Fundamentals of Green Steel Production: On the Role of Gas Pressure During Hydrogen Reduction of Iron Ores.

Out of the multitude of researched processing routes for sustainable ironmaking, hydrogen-based direct reduction and hydrogen plasma smelting reduction (HyPSR) are currently the most promising candidates for a successful industrial application. Both processes operate under gaseous atmospheres, which turn the partial and absolute pressure of hydrogen into a relevant process parameter. Here, we present first insights into the influence of total pressure and concentration of hydrogen on the reduction of hematite, focusing on the more pressure-sensitive route (HyPSR). The effect of pressure on the dissociation of H2 molecules into metastable H atoms or H+ ions,- and the overall hydrogen utilization is discussed using a thermodynamic approach. Validation experiments were conducted to testify the practical feasibility of adjusting these parameters. A decrease in the total pressure of the system from 900 mbar to 450 mbar resulted in an improved hydrogen utilization, thus suggesting that a larger population of H atoms can exist in the plasma arcs ignited under 450 mbar. An increase in the hydrogen concentration to 20 vol.% lead to undesired evaporation, likely because of a parallel increase in plasma temperature. Possibilities and challenges for exploiting these pressure-related phenomena for the industrial production of green steel are outlined and discussed. Supplementary Information: The online version contains supplementary material available at 10.1007/s11837-023-05829-z.

Intercritical annealing to achieve a positive strain-rate sensitivity of mechanical properties and suppression of macroscopic plastic instabilities in multi-phase medium-Mn steels.

This study investigates the high strain-rate tensile properties of a cold-rolled medium-Mn steel (Fe-12Mn-3Al-0.05C % in mass fraction) designed to have a multi-phase microstructure and positive strain-rate sensitivity. At the intercritical annealing temperature of 585 °C, increasing the annealing time from 0.5 h to 8 h increased the phase volume fraction of ultrafine-grained (UFG) austenite from 2% to 35% by reversion. The remainder of the microstructure was composed of UFG ferrite and recovered α'-martensite (the latter resembles the cold-rolled state). Servo hydraulic tension testing and Kolsky-bar tension testing were used to measure the tensile properties from quasi-static strain rates to dynamic strain rates ( ε ˙ = 10 - 4 s - 1 to ε ˙ = 10 3 s - 1 ). The strain-rate sensitivities of the yield strength (YS) and ultimate tensile strength (UTS) were positive for both annealing times. Tensile properties and all non-contact imaging modalities (infrared imaging and digital image correlation) indicated an advantageous suppression of Lüders bands and Portevin Le Chatelier (PLC) bands (a critical challenge in multi-phase medium-Mn steel design) due to the unique combination of microstructural constituents and overall composition. Fracture surfaces of specimens annealed for 0.5 h showed some instances of localized cleavage fracture (approximately 30 µm wide areas and lath-like ridges). Specimens annealed for 8 h maintained a greater product of strength and elongation by at least 2.5 GPa % (on average for each strain rate). The relevant processing-structure-property relationships are discussed in the context of recommendations for design strategies concerning multi-phase steels such that homogeneous deformation behavior and positive strain-rate sensitivities can be achieved.

Experimental and numerical study of mechanical properties of multi-phase medium-Mn TWIP-TRIP steel: influences of strain rate and phase constituents.

