Towards load-bearing biomedical titanium-based alloys: From essential requirements to future developments

The use of biomedical metallic materials in research and clinical applications has been an important focus and a significant area of interest, primarily owing to their role in enhancing human health and extending human lifespan. This article, particularly on titanium-based alloys, explores exceptional properties that can address bone health issues amid the growing challenges posed by an aging population. Although stainless steel, magnesium-based alloys, cobalt-based alloys, and other metallic materials are commonly employed in medical applications, limitations such as toxic elements, high elastic modulus, and rapid degradation rates limit their widespread biomedical applications. Therefore, titanium-based alloys have emerged as top-performing materials, gradually replacing their counterparts in various applications. This article extensively examines and highlights titanium-based alloys, along with an in-depth discussion of currently utilized metallic biomedical materials and their inherent limitations. To begin with, the essential requirements for load-bearing biomaterials are introduced. Then, the biomedical metallic materials are summarized and compared. Afterward, the microstructure, properties, and preparations of titanium-based alloys are explored. Furthermore, various surface modification methods are discussed to enhance biocompatibility, wear resistance, and corrosion resistance. Finally, the article proposes the development path for titanium-based alloys in conjunction with additive manufacturing and the novel alloy nitinol

Nanomaterials by severe plastic deformation: review of historical developments and recent advances

International audienceSevere 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

Spark Plasma Sintered High-Entropy Alloys: An Advanced Material for Aerospace Applications

High-entropy alloys (HEAs) are materials of high property profiles with enhanced strength-to-weight ratios and high temperature-stress-fatigue capability as well as strong oxidation resistance strength. HEAs are multi-powder-based materials whose microstructural and mechanical properties rely strongly on stoichiometry combination of powders as well as the consolidation techniques. Spark plasma sintering (SPS) has a notable processing edge in processing HEAs due to its fast heating schedule at relatively lower temperature and short sintering time. Therefore, major challenges such as grain growth, porosity, and cracking normally encountered in conventional consolidation like casting are bypassed to produce HEAs with good densification. SPS parameters such as heating rate, temperature, pressure, and holding time can be utilized as design criteria in software like Minitab during design of experiment (DOE) to select a wide range of values at which the HEAs may be produced as well as to model the output data collected from mechanical characterization. In addition to this, the temperature-stress-fatigue response of developed HEAs can be analyzed using finite element analysis (FEA) to have an in-depth understanding of the detail of inter-atomic interactions that inform the inherent material properties

High Entropy Materials: Challenges and Prospects

This book is a reprint of a special issue of Metals (ISSN 2075-4701), titled High Entropy Materials: Challenges and Prospects. It is a compilation of nine articles from different aspects of high-entropy materials. The book primarily focuses on high-entropy alloys, the first emergent high-entropy materials, but also covers high-entropy ceramics and high-entropy composites, which are the extensions of high-entropy alloys. The articles on high-entropy alloys cover some important facets in the field such as phase structures, mechanical properties, laser beam welding, design of soft magnetic alloys, and potential as biomaterials. In addition, there are one article introducing the potential of using high-entropy carbides as hard metals for machining, and one another on high-entropy composite studying the microstructures and tribological properties of the FeCoNiCuAl-TiC composite. The goal of this reprinted book is essentially two-fold. In the first place, it offers a platform for researchers in the broad field of high-entropy materials to communicate their views and recent research on the subject. Next, it reports challenges in the sub-fields of high-entropy materials and inspires researchers to continue to practice diligence to resolve these challenges and advance high-entropy materials solidly. We hope that readers in the field feel encouraged, inspired, and challenged by the book, and readers outside the field can grasp some basic ideals of high-entropy materials and their potential to the society as a family of novel materials

High entropy alloys obtained by field assisted powder metallurgy route: SPS and microwave heating

The aim of this work was to investigate the field assisted powder metallurgy route for producing HEAs at equimolar composition, i.e. FeCoNiCrAl, starting from metal powders. Both mixed, mechanically activated and mechanically alloyed powders have been used. The powders obtained by mechanical alloying were synthesized only by SPS, whereas the remaining ones were sintered by SPS or microwave heating. The investigated field assisted sintering techniques allowed an extremely short alloying time, high energy density on the load and negligible contamination by the surrounding environment. Both the conducted sintering-synthesis technology resulted not definitive to produce chemical homogeneity and to obtain a single stable structure. Thus a subsequently heat treatment was required. The post heat treatment, indeed, led to a single crystalline structure (FCC) and the material was fully recrystallized. After heat treatment samples are isomorphic: they exhibit two different phases with the same FCC cell, but different chemical composition, in detail Fe-Cr richer and Al-Ni richer. SPS-ed samples present a reduced porosity, while microwave processed ones are much more porous and this is reflected in the mechanical properties

