reduce the risk of catastrophic reaction between the cladding and its environment in the case of a loss of coolant accident situation but also, for example, allow for higher fuel burnup during normal plant operation.
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NASA’s state-of-the-art ablative materials are composed of a three-dimensional network of carbon fibers impregnated with polymers that dissipate thermal energy through pyrolysis. A fundamental understanding of the decomposition mechanisms and pyrolysis product distributions of various classes of polymers is instrumental in the design of new ablative materials. Furthermore, innovative experiments are essential to the continuous modernization of material response models by providing high-fidelity data. Thus, an apparatus has been designed to measure pyrolysis products from polymers and composite materials by implementing in-situ mass spectrometric techniques. Initial results from experiments performed on siloxane resins and a common phenolic resin will be discussed. Both classes of polymers exhibit heating-rate-dependent decomposition mechanisms. At the onset of heating, phenolic polymers decompose through competitive reactions to form gaseous products and a carbonaceous char. Gas phase products of phenolic resins are typically composed of molecular hydrogen, water, and aromatic hydrocarbons. Pyrolysis products from siloxane polymers include molecular hydrogen, small molecules, and cyclic oligomers from the polymer backbone.
NASA’s state-of-the-art ablative materials are composed of a three-dimensional network of carbon fibers impregnated with polymers that dissipate thermal energy through pyrolysis. A fundamental understanding of the decomposition mechanisms and pyrolysis product distributions of various classes of polymers is instrumental in the design of new ablative materials. Furthermore, innovative experiments are essential to the continuous modernization of material response models by providing high-fidelity data. Thus, an apparatus has been designed to measure pyrolysis products from polymers and composite materials by implementing in-situ mass spectrometric techniques. Initial results from experiments performed on siloxane resins and a common phenolic resin will be discussed. Both classes of polymers exhibit heating-rate-dependent decomposition mechanisms. At the onset of heating, phenolic polymers decompose through competitive reactions to form gaseous products and a carbonaceous char. Gas phase products of phenolic resins are typically composed of molecular hydrogen, water, and aromatic hydrocarbons. Pyrolysis products from siloxane polymers include molecular hydrogen, small molecules, and cyclic oligomers from the polymer.
Rod-shaped Fe5C2 and core/shell Fe5C2/SiO2 nanocrystals were synthesized via a solution-based chemical method. Structural analysis confirmed the monoclinic phase of Fe5C2 with space group C2/c. Zero-field-cooling (ZFC) and field-cooling (FC) magnetization curves revealed distinct magnetic behaviors: uncoated Fe5C2 exhibited a low-temperature FC plateau indicative of strong dipolar interactions, while Fe5C2/SiO2 showed a monotonic increase in FC magnetization, suggesting reduced dipolar interactions due to SiO2 surface passivation. Isothermal remanent magnetization (IRM) and DC demagnetization (DCD) measurements supported this trend, with δM plots confirming weaker dipolar interactions in the coated sample. Bloch’s law fitting of temperature-dependent saturation magnetization showed a smaller Bloch’s constant for pure Fe5C2 and a larger value for Fe5C2/SiO2, reflecting enhanced surface disorder and reduced exchange coupling in the latter. Notably, Fe5C2/SiO2 demonstrated increased coercivity, attributed to decreased dipolar interaction and elevated surface anisotropy. Kneller’s law fitting yielded higher blocking temperatures for Fe5C2 (476 K) than Fe5C2/SiO2 (456 K), highlighting the impact of dipolar interactions on magnetic relaxation. These findings illustrate how SiO2 coatings effectively modulate dipolar interactions and enhance coercivity in Fe5C2 nanocrystals.
In this work, we report the impact of Si substitution on the structural and magnetic properties of Fe3CoB2 nanocrystallites as a rare-earth-free hard-magnet candidate. X-ray diffraction confirmed the formation of the tetragonal phase with an average crystallite size of ∼40 nm, while the transmission electron microscopy image revealed nanosized crystallites embedded in an amorphous matrix. Room-temperature Mössbauer spectra exhibited two sextets and two doublets, indicating magnetically ordered Fe sites in the tetragonal phase along with high-spin paramagnetic FeIII species in disordered regions. ZFC–FC magnetization curves displayed field-dependent blocking behavior, consistent with paramagnetic Fe species. Singular point detection measurements revealed a high anisotropy field of ∼10.7 kOe in the pristine Fe3CoB2, and systematically decreased with Si substitution. Magnetization measurements revealed a monotonic decrease in saturation magnetization with Si content, while coercivity was observed to increase, likely due to microstructural refinement. These results establish Fe3CoB2 as a rare-earth-free material with strong magnetic anisotropy, ideal for hard magnets.
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