Thermal Kinetics and Nitriding Effect of Ammonia-Based Direct Reduction of Iron Oxides.

Ammonia is a promising alternative hydrogen carrier that can be utilized for the solid-state reduction of iron oxides for sustainable ironmaking due to its easy transportation and high energy density. The main challenge for its utilization on an industrial scale is to understand the reaction kinetics under different process conditions and the associated nitrogen incorporation in the reduced material that originates from ammonia decomposition. In this work, the effect of temperature on the reduction efficiency and nitride formation is investigated through phase, local chemistry, and gas evolution analysis. The effects of inherent reactions and diffusion on phase formation and chemistry evolution are discussed in relation to the reduction temperature. The work also discusses nitrogen incorporation into the material through both spontaneous and in-process nitriding, which fundamentally affects the structure and chemistry of the reduced material. Finally, the effect of nitrogen incorporation on the reoxidation tendency of the ammonia-based reduced material is investigated and compared with that of the hydrogen-based reduced counterpart. The results provide a fundamental understanding of the reduction and nitriding for iron oxides exposed to ammonia at temperatures from 500 to 800 °C, serving as a basis for exploitation and upscaling of ammonia-based direct reduction for future green steel production.

Thermodynamics-Guided High-Throughput Discovery of Eutectic High-Entropy Alloys for Rapid Solidification.

Excellent castability, significantly refined microstructure, and good mechanical properties make eutectic high-entropy alloys (EHEAs) a natural fit for rapid solidification processes, e.g., additive manufacturing. Previous investigations have focused on developing EHEAs through trial and error and mixing known binary eutectic materials. However, eutectic compositions obtained from near-equilibrium conditions do not guarantee a fully eutectic microstructure under rapid solidifications. In this work, a thermodynamically guided high-throughput framework is proposed to design EHEAs for rapid solidification. Empirical formulas derived from past experimental observations and thermodynamic computations are applied and considered phase growth kinetics under rapid solidification (skewed phase diagram). The designed alloy candidate, Co25.6Fe17.9Ni22.4Cr19.1Ta8.9Al6.1 (wt.%), contains nanostructured eutectic lamellar and shows a high Vickers hardness of 675 Hv. In addition to this specific composition, the alloy design toolbox enables the development of new EHEAs for rapid solidification without the limitation of previous knowledge.

Shearing brittle intermetallics enhances cryogenic strength and ductility of steels.

Precipitates are crucial for crafting mechanically strong metallic materials. In this work, we report the dislocation cutting of B2 (ordered body-centered cubic) nanoprecipitates, typically considered nonshearable intermetallics, in a lightweight compositionally complex steel during cryogenic tensile loading. Shearing is enabled by the high strength level for dislocation glide within the austenitic matrix, attributed to the substantial strengthening from subnanoscale local chemical ordering zones and the pronounced solid solution strengthening from the multiprincipal elements in the matrix. This mechanism not only harnesses the intense strengthening and strain hardening provided by otherwise impenetrable brittle nanoprecipitates but also introduces ductility through their sequential shearing with ongoing deformation. Our steel thus showcases ultrahigh cryogenic tensile strength up to 2 gigapascal at a remarkable tensile elongation of 34%. This study reveals a new strategy for designing high-performance structural materials.

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.

How solute atoms control aqueous corrosion of Al-alloys.

Aluminum alloys play an important role in circular metallurgy due to their good recyclability and 95% energy gain when made from scrap. Their low density and high strength translate linearly to lower greenhouse gas emissions in transportation, and their excellent corrosion resistance enhances product longevity. The durability of Al alloys stems from the dense barrier oxide film strongly bonded to the surface, preventing further degradation. However, despite decades of research, the individual elemental reactions and their influence on the nanoscale characteristics of the oxide film during corrosion in multicomponent Al alloys remain unresolved questions. Here, we build up a direct correlation between the near-atomistic picture of the corrosion oxide film and the solute reactivity in the aqueous corrosion of a high-strength Al-Zn-Mg-Cu alloy. We reveal the formation of nanocrystalline Al oxide and highlight the solute partitioning between the oxide and the matrix and segregation to the internal interface. The sharp decrease in partitioning content of Mg in the peak-aged alloy emphasizes the impact of heat treatment on the oxide stability and corrosion kinetics. Through H isotopic labelling with deuterium, we provide direct evidence that the oxide acts as a trap for this element, pointing at the essential role of the Al oxide might act as a kinetic barrier in preventing H embrittlement. Our findings advance the mechanistic understanding of further improving the stability of Al oxide, guiding the design of corrosion-resistant alloys for potential applications.

