Fabrication of Layered SiC/C/Si/MeSi2/Me Ceramic-Metal Composites via Liquid Silicon Infiltration of Metal-Carbon Matrices.

The growing demand for composite materials capable of enduring prolonged loads in high-temperature and aggressive environments presents pressing challenges for materials scientists. Ceramic materials composed of silicon carbide largely possess high mechanical strength at a relatively low density, even at elevated temperatures. However, they are inherently brittle in nature, leading to concerns about their ability to fracture. The primary objective of this study was to develop a novel technique for fabricating layered composite materials by incorporating SiC-based ceramics, refractory metals, and their silicides as integral constituents. These layered composites were produced through the liquid-phase siliconization method applied to metal-carbon blanks. Analysis of the microstructure of the resultant materials revealed that when a metal element interacts with molten silicon, it leads to the formation of a layer of metal silicide on the metal's surface. Furthermore, three-point bending tests exhibited an enhancement in the bending strength of the layered composite in comparison to the base silicon carbide ceramics. Additionally, the samples demonstrated a quasi-plastic nature during the process of destruction.

Effect of High-Pressure Torsion on Phase Formation and Mechanical Properties of a High-Entropy TiZrHfMoCrCo Alloy.

This investigation delved into the alterations in the mechanical properties of a TiZrHfMoCrCo high-entropy alloy due to phase transformations induced by high-pressure torsion (HPT). The alloy's genesis involved levitation melting within an argon atmosphere, presenting two distinct states for analysis: the initial, post-manufacturing state and the state subsequent to HPT treatment. The original alloy featured a composition comprising a singular A2 phase with a bcc lattice and two Laves phases, C15 and C14. The HPT process triggered significant phase modifications: a retention of one C15 Laves phase and decomposition of the bcc phase into two distinct phases exhibiting different bcc lattice parameters. The HPT-induced effect prominently manifests as strong grain refinement. However, scanning electron microscopy (SEM) observations unveiled persistent inhomogeneities at a micron scale both before and after HPT treatment. Thus, grain refinement occurs separately within each of the bcc and Laves phases, visible in the light, dark, and gray areas in SEM images, while mixing does not occur on the scale of several microns. The examination of Ti, Cr, Co, Zr, Mo, and Hf via X-ray absorption spectroscopy (EXAFS) at specific K-edges and L3-edge revealed that the HPT treatment conserves the local atomic environment of metal atoms, albeit with a slight elevation in static disorder. Assessments through microhardness and three-point bending tests demonstrated the material's inherent hardness and brittleness. The microhardness, standing at a substantial value of 600 HV, displayed negligible augmentation post-HPT. However, the microhardness of individual phases exhibited a notable alteration, nearly doubling in magnitude.

Influence of the Phase Composition of Titanium Alloys on Cell Adhesion and Surface Colonization.

The pivotal role of metal implants within the host's body following reconstructive surgery hinges primarily on the initial phase of the process: the adhesion of host cells to the implant's surface and the subsequent colonization by these cells. Notably, titanium alloys represent a significant class of materials used for crafting metal implants. This study, however, marks the first investigation into how the phase composition of titanium alloys, encompassing the volume fractions of the α, ß, and ω phases, influences cell adhesion to the implant's surface. Moreover, the research delves into the examination of induced hemolysis and cytotoxicity. To manipulate the phase composition of titanium alloys, various parameters were altered, including the chemical composition of titanium alloys with iron and niobium, annealing temperature, and high-pressure torsion parameters. By systematically adjusting these experimental parameters, we were able to discern the distinct impact of phase composition. As a result, the study unveiled that the colonization of the surfaces of the examined Ti-Nb and Ti-Fe alloys by human multipotent mesenchymal stromal cells exhibits an upward trend with the increasing proportion of the ω phase, concurrently accompanied by a decrease in the α and ß phases. These findings signify a new avenue for advancing Ti-based alloys for both permanent implants and temporary fixtures, capitalizing on the ability to regulate the volume fractions of the α, ß, and ω phases. Furthermore, the promising characteristics of the ω phase suggest the potential emergence of a third generation of biocompatible Ti alloys, the ω-based materials, following the first-generation α-Ti alloys and second-generation ß alloys.

Topology of WC/Co Interfaces in Cemented Carbides.