DERIVATION, EXPLORATION AND EVALUATION OF NON-EQUIATOMIC HIGH ENTROPY ALLOYS

High-entropy alloys (HEAs) are a class of multicomponent alloys based on an innovative alloying strategy that employs multi-principle elements in relatively high concentrations. Commonly defined as alloys that contain at least five principal elements, each with a concentration between 5 and 35 at %. The term entropy refers to the excess configurational entropy associated with HEAs, which is thought to facilitate the formation of solid solutions. The design strategy results in vast compositional space for exploration and innovative potential triggering a renaissance in physical metallurgy. These alloys may have favorable properties compared to conventional dilute solid solutions, but their preeminent complexity and relative novelty mean that they are difficult to design and explore. Numerous studies in this field have explored and developed these alloys motivated by the primary HEA concept, which postulates that maximum configurational entropy can be achieved through equiatomic ratios, which, in turn, will stabilize single-phase solid solutions. However, a growing number of studies have shown that entropic stabilization alone is insufficient, and the optimal balance may be found in non-equiatomic mixtures. The primary objective of this work is to develop and evaluate single-phase non-equiatomic HEAs with unique compositions that will improve fundamental understanding and/or raise new questions and challenges. The findings in this work address multiple aspects of HEA development, focusing on methodology, discovery, and physical properties. For the first part of this work, the association between the thermal history and the resultant phases and microstructures is investigated for the equiatomic CrMnFeCoNiCu system. Motivated by the natural phenomena of crystal growth and conditions of equilibrium, we introduced a method that is applicable to HEA development, where controlled processing conditions decide the most probable and stable composition. This is demonstrated by cooling an equiatomic CrMnFeCoNiCu from the melt within 3 days. This results in large Cr-rich precipitates and almost a Cr-free matrix with compositions within the MnFeCoNiCu system. From this juncture, it is argued that the most stable composition is within the MnFeCoNiCu system and not within the CrMnFeCoNi system. With further optimization and evaluation, a unique non-equiatomic alloy, Mn17Fe21Co24Ni24Cu14 is derived. The alloy solidifies and recrystallizes into single-phase FCC phase and can be used in fundamental studies that contrast the equiatomic counterpart. The second part of this work utilizes a thin-film combinatorial approach to develop a compositional and structural library for the OsRuWCo alloy system. A total of 24 unique compositions were produced, representing a structural library in which amorphous hexagonal closed-pack structures hexagonal closed-pack structures and single phase hexagonal close-pack (HCP) structures are identified. From a selected film composition, a new high-entropy bulk alloy with OsRuWCo in nonequiatomic portions was synthesized. The alloy exhibited a single-phase HCP structure in the as-cast state. Three derivatives from this system were also produced considering heats of mixing, atomic size, and binary solubility. These derivatives are OsRuWCoIr, OsRuWCoFe, and OsRuWCoMoRe and all exhibit single-phase HCP as-cast structures, based on x-ray diffraction and electron microscopy. Additionally, this large compositional space was utilized to evaluate conventional parameters that describe high-entropy alloys. Trends illustrating the evolution from amorphous to crystalline phases are discussed. A further part of this work evaluates the strengthening due to grain size reduction for the newly developed Mn17Fe21Co24Ni24Cu14. Tensile tests were performed on samples with microstructure with grain size ranging from ~7 um to 120 µm. The study addresses a significant challenge in HEA research in which the available sample size in laboratory settings hinders mechanical testing and evaluation of HEAs in tension. This is overcome by developing a furnace casting method that produces ingots large enough to produce multiple tensile specimens. The alloy exhibits excellent strengthening tendencies with an increase in yield stress based on square root scaling taking the form and the form with an unconstrained scaling exponent. Furthermore, the strengthening phenomena and the physical interpretation of the observed strengthening in HEAs are evaluated with discussions aimed at answering the fundamental question: “Do HEAs exhibit exceptional size effects?

Advanced Powder Metallurgy Technologies

Powder metallurgy is a group of advanced processes used for the synthesis, processing, and shaping of various kinds of materials. Initially inspired by ceramics processing, the methodology comprising the production of a powder and its transformation to a compact solid product has attracted attention since the end of World War II. At present, many technologies are availabe for powder production (e.g., gas atomization of the melt, chemical reduction, milling, and mechanical alloying) and its consolidation (e.g., pressing and sintering, hot isostatic pressing, and spark plasma sintering). The most promising methods can achieve an ultra-fine or nano-grained powder structure, and preserve it during consolidation. Among these methods, mechanical alloying and spark plasma sintering play a key role. This book places special focus on advances in mechanical alloying, spark plasma sintering, and self-propagating high-temperature synthesis methods, as well as on the role of these processes in the development of new materials