In the current work we investigate the room temperature tensile properties of a medium-Mn twinning- and transformation-induced plasticity (TWIP-TRIP) steel from quasi-static to low-dynamic strain rates ( ε ˙ = 10 - 4 s - 1 to ε ˙ = 10 2 s - 1 ). The multi-phase microstructure consists of coarse-grained recovered α' -martensite (inherited from the cold-rolled microstructure), multiple morphologies of ultrafine-grained (UFG) austenite (equiaxed, rod-like and plate-like), and equiaxed UFG ferrite. The multi-phase material exhibits a positive strain-rate sensitivity for yield and ultimate tensile strengths. Thermal imaging and digital image correlation allow for in situ measurements of temperature and local strain in the gauge length during tensile testing, but Lüders bands and Portevin Le Chatelier bands are not observed. A finite-element model uses empirical evidence from electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM), plus constitutive equations to dissect the microstructural influences of grain size, dislocation density and TWIP-TRIP driving forces on tensile properties. Calibration of tensile properties not only captures the strain rate sensitivity of the multi-phase TWIP-TRIP steel, but also provides opportunity for a complete parametric analysis by changing one variable at a time (phase fraction, grain size, strain-induced twin fraction and strain-induced ε-martensite fraction). An equivalent set of high-rate mechanical properties can be matched by changing either the austenite phase fraction or the ratio of twinning vs. transformation to ε-martensite. This experimental-computational framework enables the prediction of mechanical properties in multi-phase steels beyond the experimental regime by tuning variables that are relevant to the alloy design process.

Complex Nanotwin Substructure of an Asymmetric Σ9 Tilt Grain Boundary in a Silicon Polycrystal.

Grain boundaries in materials have substantial influences on device properties, for instance on mechanical stability or electronic minority carrier lifetime in multicrystalline silicon solar cells. This applies especially to asymmetric, less ordered or faceted interface portions. Here, we present the complex atomic interface structure of an asymmetric Σ9 tilt grain boundary in silicon, observed by high resolution scanning transmission electron microscopy (HR-STEM) and explained by atomistic modeling and computer simulation. Structural optimization of interface models for the asymmetric Σ9 and related symmetrical Σ9 and Σ3 tilt grain boundaries, by means of molecular-statics simulations with empirical silicon potentials in combination with first-principles calculations, results in a faceted asymmetric interface structure, whose grain-boundary energy is so low that it is likely to exist. The simulated local atomic structures match the observed HR-STEM images very well.

Atomic-scale quantification of grain boundary segregation in nanocrystalline material.

Grain boundary segregation leads to nanoscale chemical variations that can alter a material's performance by orders of magnitude (e.g., embrittlement). To understand this phenomenon, a large number of grain boundaries must be characterized in terms of both their five crystallographic interface parameters and their atomic-scale chemical composition. We demonstrate how this can be achieved using an approach that combines the accuracy of structural characterization in transmission electron microscopy with the 3D chemical sensitivity of atom probe tomography. We find a linear trend between carbon segregation and the misorientation angle ω for low-angle grain boundaries in ferrite, which indicates that ω is the most influential crystallographic parameter in this regime. However, there are significant deviations from this linear trend indicating an additional strong influence of other crystallographic parameters (grain boundary plane, rotation axis). For high-angle grain boundaries, no general trend between carbon excess and ω is observed; i.e., the grain boundary plane and rotation axis have an even higher influence on the segregation behavior in this regime. Slight deviations from special grain boundary configurations are shown to lead to unexpectedly high levels of segregation.

A sustainable ultra-high strength Fe18Mn3Ti maraging steel through controlled solute segregation and α-Mn nanoprecipitation.

The enormous magnitude of 2 billion tons of alloys produced per year demands a change in design philosophy to make materials environmentally, economically, and socially more sustainable. This disqualifies the use of critical elements that are rare or have questionable origin. Amongst the major alloy strengthening mechanisms, a high-dispersion of second-phase precipitates with sizes in the nanometre range is particularly effective for achieving ultra-high strength. Here, we propose an alternative segregation-based strategy for sustainable steels, free of critical elements, which are rendered ultrastrong by second-phase nano-precipitation. We increase the Mn-content in a supersaturated, metastable Fe-Mn solid solution to trigger compositional fluctuations and nano-segregation in the bulk. These fluctuations act as precursors for the nucleation of an unexpected α-Mn phase, which impedes dislocation motion, thus enabling precipitation strengthening. Our steel outperforms most common commercial alloys, yet it is free of critical elements, making it a new platform for sustainable alloy design.

The hidden structure dependence of the chemical life of dislocations.

