Green steel from red mud through climate-neutral hydrogen plasma reduction.

Red mud is the waste of bauxite refinement into alumina, the feedstock for aluminium production1. With about 180 million tonnes produced per year1, red mud has amassed to one of the largest environmentally hazardous waste products, with the staggering amount of 4 billion tonnes accumulated on a global scale1. Here we present how this red mud can be turned into valuable and sustainable feedstock for ironmaking using fossil-free hydrogen-plasma-based reduction, thus mitigating a part of the steel-related carbon dioxide emissions by making it available for the production of several hundred million tonnes of green steel. The process proceeds through rapid liquid-state reduction, chemical partitioning, as well as density-driven and viscosity-driven separation between metal and oxides. We show the underlying chemical reactions, pH-neutralization processes and phase transformations during this surprisingly simple and fast reduction method. The approach establishes a sustainable toxic-waste treatment from aluminium production through using red mud as feedstock to mitigate greenhouse gas emissions from steelmaking.

Hydrogen trapping and embrittlement in high-strength Al alloys.

Ever more stringent regulations on greenhouse gas emissions from transportation motivate efforts to revisit materials used for vehicles1. High-strength aluminium alloys often used in aircrafts could help reduce the weight of automobiles, but are susceptible to environmental degradation2,3. Hydrogen 'embrittlement' is often indicated as the main culprit4; however, the exact mechanisms underpinning failure are not precisely known: atomic-scale analysis of H inside an alloy remains a challenge, and this prevents deploying alloy design strategies to enhance the durability of the materials. Here we performed near-atomic-scale analysis of H trapped in second-phase particles and at grain boundaries in a high-strength 7xxx Al alloy. We used these observations to guide atomistic ab initio calculations, which show that the co-segregation of alloying elements and H favours grain boundary decohesion, and the strong partitioning of H into the second-phase particles removes solute H from the matrix, hence preventing H embrittlement. Our insights further advance the mechanistic understanding of H-assisted embrittlement in Al alloys, emphasizing the role of H traps in minimizing cracking and guiding new alloy design.

A mechanically strong and ductile soft magnet with extremely low coercivity.

Soft magnetic materials (SMMs) serve in electrical applications and sustainable energy supply, allowing magnetic flux variation in response to changes in applied magnetic field, at low energy loss1. The electrification of transport, households and manufacturing leads to an increase in energy consumption owing to hysteresis losses2. Therefore, minimizing coercivity, which scales these losses, is crucial3. Yet meeting this target alone is not enough: SMMs in electrical engines must withstand severe mechanical loads; that is, the alloys need high strength and ductility4. This is a fundamental design challenge, as most methods that enhance strength introduce stress fields that can pin magnetic domains, thus increasing coercivity and hysteresis losses5. Here we introduce an approach to overcome this dilemma. We have designed a Fe-Co-Ni-Ta-Al multicomponent alloy (MCA) with ferromagnetic matrix and paramagnetic coherent nanoparticles (about 91 nm in size and around 55% volume fraction). They impede dislocation motion, enhancing strength and ductility. Their small size, low coherency stress and small magnetostatic energy create an interaction volume below the magnetic domain wall width, leading to minimal domain wall pinning, thus maintaining the soft magnetic properties. The alloy has a tensile strength of 1,336 MPa at 54% tensile elongation, extremely low coercivity of 78 A m-1 (less than 1 Oe), moderate saturation magnetization of 100 A m2 kg-1 and high electrical resistivity of 103 µΩ cm.

High-strength Damascus steel by additive manufacturing.

Laser additive manufacturing is attractive for the production of complex, three-dimensional parts from metallic powder using a computer-aided design model1-3. The approach enables the digital control of the processing parameters and thus the resulting alloy's microstructure, for example, by using high cooling rates and cyclic re-heating4-10. We recently showed that this cyclic re-heating, the so-called intrinsic heat treatment, can trigger nickel-aluminium precipitation in an iron-nickel-aluminium alloy in situ during laser additive manufacturing9. Here we report a Fe19Ni5Ti (weight per cent) steel tailor-designed for laser additive manufacturing. This steel is hardened in situ by nickel-titanium nanoprecipitation, and martensite is also formed in situ, starting at a readily accessible temperature of 200 degrees Celsius. Local control of both the nanoprecipitation and the martensitic transformation during the fabrication leads to complex microstructure hierarchies across multiple length scales, from approximately 100-micrometre-thick layers down to nanoscale precipitates. Inspired by ancient Damascus steels11-14-which have hard and soft layers, originally introduced via the folding and forging techniques of skilled blacksmiths-we produced a material consisting of alternating soft and hard layers. Our material has a tensile strength of 1,300 megapascals and 10 per cent elongation, showing superior mechanical properties to those of ancient Damascus steel12. The principles of in situ precipitation strengthening and local microstructure control used here can be applied to a wide range of precipitation-hardened alloys and different additive manufacturing processes.