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.

Strong and ductile high temperature soft magnets through Widmanstätten precipitates.

Fast growth of sustainable energy production requires massive electrification of transport, industry and households, with electrical motors as key components. These need soft magnets with high saturation magnetization, mechanical strength, and thermal stability to operate efficiently and safely. Reconciling these properties in one material is challenging because thermally-stable microstructures for strength increase conflict with magnetic performance. Here, we present a material concept that combines thermal stability, soft magnetic response, and high mechanical strength. The strong and ductile soft ferromagnet is realized as a multicomponent alloy in which precipitates with a large aspect ratio form a Widmanstätten pattern. The material shows excellent magnetic and mechanical properties at high temperatures while the reference alloy with identical composition devoid of precipitates significantly loses its magnetization and strength at identical temperatures. The work provides a new avenue to develop soft magnets for high-temperature applications, enabling efficient use of sustainable electrical energy under harsh operating conditions.

Enhancing corrosion-resistant alloy design through natural language processing and deep learning.

We propose strategies that couple natural language processing with deep learning to enhance machine capability for corrosion-resistant alloy design. First, accuracy of machine learning models for materials datasets is often limited by their inability to incorporate textual data. Manual extraction of numerical parameters from descriptions of alloy processing or experimental methodology inevitably leads to a reduction in information density. To overcome this, we have developed a fully automated natural language processing approach to transform textual data into a form compatible for feeding into a deep neural network. This approach has resulted in a pitting potential prediction accuracy substantially beyond state of the art. Second, we have implemented a deep learning model with a transformed-input feature space, consisting of a set of elemental physical/chemical property-based numerical descriptors of alloys replacing alloy compositions. This helped identification of those descriptors that are most critical toward enhancing their pitting potential. In particular, configurational entropy, atomic packing efficiency, local electronegativity differences, and atomic radii differences proved to be the most critical.

The Fate of Water in Hydrogen-Based Iron Oxide Reduction.

Gas-solid reactions are important for many redox processes that underpin the energy and sustainability transition. The specific case of hydrogen-based iron oxide reduction is the foundation to render the global steel industry fossil-free, an essential target as iron production is the largest single industrial emitter of carbon dioxide. This perception of gas-solid reactions has not only been limited by the availability of state-of-the-art techniques which can delve into the structure and chemistry of reacted solids, but one continues to miss an important reaction partner that defines the thermodynamics and kinetics of gas phase reactions: the gas molecules. In this investigation, cryogenic-atom probe tomography is used to study the quasi in situ evolution of iron oxide in the solid and gas phases of the direct reduction of iron oxide by deuterium gas at 700°C. So far several unknown atomic-scale characteristics are observed, including, D2 accumulation at the reaction interface; formation of a core (wüstite)-shell (iron) structure; inbound diffusion of D through the iron layer and partitioning of D among phases and defects; outbound diffusion of oxygen through the wüstite and/or through the iron to the next free available inner/outer surface; and the internal formation of heavy nano-water droplets at nano-pores.

Atomic motifs govern the decoration of grain boundaries by interstitial solutes.

