Montanuniversität Leoben

High-entropy alloys are equiatomic, multi-element systems that can crystallize as a single phase, despite containing multiple elements with different crystal structures. A rationale for this is that the configurational entropy contribution to the total free energy in alloys with five or more major elements may stabilize the solid-solution state relative to multiphase microstructures. We examined a five-element high-entropy alloy, CrMnFeCoNi, which forms a single-phase face-centered cubic solid solution, and found it to have exceptional damage tolerance with tensile strengths above 1 GPa and fracture toughness values exceeding 200 MPa·m(1/2). Furthermore, its mechanical properties actually improve at cryogenic temperatures; we attribute this to a transition from planar-slip dislocation activity at room temperature to deformation by mechanical nanotwinning with decreasing temperature, which results in continuous steady strain hardening.

Natural materials such as bone, tooth, and nacre are nanocomposites of proteins and minerals with superior strength. Why is the nanometer scale so important to such materials? Can we learn from this to produce superior nanomaterials in the laboratory? These questions motivate the present study where we show that the nanocomposites in nature exhibit a generic mechanical structure in which the nanometer size of mineral particles is selected to ensure optimum strength and maximum tolerance of flaws (robustness). We further show that the widely used engineering concept of stress concentration at flaws is no longer valid for nanomaterial design.

High-entropy alloys are an intriguing new class of metallic materials that derive their properties from being multi-element systems that can crystallize as a single phase, despite containing high concentrations of five or more elements with different crystal structures. Here we examine an equiatomic medium-entropy alloy containing only three elements, CrCoNi, as a single-phase face-centred cubic solid solution, which displays strength-toughness properties that exceed those of all high-entropy alloys and most multi-phase alloys. At room temperature, the alloy shows tensile strengths of almost 1 GPa, failure strains of ∼70% and KJIc fracture-toughness values above 200 MPa m(1/2); at cryogenic temperatures strength, ductility and toughness of the CrCoNi alloy improve to strength levels above 1.3 GPa, failure strains up to 90% and KJIc values of 275 MPa m(1/2). Such properties appear to result from continuous steady strain hardening, which acts to suppress plastic instability, resulting from pronounced dislocation activity and deformation-induced nano-twinning.

An equiatomic CoCrFeMnNi high-entropy alloy (HEA), produced by arc melting and drop casting, was subjected to severe plastic deformation (SPD) using high-pressure torsion. This process induced substantial grain refinement in the coarse-grained casting leading to a grain size of approximately 50 nm. As a result, strength increased significantly to 1950 MPa, and hardness to ∼520 HV. Analyses using transmission electron microscopy (TEM) and 3-dimensional atom probe tomography (3D-APT) showed that, after SPD, the alloy remained a true single-phase solid solution down to the atomic scale. Subsequent investigations characterized the evolution of mechanical properties and microstructure of this nanocrystalline HEA upon annealing. Isochronal (for 1 h) and isothermal heat treatments were performed followed by microhardness and tensile tests. The isochronal anneals led to a marked hardness increase with a maximum hardness of ∼630 HV at about 450 °C before softening set in at higher temperatures. The isothermal anneals, performed at this peak hardness temperature, revealed an additional hardness rise to a maximum of about 910 HV after 100 h. To clarify this unexpected annealing response, comprehensive microstructural analyses were performed using TEM and 3D-APT. New nano-scale phases were observed to form in the originally single-phase HEA. After times as short as 5 min at 450 °C, a NiMn phase and Cr-rich phase formed. With increasing annealing time, their volume fractions increased and a third phase, FeCo, also formed. It appears that the surfeit of grain boundaries in the nanocrystalline HEA offer many fast diffusion pathways and nucleation sites to facilitate this phase decomposition. The hardness increase, especially for the longer annealing times, can be attributed to these nano-scaled phases embedded in the HEA matrix. The present results give new valuable insights into the phase stability of single-phase high-entropy alloys as well as the mechanisms controlling the mechanical properties of nanostructured multiphase composites.