Dislocations are one-dimensional defects in crystals, enabling their deformation, mechanical response, and transport properties. Less well known is their influence on material chemistry. The severe lattice distortion at these defects drives solute segregation to them, resulting in strong, localized spatial variations in chemistry that determine microstructure and material behavior. Recent advances in atomic-scale characterization methods have made it possible to quantitatively resolve defect types and segregation chemistry. As shown here for a Pt-Au model alloy, we observe a wide range of defect-specific solute (Au) decoration patterns of much greater variety and complexity than expected from the Cottrell cloud picture. The solute decoration of the dislocations can be up to half an order of magnitude higher than expected from classical theory, and the differences are determined by their structure, mutual alignment, and distortion field. This opens up pathways to use dislocations for the compositional and structural nanoscale design of advanced materials.

Identification of epsilon martensite in a Fe-based shape memory alloy by means of EBSD.

Ferrous shape memory alloys (SMAs) are often thought to become a new, important group of SMAs. The shape memory effect in these alloys is based on the reversible, stress-induced martensitic transformation of austenite to epsilon martensite. The identification and quantification of epsilon martensite is crucial when evaluating the shape memory behaviour of this material. Previous work displayed that promising results were obtained when studying the evolution of the amount of epsilon martensite after different processing steps with Electron BackScatter Diffraction (EBSD). The present work will discuss in detail, on the one hand, the challenges and opportunities arising during the identification of epsilon martensite by means of EBSD and, on the other hand, the possible interpretations that might be given to these findings. It will be illustrated that although the specific nature of the austenite to epsilon martensite transformation can still cause some points of discussion, EBSD has a high potential for identifying epsilon martensite.

Effect of aspect ratio on transverse diffusive broadening: a lattice Boltzmann study.

We study scaling laws characterizing the interdiffusive zone between two miscible fluids flowing side by side in a Y-shape laminar micromixer using the lattice Boltzmann method. The lattice Boltzmann method solves the coupled three-dimensional (3D) hydrodynamics and mass transfer equations and incorporates intrinsic features of 3D flows related to this problem. We observe the different power-law regimes occurring at the center of the channel and close to the top/bottom wall. The extent of the interdiffusive zone scales as the square root of the axial distance at the center of the channel. At the top/bottom wall, we find an exponent 1/3 at early stages of mixing as observed in the experiments of Ismagilov [Appl. Phys. Lett. 76, 2376 (2000)]. At a larger distance from the entrance, the scaling exponent close to the walls changes to 1/2 [J.-B. Salmon and A. Adjari, J. Appl. Phys. 101, 074902 (2007)]. Here, we focus on the effect of the finite aspect ratio on diffusive broadening. Interestingly, we find the same scaling laws regardless of the channel's aspect ratio. However, the point at which the exponent 1/3 characterizing the broadening at the top/bottom wall reverts to the normal diffusive behavior downstream strongly depends on the aspect ratio. We propose an interpretation of this observation in terms of the shear rate at the side walls. A criterion for the range of aspect ratios with non-negligible effect on diffusive broadening is also provided.

Influence of microstructure on deformation anisotropy of mineralized cuticle from the lobster Homarus americanus.

The exoskeleton of the American lobster Homarus americanus is a hierarchically organized nano-composite material consisting of organic chitin-protein fibers associated with inorganic calcium carbonate. The presence of a well-developed and periodically arranged pore canal system leads to a honeycomb-like structure. The concomitant presence of the twisted plywood arrangement of the mineralized chitin-protein fibers alters the elastic properties, the deformation behavior, and fracture behavior compared to classical honeycomb structures. By performing compression tests in various directions of the cuticle we examined the anisotropic elastic-plastic deformation and fracture behavior of mineralized parts of the exoskeleton. By applying digital image correlation during compression testing, the evolution of the elastic-plastic deformation at the microscopic scale was observed with high resolution and simultaneously global stress and strain data were acquired. Shear tests were performed in order to determine the fracture energy for different shear planes and directions. The investigation of the microstructure after plastic deformation revealed the underlying deformation mechanisms of lobster endocuticle from the claws under different loading conditions. For evaluating the effect of hydration the samples were tested both in the dry and in the wet state.