Chemo-mechanical failure mechanisms of the silicon anode in solid-state batteries.

Silicon is a promising anode material due to its high theoretical specific capacity, low lithiation potential and low lithium dendrite risk. Yet, the electrochemical performance of silicon anodes in solid-state batteries is still poor (for example, low actual specific capacity and fast capacity decay), hindering practical applications. Here the chemo-mechanical failure mechanisms of composite Si/Li6PS5Cl and solid-electrolyte-free silicon anodes are revealed by combining structural and chemical characterizations with theoretical simulations. The growth of the solid electrolyte interphase at the Si|Li6PS5Cl interface causes severe resistance increase in composite anodes, explaining their fast capacity decay. Solid-electrolyte-free silicon anodes show sufficient ionic and electronic conductivities, enabling a high specific capacity. However, microscale void formation during delithiation causes larger mechanical stress at the two-dimensional interfaces of these anodes than in composite anodes. Understanding these chemo-mechanical failure mechanisms of different anode architectures and the role of interphase formation helps to provide guidelines for the design of improved electrode materials.

The Materials Science behind Sustainable Metals and Alloys.

Production of metals stands for 40% of all industrial greenhouse gas emissions, 10% of the global energy consumption, 3.2 billion tonnes of minerals mined, and several billion tonnes of by-products every year. Therefore, metals must become more sustainable. A circular economy model does not work, because market demand exceeds the available scrap currently by about two-thirds. Even under optimal conditions, at least one-third of the metals will also in the future come from primary production, creating huge emissions. Although the influence of metals on global warming has been discussed with respect to mitigation strategies and socio-economic factors, the fundamental materials science to make the metallurgical sector more sustainable has been less addressed. This may be attributed to the fact that the field of sustainable metals describes a global challenge, but not yet a homogeneous research field. However, the sheer magnitude of this challenge and its huge environmental effects, caused by more than 2 billion tonnes of metals produced every year, make its sustainability an essential research topic not only from a technological point of view but also from a basic materials research perspective. Therefore, this paper aims to identify and discuss the most pressing scientific bottleneck questions and key mechanisms, considering metal synthesis from primary (minerals), secondary (scrap), and tertiary (re-mined) sources as well as the energy-intensive downstream processing. Focus is placed on materials science aspects, particularly on those that help reduce CO2 emissions, and less on process engineering or economy. The paper does not describe the devastating influence of metal-related greenhouse gas emissions on climate, but scientific approaches how to solve this problem, through research that can render metallurgy fossil-free. The content is considering only direct measures to metallurgical sustainability (production) and not indirect measures that materials leverage through their properties (strength, weight, longevity, functionality).

Strategies for improving the sustainability of structural metals.

Metallic materials have enabled technological progress over thousands of years. The accelerated demand for structural (that is, load-bearing) alloys in key sectors such as energy, construction, safety and transportation is resulting in predicted production growth rates of up to 200 per cent until 2050. Yet most of these materials require a lot of energy when extracted and manufactured and these processes emit large amounts of greenhouse gases and pollution. Here we review methods of improving the direct sustainability of structural metals, in areas including reduced-carbon-dioxide primary production, recycling, scrap-compatible alloy design, contaminant tolerance of alloys and improved alloy longevity. We discuss the effectiveness and technological readiness of individual measures and also show how novel structural materials enable improved energy efficiency through their reduced mass, higher thermal stability and better mechanical properties than currently available alloys.

Publisher Correction: Enhanced strength and ductility in a high-entropy alloy via ordered oxygen complexes.

Change history: In this Letter, owing to a production error, all the data points (except the two points for O-2 and N-2, respectively) were missing in Fig. 1b. The figure has been corrected online.

The dual role of martensitic transformation in fatigue crack growth.

Deformation-induced martensitic transformation (DIMT) has been used for designing high-performance alloys to prevent structural failure under static loads. Its effectiveness against fatigue, however, is unclear. This limits the application of DIMT for parts that are exposed to variable loads, although such scenarios are the rule and not the exception for structural failure. Here we reveal the dual role of DIMT in fatigue crack growth through in situ observations. Two antagonistic fatigue mechanisms mediated by DIMT are identified, namely, transformation-mediated crack arresting, which prevents crack growth, and transformation-mediated crack coalescence, which promotes crack growth. Both mechanisms are due to the hardness and brittleness of martensite as a transformation product, rather than to the actual transformation process itself. In fatigue crack growth, the prevalence of one mechanism over the other critically depends on the crack size and the mechanical stability of the parent austenite phase. Elucidating the two mechanisms and their interplay allows for the microstructure design and safe use of metastable alloys that experience fatigue loads. The findings also generally reveal how metastable alloy microstructures must be designed for materials to be fatigue-resistant.