Abstract After almost three decades of intensive fundamental research and development activities, intermetallic titanium aluminides based on the ordered γ‐TiAl phase have found applications in automotive and aircraft engine industry. The advantages of this class of innovative high‐temperature materials are their low density and their good strength and creep properties up to 750 °C as well as their good oxidation and burn resistance. Advanced TiAl alloys are complex multi‐phase alloys which can be processed by ingot or powder metallurgy as well as precision casting methods. Each process leads to specific microstructures which can be altered and optimized by thermo‐mechanical processing and/or subsequent heat treatments. The background of these heat treatments is at least twofold, i.e., concurrent increase of ductility at room temperature and creep strength at elevated temperature. This review gives a general survey of engineering γ‐TiAl based alloys, but concentrates on β‐solidifying γ‐TiAl based alloys which show excellent hot‐workability and balanced mechanical properties when subjected to adapted heat treatments. The content of this paper comprises alloy design strategies, progress in processing, evolution of microstructure, mechanical properties as well as application‐oriented aspects, but also shows how sophisticated ex situ and in situ methods can be employed to establish phase diagrams and to investigate the evolution of the micro‐ and nanostructure during hot‐working and subsequent heat treatments.

Raman spectroscopy uses the inelastic scattering of electromagnetic radiation by molecules. Monochromatic light of a laser interacts with phonons, the vibrational modes in the crystal lattice. The energy of the scattered light is shifted by the scattering. The shifts in energy yield the Raman spectrum that is specific for each mineral because the phonons are specific for each mineral.

Abstract Although many companies investigate sustainability management and publish sustainability reports, their main focus in this endeavour remains unclear. Often, it seems that sustainability issues are pursued more coincidentally than with a clear strategy. On one hand, research is done for the identification and determination of distinct aspects concerning economic, ecological and social dimensions of sustainability. Guidelines to develop a sustainability report are popular examples of this. On the other hand, scientific effort is recognizable regarding the establishment of specific sustainability strategies, e.g. strategies that focus on internal/external orientation of sustainability commitment. Strategies should be designed to work to improve performance in terms of the issues identified, but in many cases the link between aspects and sustainability strategies is missing in practice. This paper aims to narrow this gap by developing specific aspect profiles for sustainability strategies. Relating to the characteristics of various sustainability strategies, key sustainability issues are determined, which have to be implemented in order to reach defined sustainability goals efficiently. The paper helps companies that already commit to sustainability to verify whether they are consistent in the implementation of a distinct sustainability strategy. Copyright © 2010 John Wiley & Sons, Ltd and ERP Environment.

The issue of stress in thin films and functional coatings is a persistent problem in materials science and technology that has congregated many efforts, both from experimental and fundamental points of view, to get a better understanding on how to deal with, how to tailor, and how to manage stress in many areas of applications. With the miniaturization of device components, the quest for increasingly complex film architectures and multiphase systems and the continuous demands for enhanced performance, there is a need toward the reliable assessment of stress on a submicron scale from spatially resolved techniques. Also, the stress evolution during film and coating synthesis using physical vapor deposition (PVD), chemical vapor deposition, plasma enhanced chemical vapor deposition (PECVD), and related processes is the result of many interrelated factors and competing stress sources so that the task to provide a unified picture and a comprehensive model from the vast amount of stress data remains very challenging. This article summarizes the recent advances, challenges, and prospects of both fundamental and applied aspects of stress in thin films and engineering coatings and systems, based on recent achievements presented during the 2016 Stress Workshop entitled “Stress Evolution in Thin Films and Coatings: from Fundamental Understanding to Control.” Evaluation methods, implying wafer curvature, x-ray diffraction, or focused ion beam removal techniques, are reviewed. Selected examples of stress evolution in elemental and alloyed systems, graded layers, and multilayer-stacks as well as amorphous films deposited using a variety of PVD and PECVD techniques are highlighted. Based on mechanisms uncovered by in situ and real-time diagnostics, a kinetic model is outlined that is capable of reproducing the dependence of intrinsic (growth) stress on the grain size, growth rate, and deposited energy. The problems and solutions related to stress in the context of optical coatings, inorganic coatings on plastic substrates, and tribological coatings for aerospace applications are critically examined. This review also suggests strategies to mitigate excessive stress levels from novel coating synthesis perspectives to microstructural design approaches, including the ability to empower crack-based fabrication processes, pathways leading to stress relaxation and compensation, as well as management of the film and coating growth conditions with respect to energetic ion bombardment. Future opportunities and challenges for stress engineering and stress modeling are considered and outlined.

