Synthesis of Tungsten Carbides in a Copper Matrix by Spark Plasma Sintering: Microstructure Formation Mechanisms and Properties of the Consolidated Materials.

In this study, the synthesis of tungsten carbides in a copper matrix by spark plasma sintering (SPS) is conducted and the microstructure formation mechanisms of the composite materials are investigated. The reaction mixtures were prepared by the high-energy mechanical milling (MM) of W, C and Cu powders. The influence of the MM time and SPS temperature on the tungsten carbide synthesis in an inert copper matrix was analyzed. It was demonstrated that the milling duration is a critical factor for creating the direct contacts between the W and C reactants and increasing the reactive transformation degree. A WC-W2C-Cu composite was fabricated from the W-C-3Cu powder mixture milled for 10 min and subjected to SPS at a temperature of 980 °C for 5 min. The formation of unconventional microstructures with Cu-rich regions is related to inter-particle melting during SPS. The WC-W2C-Cu composite showed a promising combination of mechanical and functional properties: a hardness of 300 HV, an electrical conductivity of 24% of the International Annealed Copper Standard, a residual porosity of less than 5%, a coefficient of friction in pair with a WC-6Co counterpart of 0.46, and a specific wear rate of the material of 0.52 × 10-5 mm3 N-1 m-1.

Powder Metallurgy: Materials and Processing.

This Special Issue (SI) of Materials, "Powder Metallurgy: Materials and Processing", focuses on the fundamental and applied aspects of materials fabrication by powder metallurgy [...].

Silver nanoparticle-modified melt-blown polypropylene: Antibacterial and antifungal properties and antiviral activity against SARS-CoV-2.

Melt-blown polymer fiber materials are frequently used in the face mask manufacturing. In the present work, a melt-blown polypropylene tape was modified by silver nanoparticles using chemical metallization. The silver coatings on the fiber surface consisted of crystallites 4-14 nm in size. For the first time, these materials were comprehensively tested for antibacterial, antifungal and antiviral activity. The silver-modified materials showed antibacterial and antifungal activities, especially at high concentrations of silver, and were found to be efficient against the SARS-CoV-2 virus. The silver-modified fiber tape can be used in the face mask manufacturing and as an antimicrobial and antiviral component in filters of liquid and gaseous media.

Hydroxyapatite Double Substituted with Zinc and Silicate Ions: Possibility of Mechanochemical Synthesis and In Vitro Properties.

In this study, the mechanochemical synthesis of substituted hydroxyapatite (HA) containing zinc and silicon ions having a chemical formula of Ca10-xZnx(PO4)6-x(SiO4)x(OH)2-x, where x = 0.2, 0.6, 1.0, 1.5, and 2.0, was carried out. The synthesized materials were characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and inductively coupled plasma spectroscopy. We found that HA co-substituted with zinc and silicate formed up to x = 1.0. At higher concentrations of the substituents, the formation of large amounts of an amorphous phase was observed. The cytotoxicity and biocompatibility of the co-substituted HA was studied in vitro on Hek293 and MG-63 cell lines. The HA co-substituted with zinc and silicate demonstrated high biocompatibility; the lowest cytotoxicity was observed at x = 0.2. For this composition, good proliferation of MG-63 osteoblast-like cells and an increased solubility compared with that of HA were detected. These properties allow us to recommend the synthesized material for medical applications, namely, for the restoration of bone tissue and manufacture of biodegradable implants.

Metallic Glass-Reinforced Metal Matrix Composites: Design, Interfaces and Properties.

When metals are modified by second-phase particles or fibers, metal matrix composites (MMCs) are formed. In general, for a given metallic matrix, reinforcements differing in their chemical nature and particle size/morphology can be suitable while providing different levels of strengthening. This article focuses on MMCs reinforced with metallic glasses and amorphous alloys, which are considered as alternatives to ceramic reinforcements. Early works on metallic glass (amorphous alloy)-reinforced MMCs were conducted in 1982-2005. In the following years, a large number of composites have been obtained and tested. Metallic glass (amorphous alloy)-reinforced MMCs have been obtained with matrices of Al and its alloys, Mg and its alloys, Ti alloys, W, Cu and its alloys, Ni, and Fe. Research has been extended to new compositions, new design approaches and fabrication methods, the chemical interaction of the metallic glass with the metal matrix, the influence of the reaction products on the properties of the composites, strengthening mechanisms, and the functional properties of the composites. These aspects are covered in the present review. Problems to be tackled in future research on metallic glass (amorphous alloy)-reinforced MMCs are also identified.