Three-dimensional EBSD study on the relationship between triple junctions and columnar grains in electrodeposited Co-Ni films.

Electrodeposited nanocrystalline materials are expected to have a homogeneous grain size and a narrow grain size distribution. In Co-Ni electrodeposited films, however, under certain conditions an undesired columnar grain structure is formed. Fully automated three-dimensional (3D) orientation microscopy, consisting of a combination of precise material removal by focussed ion beam and subsequent electron backscatter diffraction (EBSD) analysis, was applied to fully characterize the grain boundaries of these columnar grains in order to gain further understanding on their formation mechanisms. Two-dimensional orientation microscopy on these films indicated that the development of columnar grains could be related to the formation of low-energy triple junctions. 3D EBSD allowed us to verify this suggestion and to determine the boundary planes of these triples. The triplets are formed by grain boundaries of different quality, a coherent twin on the {1011} plane, an incoherent twin and a large-angle grain boundary. These three boundaries are related to each other by a rotation about the <1120> direction. A second particularity of the columnar grains is the occurrence of characteristic orientation gradients created by regular defects in the grain. Transmission electron microscopy was applied to investigate the character of the defects. For this purpose, a sample was prepared with the focussed ion beam from the last slice of the 3D EBSD investigation. From the TEM and 3D EBSD observations, a growth mechanism of the columnar grains is proposed.

Profile blunting and flow blockage in a yield-stress fluid: a molecular dynamics study.

The flow of a simple glass forming system (a 80:20 binary Lennard-Jones mixture) through a planar channel is studied via molecular dynamics simulations. The flow is driven by an external body force similar to gravity. Previous studies show that the model exhibits both a static [F. Varnik, J. Chem. Phys. 120, 2788 (2004)] and a dynamic [F. Varnik and O. Henrich, Phys. Rev. B 73, 174209 (2006)] yield stress in the glassy phase. These observations are corroborated by the present work, where we investigate how the presence of a yield stress may affect the system behavior in a Poiseuille-type flow geometry. In particular, we observe a blunted velocity profile across the channel: A relatively wide region in the channel center flows with a constant velocity (zero shear rate) followed by a nonlinear change of the shear rate as the walls are approached. The observed velocity gradients are compared to those obtained from the knowledge of the shear stress across the channel and the flow curves (stress versus shear rate), the latter being determined in our previous simulations of homogeneous shear flow. Furthermore, using the value of the (dynamic) yield stress known from previous simulations, we estimate the threshold body force for a complete arrest of the flow. Indeed, a blockage is observed as the imposed force falls below this threshold value. Small but finite shear rates are observed at stresses above the dynamic but below the static yield stress. We discuss the possible role of the stick-slip-like motion for this observation.

Prototyping artificial jaws for the robotic dental testing simulator.

This paper presents a robot periphery prototyped for the six-degrees-of-freedom robotic dental testing simulator, simulating the wear of materials on dental components, such as individual teeth, crowns, bridges, or a full set of teeth. The robot periphery consists of the artificial jaws and compliance module. The jaws have been reverse engineered and represent a human-like mandible and maxilla with artificial teeth. Each clinically fabricated tooth consists of a crown and glass ceramic roots which are connected using resin cement. Normal clinical occlusion of the artificial jaws assembly was emulated by a dental articulator based on 'Andrew's six keys to occlusion'. The radii of the von Spee curve, the Monson curve, and the Wilson curve were also measured as important jaw characteristic indicators to aid normal occlusion. A compliance module had to be built between the lower jaw and the robot platform to sustain the fluctuating forces that occur during normal chewing in the occlusal contact areas, where these high bite forces are major causes of dental component failure. A strain gauge force transducer has been integrated into the machined lower jaw, underneath the second molars, to measure axial biting forces applied to the posterior teeth. The experiments conducted have shown that the sensor is able to sense small changes in the compression force satisfactorily, when applied perpendicular to the occlusal surfaces of the teeth.