Additive manufacturing (AM), also known as 3D printing or rapid prototyping, is gaining increasing attention due to its ability to produce parts with added functionality and increased complexities in geometrical design, on top of the fact that it is theoretically possible to produce any shape without limitations. However, most of the research on additive manufacturing techniques are focused on the development of materials/process parameters/products design with different additive manufacturing processes such as selective laser melting, electron beam melting, or binder jetting. However, we do not have any guidelines that discuss the selection of the most suitable additive manufacturing process, depending on the material to be processed, the complexity of the parts to be produced, or the design considerations. Considering the very fact that no reports deal with this process selection, the present manuscript aims to discuss the different selection criteria that are to be considered, in order to select the best AM process (binder jetting/selective laser melting/electron beam melting) for fabricating a specific component with a defined set of material properties.

Additive manufacturing (AM) is the fabrication of real three-dimensional objects from metals, ceramics, or plastics by adding material, usually as layers. There are several variants of AM; among them material extrusion (ME) is one of the most versatile and widely used. In MEAM, molten or viscous materials are pushed through an orifice and are selectively deposited as strands to form stacked layers and subsequently a three-dimensional object. The commonly used materials for MEAM are thermoplastic polymers and particulate composites; however, recently innovative formulations of highly-filled polymers (HP) with metals or ceramics have also been made available. MEAM with HP is an indirect process, which uses sacrificial polymeric binders to shape metallic and ceramic components. After removing the binder, the powder particles are fused together in a conventional sintering step. In this review the different types of MEAM techniques and relevant industrial approaches for the fabrication of metallic and ceramic components are described. The composition of certain HP binder systems and powders are presented; the methods of compounding and filament making HP are explained; the stages of shaping, debinding, and sintering are discussed; and finally a comparison of the parts produced via MEAM-HP with those produced via other manufacturing techniques is presented.

Two new sets of optical data, i.e., values for the real (ε1) and imaginary (ε2) parts of the complex dielectric constant as well as the energy loss function (ELF) (Im{−1∕ε}), are presented for 16 elemental metals (Ti, V, Fe, Co, Ni, Cu, Zn, Mo, Pd, Ag, Ta, W, Pt, Au, Pb, and Bi) and 1 semimetal (Te) and are compared to available data in the literature. One data set is obtained from density functional theory (DFT) calculations and gives ε from the infrared to the soft x-ray range of wavelengths. The other set of optical constants, derived from experimental reflection electron energy-loss spectroscopy (REELS) spectra, provides reliable optical data from the near-ultraviolet to the soft x-ray regime. The two data sets exhibit very good mutual consistency and also, overall, compare well with optical data found in the literature, most of which were determined several decades ago. However, exceptions to this rule are also found in some instances, some of them systematic, where the DFT and REELS mutually agree significantly better than with literature data. The accuracy of the experimental data is estimated to be better than 10% for the ELF and ε2 as well as for ε1 for energies above 10eV. For energies below 10eV, the uncertainty in ε1 in the experimental data may exceed 100%, which is a consequence of the fact that energy-loss measurements mainly sample the absorptive part of the dielectric constant. Electron inelastic-scattering data, i.e., the differential inverse inelastic mean free path (IMFP) as well the differential and total surface excitation probabilities are derived from the experimental data. Furthermore, the total electron IMFP is calculated from the determined optical constants by employing linear response theory for energies between 200 and 3000eV. In the latter case, the consistency between the DFT and the REELS data is excellent (better than 5% for all considered elements over the entire energy range considered) and a very good agreement with earlier results is also obtained, except for a few cases for which the earlier optical data deviate significantly from those obtained here.