WC-Co cemented carbides build one of the important classes of metal matrix composites. We show in this paper that the use of machine vision methods makes it possible to obtain sufficiently informative statistical data on the topology of the interfaces between tungsten carbide grains (WC) and a cobalt matrix (Co). For the first time, the outlines of the regions of the cobalt binder were chosen as a tool for describing the structure of cemented carbides. Numerical processing of micrographs of cross sections of three WC-Co alloys, which differ in the average grain size, was carried out. The distribution density of the angles in the contours of cobalt "lakes" is bimodal. The peaks close to 110° (so-called outcoming angles) correspond to the contacts between the cobalt binder and the WC/WC grain boundaries. The peaks close to 240° (or incoming angles) correspond to the WC "capes" contacting the cobalt "lakes" and are determined by the angles between facets of WC crystallites. The distribution density of the linear dimensions of the regions of the cobalt binder, approximated with ellipses, were also obtained. The distribution density exponentially decreases with the lengths of the semi-axes of the ellipsoid, approximating the area of the cobalt binder. The possible connection between the obtained data on the shape of cobalt areas and the crack trajectories in cemented carbides is discussed.

Faceting/Roughening of WC/Binder Interfaces in Cemented Carbides: A Review.

Hardmetals (or cemented carbides) were invented a hundred years ago and became one of the most important materials in engineering. The unique conjunction of fracture toughness, abrasion resistance and hardness makes WC-Co cemented carbides irreplaceable for numerous applications. As a rule, the WC crystallites in the sintered WC-Co hardmetals are perfectly faceted and possess a truncated trigonal prism shape. However, the so-called faceting-roughening phase transition can force the flat (faceted) surfaces or interfaces to become curved. In this review, we analyze how different factors can influence the (faceted) shape of WC crystallites in the cemented carbides. Among these factors are the modification of fabrication parameters of usual WC-Co cemented carbides; alloying of conventional cobalt binder using various metals; alloying of cobalt binder using nitrides, borides, carbides, silicides, oxides; and substitution of cobalt with other binders, including high entropy alloys (HEAs). The faceting-roughening phase transition of WC/binder interfaces and its influence on the properties of cemented carbides is also discussed. In particular, the increase in the hardness and fracture toughness of cemented carbides correlates with transition of WC crystallites from a faceted to a rounded shape.

Phase Transformations Caused by Heat Treatment and High-Pressure Torsion in TiZrHfMoCrCo Alloy.

In this work the high-entropy alloy studied contained six components, Ti/Zr/Hf/Mo/Cr/Co, and three phases, namely one phase with body-centered cubic lattice (BCC) and two Laves phases C14 and C15. A series of annealings in the temperature range from 600 to 1000 °C demonstrated not only a change in the microstructure of the TiZrHfMoCrCo alloy, but also the modification of phase composition. After annealing at 1000 °C the BCC phase almost fully disappeared. The annealing at 600 and 800 °C leads to the formation of new Laves phases. After high-pressure torsion (HPT) of the as-cast TiZrHfMoCrCo alloy, the grains become very small, the BCC phase prevails, and C14 Laves phase completely disappears. This state is similar to the state after annealing at high effective temperature Teff. The additional annealing at 1000 °C after HPT returns the phase composition back to the state similar to that of the as-cast alloy after annealing at 1000 °C. At 1000 °C the BCC phase completely wets the C15/C15 grain boundaries (GBs). At 600 and 800 °C the GB wetting is incomplete. The big spread of nanohardness and Young's modulus for the BCC phase and (C15 + C14) Laves phases is observed.

Formation and Thermal Stability of the ω-Phase in Ti-Nb and Ti-Mo Alloys Subjected to HPT.

This paper discusses the features of ω-phase formation and its thermal stability depending on the phase composition, alloying element and the grain size of the initial microstructure of Ti-Nb and Ti-Mo alloys subjected to high-pressure torsion (HPT) deformation. In the case of two-phase Ti-3wt.% Nb and Ti-20wt.% Nb alloys with different volume fractions of α- and ß-phases, a complete ß→ω phase transformation and partial α→ω transformation were found. The dependence of the α→ω transformation on the concentration of the alloying element was determined: the greater content of Nb in the α-phase, the lower the amount of ω-phase that was formed from it. In the case of single-phase Ti-Mo alloys, it was found that the amount of ω-phase formed from the coarse-grained ß-phase of the Ti-18wt.% Mo alloy was less than the amount of the ω-phase formed from the fine α'-martensite of the Ti-2wt.% Mo alloy. This was despite the fact that the ω-phase is easier to form from the ß-phase than from the α- or α'-phase. It is possible that the grain size of the microstructure also affected the phase transformation, namely, the fine martensitic plates more easily gain deformation and overcome the critical shear stresses necessary for the phase transformation. It was also found that the thermal stability of the ω-phase in the Ti-Nb and Ti-Mo alloys increased with the increasing concentration of Nb or Mo.