Phase nucleation through confined spinodal fluctuations at crystal defects evidenced in Fe-Mn alloys.

Analysis and design of materials and fluids requires understanding of the fundamental relationships between structure, composition, and properties. Dislocations and grain boundaries influence microstructure evolution through the enhancement of diffusion and by facilitating heterogeneous nucleation, where atoms must overcome a potential barrier to enable the early stage of formation of a phase. Adsorption and spinodal decomposition are known precursor states to nucleation and phase transition; however, nucleation remains the less well-understood step in the complete thermodynamic sequence that shapes a microstructure. Here, we report near-atomic-scale observations of a phase transition mechanism that consists in solute adsorption to crystalline defects followed by linear and planar spinodal fluctuations in an Fe-Mn model alloy. These fluctuations provide a pathway for austenite nucleation due to the higher driving force for phase transition in the solute-rich regions. Our observations are supported by thermodynamic calculations, which predict the possibility of spinodal decomposition due to magnetic ordering.

The influence of sterilization processes on the micromechanical properties of carbon fiber-reinforced PEEK composites for bone implant applications.

The effect of sterilization on the structural integrity of the thermoplastic matrix composite polyetheretherketone (PEEK) reinforced with carbon fibers (CF) is investigated by nanoindentation and nanoscratch tests. The use of the material as a medical implant grade requires a detailed understanding of the micromechanical properties which primarily define its in vivo behavior. Sterilization is a mandatory process for such materials used in medical applications like bone implants. The steam and gamma radiation sterilization processes employed in this study are at sufficient levels to affect the micromechanical properties of some polymer materials, particularly in the interphase region between the polymer matrix and the reinforcing fibers. Nanoindentation and nanoscratch tests are used in this work to reveal local gradients in the hardness and the elastic properties of the interphase regions. Both methods help to explore microscopic changes in the hardness, reduced stiffness and scratch resistance in the interphase region and in the bulk polymer matrix due to the different sterilization processes employed. The results reveal that neither steam nor gamma radiation sterilization entails significant changes of the reduced elastic modulus, hardness or coefficient of friction in the bulk polymer matrix. However, minor material changes of the PEEK matrix were observed in the interphase region. Of the two sterilization methods used, the steam treatment has a more significant influence on these small changes in this region and appears to increase slightly the thickness of the interphase zone.

Preferred crystallographic texture of alpha-chitin as a microscopic and macroscopic design principle of the exoskeleton of the lobster Homarus americanus.

The crystallographic texture of the crystalline alpha-chitin matrix in the biological composite material forming the exoskeleton of the lobster Homarus americanus has been determined using synchrotron X-ray pole figure measurements and the calculation of orientation distribution functions. The study has two objectives. The first one is to elucidate crystallographic building principles via the preferred synthesis of certain orientations in crystalline organic tissue. The second one is to study whether a general global design principle exists for the exoskeleton which uses preferred textures relative to the local coordinate system throughout the lobster cuticle. The first point, hence, pursues the question of the extent to which and why alpha-chitin reveals preferred textures in the lobster cuticle. The second point addresses the question of why and whether such preferred textures (and the resulting anisotropy) exist everywhere in the exoskeleton. Concerning the first aspect, a strong preference of a fiber texture of the orthorhombic alpha-chitin is observed which is characterized by a 020 crystal axis normal to the exoskeleton surface for the chitin matrix. The second question is tackled by studying samples from different parts of the carapace. While the first aspect takes a microscopic perspective at the basic structure of the biological composite, the second point aims at building a bridge between an understanding of the microstructure and the macroscopic nature of a larger biological construction. We observe that the texture is everywhere in the carapace optimized in such a way that the same crystallographic axis of the chitin matrix is parallel to the normal to the local tangent plane of the carapace. Notable differences in the texture are observed between hard mineralized parts on the one hand and soft membranous parts on the other. The study shows that the complex hierarchical microstructure of the arthropod cuticle can be well described by surprisingly simple crystallographic textures.