Corrosion Behaviour of Additively Manufactured High Entropy Alloys

Additive manufacturing (AM) is a modern manufacturing technique that facilitates the production of components layer by layer from CAD files, with more recent developments in the field leading to the ability to create these components from metal. Laser powder bed fusion (LPBF) is one of the many techniques used to manufacture metallic components and has drawn significant attention for its ability to create parts with high degrees of complexity, exceptional strength-to-weight ratios and internal structures. However, parts produced by AM are documented to suffer from build defects such as porosity, which can negatively affect not only its mechanical properties but its corrosion resistance,particularly its resistance to pitting corrosion. Whilst the mechanical properties of components produced through metal AM have been well documented since the technology’s inception, there are significant knowledge gaps in understanding the corrosion behaviour of metals produced in this way.This thesis aims to expand upon the current understanding of this manufacturing method with a particular focus on its corrosion resistance. High Entropy Alloys (HEAs) are a class of advanced materials that differ from conventional alloys in composition. Traditional alloys usually consist of one or two principal elements with smaller amounts of additional elements to impart specific properties. In contrast, HEAs are characterised by the presence of multiple principal elements in roughly equal proportions. HEAs' complex and disordered structure can result in unique mechanical, thermal, and magnetic properties. HEAs have shown promise in exhibiting high strength, hardness, and corrosion resistance, making them attractive for various engineering applications. Studies of HEAs have been increasing over recent years; however, significant knowledge gaps are still associated with this classification of materials, especially concerning their corrosion resistance. This lack of knowledge is intensified when discussing the properties of these alloys when manufactured by AM methods.LPBF was used to produce parts in 316L with process induced porosity by manipulating the process parameters to investigate the effect density has on the corrosion resistance of AM parts. The corrosion resistance of these parts were compared to their wrought counterpart using potentiodynamic polarisation. It was observed that increasing the porosity in the AM parts resulted in poorer corrosion resistance, both by weaker performance across key metrics and a greater degree of unreliability. It was also found that the AM parts proved to have a greater corrosion resistance than the wrought material. However, the decreased consistency in this resistance is often cited as a barrier these components must overcome to supplace conventionally manufactured components.316L was also produced through induction casting as well as a schedule more representative of industry that consisted of a solution anneal at 1080 °C followed by water quenching followed by a cold rolling reduction by 70 %, and a final anneal at 900 °C. The microstructures and corrosion resistance of these were investigated using SEM-EDS, XRD and potentiodynamic polarisation, and whilst the corrosion resistance of the cold rolled sample had increased, it was less than expected due to the formation of detrimental chromium carbides.A Swansea University developed AlCrFeMnNi HEA was put through the same 3 manufacturing processes to investigate their effect on the microstructure and corrosion resistance. It was found that, unlike 316L, the HEA suffered less from pitting corrosion and more from a generalised corrosion attack. Very similar corrosion results were seen across the manufacturing methods; however, the cast sample was observed to have the most consistent display of corrosion resistance.Based on the pitting resistance equivalent number, which relates the amount of Cr and Mo by wt.% in a stainless steel to its corrosion resistance, it was theorised that the addition of Mo to this HEA could also increase its corrosion resistance. The results were inconclusive; however, better corrosion resistance was seen in the AM sample of the HEA with the addition than in the AM sample without

Severe plastic deformation for producing superfunctional ultrafine-grained and heterostructured materials: An interdisciplinary review

Ultrafine-grained and heterostructured materials are currently of high interest due to their superior mechanical and functional properties. Severe plastic deformation (SPD) is one of the most effective methods to produce such materials with unique microstructure-property relationships. In this review paper, after summarizing the recent progress in developing various SPD methods for processing bulk, surface and powder of materials, the main structural and microstructural features of SPD-processed materials are explained including lattice defects, grain boundaries and phase transformations. The properties and potential applications of SPD-processed materials are then reviewed in detail including tensile properties, creep, superplasticity, hydrogen embrittlement resistance, electrical conductivity, magnetic properties, optical properties, solar energy harvesting, photocatalysis, electrocatalysis, hydrolysis, hydrogen storage, hydrogen production, CO2 conversion, corrosion resistance and biocompatibility. It is shown that achieving such properties is not limited to pure metals and conventional metallic alloys, and a wide range of materials are currently processed by SPD, including high-entropy alloys, glasses, semiconductors, ceramics and polymers. It is particularly emphasized that SPD has moved from a simple metal processing tool to a powerful means for the discovery and synthesis of new superfunctional metallic and nonmetallic materials. The article ends by declaring that the borders of SPD have been extended from materials science and it has become an interdisciplinary tool to address scientific questions such as the mechanisms of geological and astronomical phenomena and the origin of life