Jerky Motion of the Reaction Front during Discontinuous Dissolution in a Fe-13.5 at.% Zn Alloy.

This paper studies the go- and -stop movement of a receding reaction front (RF) during a discontinuous dissolution (DD) process. A special simulation procedure was applied for the DD reaction to predict a jerky motion of the RF. The Fe-13.5 at.% Zn alloy was selected in which go- and -stop behaviour was revealed in the form of characteristic lines (called "ghost lines") showing successive positions of receding RF. The results presented for the DD process are quite different from those relevant for the DP reaction at the same Fe-13.5 at.% Zn alloy in terms of go- and -stop motion and movement distance. For the presented case, the go- and -stop periods are relatively long and obtain an order of several dozen seconds, while for the DP reaction, it was only a few seconds. A similar conclusion was formulated after a comparison of the movement distance which, for the DD reaction, is usually longer by 1-2 orders of magnitude. The simulation results of the DD reaction indicate a good agreement with the experimental data presented in the literature for the same dissolution rate. It is necessary to emphasize that the simulation is the only source of data for z parameter changes during the -stop period of the DD reaction.

Structure Refinement and Fragmentation of Precipitates under Severe Plastic Deformation: A Review.

During severe plastic deformation (SPD), the processes of lattice defect formation as well as their relaxation (annihilation) compete with each other. As a result, a dynamic equilibrium is established, and a steady state is reached after a certain strain value. Simultaneously, other kinetic processes act in opposite directions and also compete with each other during SPD, such as grain refinement/growth, mechanical strengthening/softening, formation/decomposition of solid solution, etc. These competing processes also lead to dynamic equilibrium and result in a steady state (saturation), albeit after different strains. Among these steady-state phenomena, particle fragmentation during the second phase of SPD has received little attention. Available data indicate that precipitate fragmentation slows down with increasing strain, though saturation is achieved at higher strains than in the case of hardness or grain size. Moreover, one can consider the SPD-driven nanocrystallization in the amorphous phase as a process that is opposite to the fragmentation of precipitates. The size of these crystalline nanoprecipitates also saturates after a certain strain. The fragmentation of precipitates during SPD is the topic of this review.

Grain Boundary Wetting by a Second Solid Phase in the High Entropy Alloys: A Review.

In this review, the phenomenon of grain boundary (GB) wetting by the second solid phase is analyzed for the high entropy alloys (HEAs). Similar to the GB wetting by the liquid phase, the GB wetting by the second solid phase can be incomplete (partial) or complete. In the former case, the second solid phase forms in the GB of a matrix, the chain of (usually lenticular) precipitates with a certain non-zero contact angle. In the latter case, it forms in the GB continuous layers between matrix grains which completely separate the matrix crystallites. The GB wetting by the second solid phase can be observed in HEAs produced by all solidification-based technologies. The particle chains or continuous layers of a second solid phase form in GBs also without the mediation of a liquid phase, for example by solid-phase sintering or coatings deposition. To describe the GB wetting by the second solid phase, the new GB tie-lines should be considered in the two- or multiphase areas in the multicomponent phase diagrams for HEAs. The GB wetting by the second solid phase can be used to improve the properties of HEAs by applying the so-called grain boundary engineering methods.

Cellular Automata Modelling of Discontinuous Precipitation.

The fundamentals of discontinuous precipitation (DP) reaction modelling using a cellular automata (CA) method are presented. In the proposed CA model, cell states, internal variables, equations, and transition rules were defined to predict the manner of mass transport during DP reaction and to relate changes in the microstructure with corresponding changes in chemical composition. Furthermore, the concept of digital material representation (DMR) was introduced into the CA model, which allowed schematic images of the microstructure to be used as starting structures in the modelling of the DP reaction. The preliminary assumptions adopted in the proposed CA model for the DP reaction were verified by numerical simulations of the growth of discontinuous precipitates at a steady-state at the example of Al-22 at.% Zn alloy. The outcomes achieved from the CA simulations were presented in a different form than that most commonly used previously (single concentration profiles), namely as the 2D maps showing changes in Zn content accompanying the successive stages of growth of discontinuous precipitates. The model used for the description of the solute diffusion along of the reaction front (RF) allowed two-dimensional systems at the nano-scale to be treated within a reasonable simulation time. The obtained results indicate that the developed CA model was able to realistically simulate the DP reaction, which was confirmed by the visualisation of migrating RFs together with associated chemical composition changes in the microstructure.