Quantitative tests revealing hydrogen-enhanced dislocation motion in α-iron.

Hydrogen embrittlement jeopardizes the use of high-strength steels in critical load-bearing applications. However, uncertainty regarding how hydrogen affects dislocation motion, owing to the lack of quantitative experimental evidence, hinders our understanding of hydrogen embrittlement. Here, by studying the well-controlled, cyclic, bow-out motions of individual screw dislocations in α-iron, we find that the critical stress for initiating dislocation motion in a 2 Pa electron-beam-excited H2 atmosphere is 27-43% lower than that in a vacuum environment, proving that hydrogen enhances screw dislocation motion. Moreover, we find that aside from vacuum degassing, cyclic loading and unloading facilitates the de-trapping of hydrogen, allowing the dislocation to regain its hydrogen-free behaviour. These findings at the individual dislocation level can inform hydrogen embrittlement modelling and guide the design of hydrogen-resistant steels.

Enhanced strength and ductility in a high-entropy alloy via ordered oxygen complexes.

Oxygen, one of the most abundant elements on Earth, often forms an undesired interstitial impurity or ceramic phase (such as an oxide particle) in metallic materials. Even when it adds strength, oxygen doping renders metals brittle1-3. Here we show that oxygen can take the form of ordered oxygen complexes, a state in between oxide particles and frequently occurring random interstitials. Unlike traditional interstitial strengthening4,5, such ordered interstitial complexes lead to unprecedented enhancement in both strength and ductility in compositionally complex solid solutions, the so-called high-entropy alloys (HEAs)6-10. The tensile strength is enhanced (by 48.5 ± 1.8 per cent) and ductility is substantially improved (by 95.2 ± 8.1 per cent) when doping a model TiZrHfNb HEA with 2.0 atomic per cent oxygen, thus breaking the long-standing strength-ductility trade-off11. The oxygen complexes are ordered nanoscale regions within the HEA characterized by (O, Zr, Ti)-rich atomic complexes whose formation is promoted by the existence of chemical short-range ordering among some of the substitutional matrix elements in the HEAs. Carbon has been reported to improve strength and ductility simultaneously in face-centred cubic HEAs12, by lowering the stacking fault energy and increasing the lattice friction stress. By contrast, the ordered interstitial complexes described here change the dislocation shear mode from planar slip to wavy slip, and promote double cross-slip and thus dislocation multiplication through the formation of Frank-Read sources (a mechanism explaining the generation of multiple dislocations) during deformation. This ordered interstitial complex-mediated strain-hardening mechanism should be particularly useful in Ti-, Zr- and Hf-containing alloys, in which interstitial elements are highly undesirable owing to their embrittlement effects, and in alloys where tuning the stacking fault energy and exploiting athermal transformations13 do not lead to property enhancement. These results provide insight into the role of interstitial solid solutions and associated ordering strengthening mechanisms in metallic materials.

Effect of Pore Formation on Redox-Driven Phase Transformation.

When solid-state redox-driven phase transformations are associated with mass loss, vacancies are produced that develop into pores. These pores can influence the kinetics of certain redox and phase transformation steps. We investigated the structural and chemical mechanisms in and at pores in a combined experimental-theoretical study, using the reduction of iron oxide by hydrogen as a model system. The redox product (water) accumulates inside the pores and shifts the local equilibrium at the already reduced material back toward reoxidation into cubic Fe_{1-x}O (where x refers to Fe deficiency, space group Fm3[over ¯]m). This effect helps us to understand the sluggish reduction of cubic Fe_{1-x}O by hydrogen, a key process for future sustainable steelmaking.

Ultrastrong steel via minimal lattice misfit and high-density nanoprecipitation.