Grain boundaries, the two-dimensional defects between differently oriented crystals, tend to preferentially attract solutes for segregation. Solute segregation has a significant effect on the mechanical and transport properties of materials. At the atomic level, however, the interplay of structure and composition of grain boundaries remains elusive, especially with respect to light interstitial solutes like B and C. Here, we use Fe alloyed with B and C to exploit the strong interdependence of interface structure and chemistry via charge-density imaging and atom probe tomography methods. Direct imaging and quantifying of light interstitial solutes at grain boundaries provide insight into decoration tendencies governed by atomic motifs. We find that even a change in the inclination of the grain boundary plane with identical misorientation impacts grain boundary composition and atomic arrangement. Thus, it is the smallest structural hierarchical level, the atomic motifs, that controls the most important chemical properties of the grain boundaries. This insight not only closes a missing link between the structure and chemical composition of such defects but also enables the targeted design and passivation of the chemical state of grain boundaries to free them from their role as entry gates for corrosion, hydrogen embrittlement, or mechanical failure.

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.

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.

Reducing Iron Oxide with Ammonia: A Sustainable Path to Green Steel.

Iron making is the biggest single cause of global warming. The reduction of iron ores with carbon generates about 7% of the global carbon dioxide emissions to produce ≈1.85 billion tons of steel per year. This dramatic scenario fuels efforts to re-invent this sector by using renewable and carbon-free reductants and electricity. Here, the authors show how to make sustainable steel by reducing solid iron oxides with hydrogen released from ammonia. Ammonia is an annually 180 million ton traded chemical energy carrier, with established transcontinental logistics and low liquefaction costs. It can be synthesized with green hydrogen and release hydrogen again through the reduction reaction. This advantage connects it with green iron making, for replacing fossil reductants. the authors show that ammonia-based reduction of iron oxide proceeds through an autocatalytic reaction, is kinetically as effective as hydrogen-based direct reduction, yields the same metallization, and can be industrially realized with existing technologies. The produced iron/iron nitride mixture can be subsequently melted in an electric arc furnace (or co-charged into a converter) to adjust the chemical composition to the target steel grades. A novel approach is thus presented to deploying intermittent renewable energy, mediated by green ammonia, for a disruptive technology transition toward sustainable iron making.

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).

Toward the design of ultrahigh-entropy alloys via mining six million texts.

It has long been a norm that researchers extract knowledge from literature to design materials. However, the avalanche of publications makes the norm challenging to follow. Text mining (TM) is efficient in extracting information from corpora. Still, it cannot discover materials not present in the corpora, hindering its broader applications in exploring novel materials, such as high-entropy alloys (HEAs). Here we introduce a concept of "context similarity" for selecting chemical elements for HEAs, based on TM models that analyze the abstracts of 6.4 million papers. The method captures the similarity of chemical elements in the context used by scientists. It overcomes the limitations of TM and identifies the Cantor and Senkov HEAs. We demonstrate its screening capability for six- and seven-component lightweight HEAs by finding nearly 500 promising alloys out of 2.6 million candidates. The method thus brings an approach to the development of ultrahigh-entropy alloys and multicomponent materials.

Ductile 2-GPa steels with hierarchical substructure.

Mechanically strong and ductile load-carrying materials are needed in all sectors, from transportation to lightweight design to safe infrastructure. Yet, a grand challenge is to unify both features in one material. We show that a plain medium-manganese steel can be processed to have a tensile strength >2.2 gigapascals at a uniform elongation >20%. This requires a combination of multiple transversal forging, cryogenic treatment, and tempering steps. A hierarchical microstructure that consists of laminated and twofold topologically aligned martensite with finely dispersed retained austenite simultaneously activates multiple micromechanisms to strengthen and ductilize the material. The dislocation slip in the well-organized martensite and the gradual deformation-stimulated phase transformation synergistically produce the high ductility. Our nanostructure design strategy produces 2 gigapascal-strength and yet ductile steels that have attractive composition and the potential to be produced at large industrial scales.

Accelerating the design of compositionally complex materials via physics-informed artificial intelligence.

The chemical space for designing materials is practically infinite. This makes disruptive progress by traditional physics-based modeling alone challenging. Yet, training data for identifying composition-structure-property relations by artificial intelligence are sparse. We discuss opportunities to discover new chemically complex materials by hybrid methods where physics laws are combined with artificial intelligence.