Omega Phase Formation in Ti-3wt.%Nb Alloy Induced by High-Pressure Torsion.

It is well known that severe plastic deformation not only leads to strong grain refinement and material strengthening but also can drive phase transformations. A study of the fundamentals of α → ω phase transformations induced by high-pressure torsion (HPT) in Ti-Nb-based alloys is presented in the current work. Before HPT, a Ti-3wt.%Nb alloy was annealed at two different temperatures in order to obtain the α-phase state with different amounts of niobium. X-ray diffraction analysis, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were applied for the characterisation of phase transitions and evolution of the microstructure. A small amount of the ß-phase was found in the initial states, which completely transformed into the ω-phase during the HPT process. During HPT, strong grain refinement in the α-phase took place, as did partial transformation of the α- into the ω-phase. Therefore, two kinds of ω-phase, each with different chemical composition, were obtained after HPT. The first one was formed from the ß-phase, enriched in Nb, and the second one from the α-phase. It was also found that the transformation of the α-phase into the ω-phase depended on the Nb concentration in the α-Ti phase. The less Nb there was in the α-phase, the more of the α-phase was transformed into the ω-phase.

Discontinuous Dissolution Reaction in a Fe-13.5 at. % Zn Alloy.

The dissolution process of a lamellar structure with α and Γ phases formed during a discontinuous precipitation reaction is investigated here with a Fe-13.5 at. % Zn alloy by means of optical microscopy and scanning and transmission electron microscopy. The α phase is a solute-depleted solid solution and the Γ phase is the intermetallic compound Fe3Zn10. The examination reveals that the dissolution occurs in a discontinuous mode by a receding of the former reaction front of the discontinuous precipitation towards the position of the original grain boundary. A new solid solution in the post-dissolution area is especially inhomogeneous and reflects the former locations of the Γ lamellae ("ghost images") and the receding reaction front ("ghost lines"). A simulation procedure is applied to determine the Zn concentration profiles left in the post-dissolution region. Their shapes are mostly affected by the Zn content at the positions where the Γ lamellae have just been dissolved, which was also confirmed by the quantitative microchemical analysis.

Cytotoxicity of biodegradable magnesium alloy WE43 to tumor cells in vitro: Bioresorbable implants with antitumor activity?

In this study, a degradable magnesium alloy WE43 (Mg-3.56%Y-2.20%Nd-0.47%Zr) was used as a research object. To refine its microstructure from the initial homogenized one, the alloy was subjected to severe plastic deformation (SPD) by equal channel angular pressing (ECAP). The data presented show that coincubation of tumor LNCaP and MDA-MB-231 cells with the WE43 alloy in the homogenized and the ECAP-processed states led to a decrease in their viability and proliferation. An increase in the concentration of Annexin V(+) cells during coincubation with samples in both microstructural states investigated was also observed. This is associated with the induction of apoptosis in the cell culture through contact with the samples. Concurrently, a significant drop in the concentration of Bcl-2(+) cells occurred. It was established that ECAP led to an enhancement of the cytotoxic activity of the alloy against tumor cells. This study demonstrated that alloy WE43 can be considered as a promising candidate for application in orthopedic implants in clinical oncology, where it could play a double role of a mechanically stable, yet bioresorbable, scaffold with local antitumor activity. © 2019 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 108B:167-173, 2020.

The Effect of Equal-Channel Angular Pressing on the Microstructure, the Mechanical and Corrosion Properties and the Anti-Tumor Activity of Magnesium Alloyed with Silver.