Next-generation high-performance structural materials are required for lightweight design strategies and advanced energy applications. Maraging steels, combining a martensite matrix with nanoprecipitates, are a class of high-strength materials with the potential for matching these demands. Their outstanding strength originates from semi-coherent precipitates, which unavoidably exhibit a heterogeneous distribution that creates large coherency strains, which in turn may promote crack initiation under load. Here we report a counterintuitive strategy for the design of ultrastrong steel alloys by high-density nanoprecipitation with minimal lattice misfit. We found that these highly dispersed, fully coherent precipitates (that is, the crystal lattice of the precipitates is almost the same as that of the surrounding matrix), showing very low lattice misfit with the matrix and high anti-phase boundary energy, strengthen alloys without sacrificing ductility. Such low lattice misfit (0.03 ± 0.04 per cent) decreases the nucleation barrier for precipitation, thus enabling and stabilizing nanoprecipitates with an extremely high number density (more than 1024 per cubic metre) and small size (about 2.7 ± 0.2 nanometres). The minimized elastic misfit strain around the particles does not contribute much to the dislocation interaction, which is typically needed for strength increase. Instead, our strengthening mechanism exploits the chemical ordering effect that creates backstresses (the forces opposing deformation) when precipitates are cut by dislocations. We create a class of steels, strengthened by Ni(Al,Fe) precipitates, with a strength of up to 2.2 gigapascals and good ductility (about 8.2 per cent). The chemical composition of the precipitates enables a substantial reduction in cost compared to conventional maraging steels owing to the replacement of the essential but high-cost alloying elements cobalt and titanium with inexpensive and lightweight aluminium. Strengthening of this class of steel alloy is based on minimal lattice misfit to achieve maximal precipitate dispersion and high cutting stress (the stress required for dislocations to cut through coherent precipitates and thus produce plastic deformation), and we envisage that this lattice misfit design concept may be applied to many other metallic alloys.

Chemical heterogeneity enhances hydrogen resistance in high-strength steels.

The antagonism between strength and resistance to hydrogen embrittlement in metallic materials is an intrinsic obstacle to the design of lightweight yet reliable structural components operated in hydrogen-containing environments. Economical and scalable microstructural solutions to this challenge must be found. Here, we introduce a counterintuitive strategy to exploit the typically undesired chemical heterogeneity within the material's microstructure that enables local enhancement of crack resistance and local hydrogen trapping. We use this approach in a manganese-containing high-strength steel and produce a high dispersion of manganese-rich zones within the microstructure. These solute-rich buffer regions allow for local micro-tuning of the phase stability, arresting hydrogen-induced microcracks and thus interrupting the percolation of hydrogen-assisted damage. This results in a superior hydrogen embrittlement resistance (better by a factor of two) without sacrificing the material's strength and ductility. The strategy of exploiting chemical heterogeneities, rather than avoiding them, broadens the horizon for microstructure engineering via advanced thermomechanical processing.

Metastable high-entropy dual-phase alloys overcome the strength-ductility trade-off.

Metals have been mankind's most essential materials for thousands of years; however, their use is affected by ecological and economical concerns. Alloys with higher strength and ductility could alleviate some of these concerns by reducing weight and improving energy efficiency. However, most metallurgical mechanisms for increasing strength lead to ductility loss, an effect referred to as the strength-ductility trade-off. Here we present a metastability-engineering strategy in which we design nanostructured, bulk high-entropy alloys with multiple compositionally equivalent high-entropy phases. High-entropy alloys were originally proposed to benefit from phase stabilization through entropy maximization. Yet here, motivated by recent work that relaxes the strict restrictions on high-entropy alloy compositions by demonstrating the weakness of this connection, the concept is overturned. We decrease phase stability to achieve two key benefits: interface hardening due to a dual-phase microstructure (resulting from reduced thermal stability of the high-temperature phase); and transformation-induced hardening (resulting from the reduced mechanical stability of the room-temperature phase). This combines the best of two worlds: extensive hardening due to the decreased phase stability known from advanced steels and massive solid-solution strengthening of high-entropy alloys. In our transformation-induced plasticity-assisted, dual-phase high-entropy alloy (TRIP-DP-HEA), these two contributions lead respectively to enhanced trans-grain and inter-grain slip resistance, and hence, increased strength. Moreover, the increased strain hardening capacity that is enabled by dislocation hardening of the stable phase and transformation-induced hardening of the metastable phase produces increased ductility. This combined increase in strength and ductility distinguishes the TRIP-DP-HEA alloy from other recently developed structural materials. This metastability-engineering strategy should thus usefully guide design in the near-infinite compositional space of high-entropy alloys.

Impact of interstitial elements on the stacking fault energy of an equiatomic CoCrNi medium entropy alloy: theory and experiments.