The electronic band structure of graphene in the presence of spin-orbit coupling and transverse electric field is investigated from first principles using the linearized augmented plane-wave method. The spin-orbit coupling opens a gap of $24\text{ }\ensuremath{\mu}\text{eV}$ (0.28 K) at the $K({K}^{\ensuremath{'}})$ point. It is shown that the previously accepted value of $1\text{ }\ensuremath{\mu}\text{eV}$, coming from the $\ensuremath{\sigma}\text{\ensuremath{-}}\ensuremath{\pi}$ mixing, is incorrect due to the neglect of $d$ and higher orbitals whose contribution is dominant due to symmetry reasons. The transverse electric field induces an additional (extrinsic) Bychkov-Rashba-type splitting of $10\text{ }\ensuremath{\mu}\text{eV}$ (0.11 K) per V/nm, coming from the $\ensuremath{\sigma}\text{\ensuremath{-}}\ensuremath{\pi}$ mixing. A ``miniripple'' configuration with every other atom shifted out of the sheet by less than 1% differs little from the intrinsic case.

This review focuses on the reduction of iron oxides using hydrogen as a reducing agent. Due to increasing requirements from environmental issues, a change of process concepts in the iron and steel industry is necessary within the next few years. Currently, crude steel production is mainly based on fossil fuels, and emitting of the climate‐relevant gas carbon dioxide is integral. One opportunity to avoid or reduce greenhouse gas emissions is substituting hydrogen for carbon as an energy source and reducing agent. Hydrogen, produced via renewable energies, allows carbon‐free reduction and avoids forming harmful greenhouse gases during the reduction process. The thermodynamic and kinetic behaviors of reduction with hydrogen are summarized and discussed in this review. The effects of influencing parameters, such as temperature, type of iron oxide, grain size, etc. are shown and compared with the reduction behavior of iron oxides with carbon monoxide. Different methods to describe the kinetics of the reduction progress and the role of the apparent activation energy are shown and proofed regarding their plausibility.

The phenomenon of age hardening could be evidenced in thin film applications. A model system, Ti1−xAlxN was chosen as such coatings are known for their excellent wear resistance enabling improved machining processes like high-speed and dry cutting. Here, we show unambiguously that metastable Ti1−xAlxN coatings initially undergo spinodal decomposition into coherent cubic-phase nanometer-size domains, causing an increase in hardness at elevated temperatures. These intermediate metastable domains transform into their stable phases TiN and AlN during further thermal treatment. Activation energies for the processes indicate defect-assisted segregation of Ti and Al. The findings are corroborated by ab initio calculations. A long-standing discussion on the thermal stability of this important class of ceramics is thus resolved.

There are several facets of aluminum when it comes to sustainability. While it helps to save fuel due to its low density, producing it from ores is very energy-intensive. Recycling it shifts the balance towards higher sustainability, because the energy needed to melt aluminum from scrap is only about 5% of that consumed in ore reduction. The amount of aluminum available for recycling is estimated to double by 2050. This offers an opportunity to bring the metallurgical sector closer to a circular economy. A challenge is that large amounts of scrap are post-consumer scrap, containing high levels of elemental contamination. This has to be taken into account in more sustainable alloy design strategies. A “green aluminum” trend has already triggered a new trading platform for low-carbon aluminum at the London Metal Exchange (2020). The trend may lead to limits on the use of less-sustainable materials in future products. The shift from primary synthesis (ore reduction) to secondary synthesis (scrap melting) requires to gain better understanding of how multiple scrap-related contaminant elements act on aluminum alloys and how future alloys can be designed upfront to become scrap-compatible and composition-tolerant. The paper therefore discusses the influence of scrap-related impurities on the thermodynamics and kinetics of precipitation reactions and their mechanical and electrochemical effects; impurity effects on precipitation-free zones around grain boundaries; their effects on casting microstructures; and the possibilities presented by adjusting processing parameters and the associated mechanical, functional and chemical properties. The objective is to foster the design and production of aluminum alloys with the highest possible scrap fractions, using even low-quality scrap and scrap types which match only a few target alloys when recycled.