The effect of equal-channel angular pressing (ECAP) on the microstructure, texture, mechanical properties, corrosion resistance and cytotoxicity of two magnesium-silver alloys, Mg-2.0%Ag and Mg-4.0%Ag, was studied. Their average grain size was found to be reduced to 3.2 ± 1.4 µm and 2.8 ± 1.3 µm, respectively. Despite the substantial grain refinement, a drop in the strength characteristics of the alloys was observed, which can be attributed to the formation of inclined basal texture. On a positive side, an increase in tensile ductility to ~34% for Mg-2.0%Ag and ~27% for Mg-4.0%Ag was observed. This effect can be associated with the activity of basal and prismatic slip induced by ECAP. One of the ECAP regimes tested gave rise to a drop in the corrosion resistance of both alloys. An interesting observation was a cytotoxic effect both alloys had on tumor cells in vitro. This effect was accompanied with the release of lactate dehydrogenase, an increase in oxidative stress, coupled with the induction of NO-ions and an increase in the content of such markers of apoptosis as Annexin V and Caspase 3/7. Differences in the chemical composition and the processing history-dependent microstructure of the alloys did not have any significant effect on the magnitude of their antiproliferative effect.

Microstructure Evolution and Some Properties of Hard Magnetic FeCr30Co8 Alloy Subjected to Torsion Combined with Tension.

The hard magnetic alloy FeCr30Co8 alloy was subjected to severe plastic deformation (SPD) by torsion combined with tension in the temperature range of 750 °C to 850 °C. This range of deformation temperatures corresponds to the α solid solution on the Fe-Cr-Co phase diagram. The study of the alloy after SPD by means of X-ray diffraction (XRD) and scanning and transmission electron microscopy techniques showed the formation of a gradient microstructure with fine grain size in the surface layer and precipitation of the hard intermetallic σ-phase. Next, the magnetic and mechanical properties of the deformed alloy after short annealing at 1000 °C and magnetic treatment were studied. A slight decrease in coercive force was found, along with a significant gain in plasticity and strength. The effective deformation temperature was determined to obtain the optimal magnetic and mechanical characteristics of the alloy. This method of deformation can be applied for the improvement of the mechanical properties of some magnets (high-speed rotors) which should have good magnetic properties within their volume while maintaining good mechanical properties on the surface.

Structural and Mechanical Properties of Ti⁻Co Alloys Treated by High Pressure Torsion.

The microstructure and properties of titanium-based alloys can be tailored using severe plastic deformation. The structure and microhardness of Ti⁻4 wt.% Co alloy have been studied after preliminary annealing and following high pressure torsion (HPT). The Ti⁻4 wt.% Co alloy has been annealed at 400, 500, and 600 °C, i.e., below the temperature of eutectoid transformation in the Ti⁻4 wt.% Co system. The amount of Co dissolved in α-Ti increased with increasing annealing temperature. HPT led to the transformation of α-Ti in ω-Ti. After HPT, the amount of ω-phase in the sample annealed at 400 °C was about 80-85%, i.e., higher than in pure titanium (about 40%). However, with increasing temperature of pre-annealing, the portion of ω-phase decreased (60⁻65% at 500 °C and about 5% at 600 °C). The microhardness of all investigated samples increased with increasing temperature of pre-annealing.

Dissolution of Ag Precipitates in the Cu⁻8wt.%Ag Alloy Deformed by High Pressure Torsion.

The aim of this work was to study the influence of severe plastic deformation (SPD) on the dissolution of silver particles in Cu⁻8wt.%Ag alloys. In order to obtain different morphologies of silver particles, samples were annealed at 400, 500 and 600 °C. Subsequently, the material was subjected to high pressure torsion (HPT) at room temperature. By means of scanning and transmission electron microscopy, as well as X-ray diffraction techniques, it was found that during SPD, the dissolution of second phase was strongly affected by the morphology and volume fraction of the precipitates in the initial state. Small, heterogeneous precipitates of irregular shape dissolved more easily than those of large size, round-shaped and uniform composition. It was also found that HPT led to the increase of solubility limit of silver in the copper matrix as the result of dissolution of the second phase. This unusual phase transition is discussed with respect to diffusion activation energy and mixing enthalpy of the alloying elements.

Ferromagnetic behaviour of ZnO: the role of grain boundaries.

The possibility to attain ferromagnetic properties in transparent semiconductor oxides such as ZnO is very promising for future spintronic applications. We demonstrate in this review that ferromagnetism is not an intrinsic property of the ZnO crystalline lattice but is that of ZnO/ZnO grain boundaries. If a ZnO polycrystal contains enough grain boundaries, it can transform into the ferromagnetic state even without doping with "magnetic atoms" such as Mn, Co, Fe or Ni. However, such doping facilitates the appearance of ferromagnetism in ZnO. It increases the saturation magnetisation and decreases the critical amount of grain boundaries needed for FM. A drastic increase of the total solubility of dopants in ZnO with decreasing grain size has been also observed. It is explained by the multilayer grain boundary segregation.