We investigated the effects of interstitial N and C on the stacking fault energy (SFE) of an equiatomic CoCrNi medium entropy alloy. Results of computer modeling were compared to tensile deformation and electron microscopy data. Both N and C in solid solution increase the SFE of the face-centered cubic (FCC) alloy matrix at room temperature, with the former having a more significant effect by 240% for 0.5 at % N. Total energy calculations based on density functional theory (DFT) as well as thermodynamic modeling of the Gibbs free energy with the CALPHAD (CALculation of PHAse Diagrams) method reveal a stabilizing effect of N and C interstitials on the FCC lattice with respect to the hexagonal close-packed (HCP) CoCrNi-X (X: N, C) lattice. Scanning transmission electron microscopy (STEM) measurements of the width of dissociated ½<110> dislocations suggest that the SFE of CoCrNi increases from 22 to 42-44 mJ·m-2 after doping the alloy with 0.5 at. % interstitial N. The higher SFE reduces the nucleation rates of twins, leading to an increase in the critical stress required to trigger deformation twinning, an effect which can be used to design load-dependent strain hardening response.

Discovery and Implications of Hidden Atomic-Scale Structure in a Metallic Meteorite.

Iron and its alloys have made modern civilization possible, with metallic meteorites providing one of the human's earliest sources of usable iron as well as providing a window into our solar system's billion-year history. Here highest-resolution tools reveal the existence of a previously hidden FeNi nanophase within the extremely slowly cooled metallic meteorite NWA 6259. This new nanophase exists alongside Ni-poor and Ni-rich nanoprecipitates within a matrix of tetrataenite, the uniaxial, chemically ordered form of FeNi. The ferromagnetic nature of the nanoprecipitates combined with the antiferromagnetic character of the FeNi nanophases gives rise to a complex magnetic state that evolves dramatically with temperature. These observations extend and possibly alter our understanding of celestial metallurgy, provide new knowledge concerning the archetypal Fe-Ni phase diagram and supply new information for the development of new types of sustainable, technologically critical high-energy magnets.

On the Formation Mechanism of Column Damage Within Modular Taper Junctions.

BACKGROUND: Column damage is a unique degradation pattern observed in cobalt-chromium-molybdenum (CoCrMo) femoral head taper surfaces that resemble column-like troughs in the proximal-distal direction. We investigate the metallurgical origin of this phenomenon. METHODS: Thirty-two severely damaged CoCrMo femoral head retrievals from 7 different manufacturers were investigated for the presence of column damage and chemical inhomogeneities within the alloy microstructure via metallographic evaluation of samples sectioned off from the femoral heads. RESULTS: Column damage was found to affect 37.5% of the CoCrMo femoral heads in this study. All the column-damaged femoral heads exhibited chemical inhomogeneities within their microstructures, which comprised of regions enriched or depleted in molybdenum and chromium. Column damage appears as a dissolution of the entire surface with preferential corrosion along the molybdenum and chromium depleted regions. CONCLUSION: Molybdenum and chromium depleted zones serve as initiation sites for in vivo corrosion of the taper surface. Through crevice corrosion, the degradation spreads to the adjacent non-compositionally depleted areas of the alloy as well. Future improved alloy and processing recipes are required to ensure no chemical inhomogeneity due to segregation of solute elements are present in CoCrMo femoral heads.

Nanoglass-Nanocrystal Composite-a Novel Material Class for Enhanced Strength-Plasticity Synergy.

The properties of a material can be engineered by manipulating its atomic and chemical architecture. Nanoglasses which have been recently invented and comprise nanosized glassy particles separated by amorphous interfaces, have shown promising properties. A potential way to exploit the structural benefits of nanoglasses and of nanocrystalline materials is to optimize the composition to obtain crystals forming within the glassy particles. Here, a metastable Fe-10 at% Sc nanoglass is synthesized. A complex hierarchical microstructure is evidenced experimentally at the atomic scale. This bulk material comprises grains of a Fe90 Sc10 amorphous matrix separated by an amorphous interfacial network enriched and likely stabilized by hydrogen, and property-enhancing pure-Fe nanocrystals self-assembled within the matrix. This composite structure leads a yield strength above 2.5 GPa with an exceptional quasi-homogeneous plastic flow of more than 60% in compression. This work opens new pathways to design materials with even superior properties.

Interplay of Chemistry and Faceting at Grain Boundaries in a Model Al Alloy.

The boundary between two crystal grains can decompose into arrays of facets with distinct crystallographic character. Faceting occurs to minimize the system's free energy, i.e., when the total interfacial energy of all facets is below that of the topologically shortest interface plane. In a model Al-Zn-Mg-Cu alloy, we show that faceting occurs at investigated grain boundaries and that the local chemistry is strongly correlated with the facet character. The self-consistent coevolution of facet structure and chemistry leads to the formation of periodic segregation patterns of 5-10 nm, or to preferential precipitation. This study shows that segregation-faceting interplay is not limited to bicrystals but exists in bulk engineering Al alloys and hence affects their performance.