Comparison of the quantitative analysis performance between pulsed voltage atom probe and pulsed laser atom probe.

The difference in quantitative analysis performance between the voltage-mode and laser-mode of a local electrode atom probe (LEAP3000X HR) was investigated using a Fe-Cu binary model alloy. Solute copper atoms in ferritic iron preferentially field evaporate because of their significantly lower evaporation field than the matrix iron, and thus, the apparent concentration of solute copper tends to be lower than the actual concentration. However, in voltage-mode, the apparent concentration was higher than the actual concentration at 40K or less due to a detection loss of matrix iron, and the concentration decreased with increasing specimen temperature due to the preferential evaporation of solute copper. On the other hand, in laser-mode, the apparent concentration never exceeded the actual concentration, even at lower temperatures (20K), and this mode showed better quantitative performance over a wide range of specimen temperatures. These results indicate that the pulsed laser atom probe prevents both detection loss and preferential evaporation under a wide range of measurement conditions.

Stiff, light, strong and ductile: nano-structured High Modulus Steel.

Structural material development for lightweight applications aims at improving the key parameters strength, stiffness and ductility at low density, but these properties are typically mutually exclusive. Here we present how we overcome this trade-off with a new class of nano-structured steel - TiB2 composites synthesised in-situ via bulk metallurgical spray-forming. Owing to the nano-sized dispersion of the TiB2 particles of extreme stiffness and low density - obtained by the in-situ formation with rapid solidification kinetics - the new material has the mechanical performance of advanced high strength steels, and a 25% higher stiffness/density ratio than any of the currently used high strength steels, aluminium, magnesium and titanium alloys. This renders this High Modulus Steel the first density-reduced, high stiffness, high strength and yet ductile material which can be produced on an industrial scale. Also ideally suited for 3D printing technology, this material addresses all key requirements for high performance and cost effective lightweight design.

Complexion-mediated martensitic phase transformation in Titanium.

The most efficient way to tune microstructures and mechanical properties of metallic alloys lies in designing and using athermal phase transformations. Examples are shape memory alloys and high strength steels, which together stand for 1,500 million tons annual production. In these materials, martensite formation and mechanical twinning are tuned via composition adjustment for realizing complex microstructures and beneficial mechanical properties. Here we report a new phase transformation that has the potential to widen the application window of Ti alloys, the most important structural material in aerospace design, by nanostructuring them via complexion-mediated transformation. This is a reversible martensitic transformation mechanism that leads to a final nanolaminate structure of α″ (orthorhombic) martensite bounded with planar complexions of athermal ω (a-ω, hexagonal). Both phases are crystallographically related to the parent ß (BCC) matrix. As expected from a planar complexion, the a-ω is stable only at the hetero-interface.

A rare-earth free magnesium alloy with improved intrinsic ductility.

Metals are the backbone of manufacturing owing to their strength and formability. Compared to polymers they have high mass density. There is, however, one exception: magnesium. It has a density of only 1.7 g/cm3, making it the lightest structural material, 4.5 times lighter than steels, 1.7 times lighter than aluminum, and even slightly lighter than carbon fibers. Yet, the widespread use of magnesium is hampered by its intrinsic brittleness. While other metallic alloys have multiple dislocation slip systems, enabling their well-known ductility, the hexagonal lattice of magnesium offers insufficient modes of deformation, rendering it intrinsically brittle. We have developed a quantum-mechanically derived treasure map which screens solid solution combinations with electronic bonding, structure and volume descriptors for similarity to the ductile magnesium-rare earth alloys. Using this insight we synthesized a surprisingly simple, compositionally lean, low-cost and industry-compatible new alloy which is over 4 times more ductile and 40% stronger than pure magnesium. The alloy contains 1 wt.% aluminum and 0.1 wt.% calcium, two inexpensive elements which are compatible with downstream recycling constraints.