Severe plastic deformation (SPD) is effective in producing bulk ultrafine-grained and nanostructured materials with large densities of lattice defects. This field, also known as NanoSPD, experienced a significant progress within the past two decades. Beside classic SPD methods such as high-pressure torsion, equal-channel angular pressing, accumulative roll-bonding, twist extrusion, and multi-directional forging, various continuous techniques were introduced to produce upscaled samples. Moreover, numerous alloys, glasses, semiconductors, ceramics, polymers, and their composites were processed. The SPD methods were used to synthesize new materials or to stabilize metastable phases with advanced mechanical and functional properties. High strength combined with high ductility, low/room-temperature superplasticity, creep resistance, hydrogen storage, photocatalytic hydrogen production, photocatalytic CO2 conversion, superconductivity, thermoelectric performance, radiation resistance, corrosion resistance, and biocompatibility are some highlighted properties of SPD-processed materials. This article reviews recent advances in the NanoSPD field and provides a brief history regarding its progress from the ancient times to modernity. Abbreviations: ARB: Accumulative Roll-Bonding; BCC: Body-Centered Cubic; DAC: Diamond Anvil Cell; EBSD: Electron Backscatter Diffraction; ECAP: Equal-Channel Angular Pressing (Extrusion); FCC: Face-Centered Cubic; FEM: Finite Element Method; FSP: Friction Stir Processing; HCP: Hexagonal Close-Packed; HPT: High-Pressure Torsion; HPTT: High-Pressure Tube Twisting; MDF: Multi-Directional (-Axial) Forging; NanoSPD: Nanomaterials by Severe Plastic Deformation; SDAC: Shear (Rotational) Diamond Anvil Cell; SEM: Scanning Electron Microscopy; SMAT: Surface Mechanical Attrition Treatment; SPD: Severe Plastic Deformation; TE: Twist Extrusion; TEM: Transmission Electron Microscopy; UFG: Ultrafine Grained. © 2022 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group.

Abstract Bismuth sodium titanate (BNT)‐derived materials have seen a flurry of research interest in recent years because of the existence of extended strain under applied electric fields, surpassing that of lead zirconate titanate (PZT), the most commonly used piezoelectric. The underlying physical and chemical mechanisms responsible for such extraordinary strain levels in BNT are still poorly understood, as is the nature of the successive phase transitions. A comprehensive explanation is proposed here, combining the short‐range chemical and structural sensitivity of in situ Raman spectroscopy (under an applied electric field and temperature) with macroscopic electrical measurements. The results presented clarify the causes for the extended strain, as well as the peculiar temperature‐dependent properties encountered in this system. The underlying cause is determined to be mediated by the complex‐like bonding of the octahedra at the center of the perovskite: a loss of hybridization of the 6s 2 bismuth lone pair interacting with the oxygen p‐orbitals occurs, which triggers both the field‐induced phase transition and the loss of macroscopic ferroelectric order at the depolarization temperature.

Collagen type I is the most abundant structural protein in tendon, skin and bone, and largely determines the mechanical behaviour of these connective tissues. To obtain a better understanding of the relationship between structure and mechanical properties, tensile tests and synchrotron X-ray scattering have been carried out simultaneously, correlating the mechanical behaviour with changes in the microstructure. Because intermolecular cross-links are thought to have a great influence on the mechanical behaviour of collagen, we also carried out experiments using cross-link-deficient tail-tendon collagen from rats fed with beta-APN, in addition to normal controls. The load-elongation curve of tendon collagen has a characteristic shape with, initially, an increasing slope, corresponding to an increasing stiffness, followed by yielding and then fracture. Cross-link-deficient collagen produces a quite different curve with a marked plateau appearing in some cases, where the length of the tendon increases at constant stress. With the use of in situ X-ray diffraction, it was possible to measure simultaneously the elongation of the collagen fibrils inside the tendon and of the tendon as a whole. The overall strain of the tendon was always larger than the strain in the individual fibrils, which demonstrates that some deformation is taking place in the matrix between fibrils. Moreover, the ratio of fibril strain to tendon strain was dependent on the applied strain rate. When the speed of deformation was increased, this ratio increased in normal collagen but generally decreased in cross-link-deficient collagen, correlating to the appearance of a plateau in the force-elongation curve indicating creep. We proposed a simple structural model, which describes the tendon at a hierarchical level, where fibrils and interfibrillar matrix act as coupled viscoelastic systems. All qualitative features of the strain-rate dependence of both normal and cross-link-deficient collagen can be reproduced within this model. This complements earlier models that considered the next smallest level of hierarchy, describing the deformation of collagen fibrils in terms of changes in their molecular packing.

The continuously forming fin bony rays of zebrafish represent a simple bone model system in which mineralization is temporally and spatially resolved. The mineralized collagen fibrils of the fin bones are identical in structure to those found in all known bone materials. We study the continuous mineralization process within the tissue by using synchrotron microbeam x-ray diffraction and small-angle scattering, combined with cryo-scanning electron microscopy. The former provides information on the mineral phase and the mineral particles size and shape, whereas the latter allows high-resolution imaging of native hydrated tissues. The integration of the two techniques demonstrates that new mineral is delivered and deposited as packages of amorphous calcium phosphate nanospheres, which transform into platelets of crystalline apatite within the collagen matrix.

Peat depositional environments, the sites where and conditions under which peat accumulates, significantly influence a resultant coal's physical properties, chemical composition, and coal utilization behavior. Recognition of peat depositional environments for coal is a challenging endeavor because coal's observed compositional properties not only result from a variety of geological processes operating during peat accumulation, but also reflect the influence of adjoining or external depositional sedimentary environments and alteration during later diagenesis and/or epigenesis. The maceral or microlithotype composition of any one layer of peat can be the product of years or decades of plant growth, death, decay, and post-burial infiltration by roots in addition to the symbiotic, mutualistic, parasitic, and saprophytic relationships with non-plant biota, such as arthropods, fungi, and bacteria. The overprint of increasing thermal maturation and fluid migration through time on the resulting coal can make these relationships difficult to recognize. Therefore, published models based on maceral composition alone must be used with great caution. Lipid compositions, even from lipid-poor low-rank coals, can provide important information about depositional environments and paleoclimate, especially if combined with the results of organic petrography and paleontological studies. Just as sulfur derived from seawater provides environmental clues, the ratios of two particularly relevant trace elements rather than a single trace element can be used to interpret peat depositional environments. Epigenetic minerals, as well as their corresponding chemical compositions should not be used for such a purpose; similarly, resistant terrigenous minerals deposited during peat accumulation in many cases should be used with considerable caution. The interactions of the biota present in the peat-forming ecosystem, often determined using palynological and geochemical proxies, and their interpretation in the context of geography and paleoclimate are important means for deciphering peat depositional environments. Overall, a combination of evidence from geochemistry, mineralogy, palynology, and petrology of coal and from stratigraphy, sedimentology, and sedimentary facies of related rocks is necessary for accurate and comprehensive determination of depositional environments. The need for interdisciplinary studies is underscored by peat compositional properties, which have been greatly affected by various processes during the syngenetic, diagenetic or epigenetic stages of coal formation.