Nanoscale Detonation Carbon Demonstrates Biosafety in Human Cell Culture.

The production method of nanoscale detonation carbon (NDC) has recently been developed at Lavrentyev Institute of Hydrodynamics SB RAS. This method uses the reaction of acetylene with oxygen conducted in the detonation mode in fuel-rich acetylene-oxygen mixtures. The morphology and structural features of the NDC particles can be varied by changing the concentration of oxygen in the gaseous mixtures. The particles of NDC can serve as reinforcements in metal matrix composites and additives imparting electrical conductivity to polymer matrix composites. Before NDC can be considered for industrial applications, it is necessary to address the related biological safety concerns. The present work was aimed at determining the cytotoxicity of NDC. The NDC powders with two morphologies (obtained using different acetylene/oxygen ratios) were tested on HEK293A human cells. The NDC powder was added to the culture medium in concentrations ranging from 10 ng/mL to 400 µg/mL. The cell viability was determined by a colorimetric EZ4U test and a real-time cell analyzer xCELLigence. None of the NDC samples showed a cytotoxic effect. The results of this study allow us to recommend NDC as a safe and useful product for the development of advanced carbon-based and composite materials.

Selective Deposition of Mo2C-Containing Coatings on {100} Facets of Synthetic Diamond Crystals.

An efficient way to improve the properties of metal-diamond composites (mechanical strength, wear resistance, thermal conductivity) is the preliminary modification of the diamond surface to improve its wettability by the metal matrix. In the present work, Mo2C-containing coatings were deposited on the diamond crystals under different conditions: hot pressing (atmosphere of argon), spark plasma sintering (forevacuum), and annealing in air. The influence of the sintering parameters on the morphology and phase composition of the coatings deposited on diamond was studied. Mo2C-containing coatings were selectively deposited on the facets of synthetic diamond microcrystals by annealing of the latter with a molybdenum powder. Experiments were carried out to deposit coatings under different conditions: during hot pressing (argon atmosphere), spark plasma sintering (forevacuum), and annealing in air. The process parameters were the temperature, holding time, and concentration of molybdenum in the initial mixture. Experiments with a pre-oxidized molybdenum powder were also conducted. The coated diamond crystals were investigated by X-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. The deposition was enabled by the gas phase transport of molybdenum dioxide, MoO2, contained in the starting powder. The following sequence of the coating formation stages was proposed. First, MoO2 sublimes and is adsorbed mainly on the {100} facets of diamond. Then, it is reduced to metallic molybdenum by carbon of the diamond, which further reacts with carbon to form the Mo2C carbide phase. These processes occurred during treatment of the mixtures in the hot press and the spark plasma sintering facility. When the mixture was annealed in air, no selective deposition was observed. During annealing, MoO3 particles adhered to the diamond surface.

A Feasibility Study of High-Entropy Alloy Coating Deposition by Detonation Spraying Combined with Laser Melting.

In this work, a new two-stage approach to the deposition of high-entropy alloy coatings is proposed. At the first stage, a composite precursor coating is formed by detonation spraying of the metal powder mixtures. At the second stage, the precursor coating is re-melted by a laser, and the formation of multi-component solid solution phases can be expected upon solidification. The feasibility of the proposed approach was validated using three different mixtures of Fe, Ni, Cu, Co and Al powders. It was shown that detonation spraying allows forming composite coatings with a uniform distribution of the lamellae of different metals. The results of the structural analysis of the laser-treated coatings suggest that complete alloying occurred in the melt and face-centered cubic solid solutions formed in the coatings upon cooling.

Morphological and Structural Transformations of Fe-Pd Powder Alloys Formed by Galvanic Replacement, Annealing and Acid Treatment.

In this article, we report the preparation and structural features of Fe-Pd powder alloys formed by galvanic replacement, annealing and selective dissolution of iron via acid treatment. The alloys were studied by the X-ray diffraction phase analysis, Mössbauer spectroscopy, scanning electron microscopy, and energy-dispersive spectroscopy. The Fe@Pd core-shell particles were obtained by a galvanic replacement reaction occurring upon treatment of a body-centered cubic (bcc) iron powder by a solution containing PdCl42- ions. It was found that the shells are a face-centered cubic (fcc) Pd(Fe) solid solution. HCl acid treatment of the Fe@Pd core-shell particles resulted in the formation of hollow Pd-based particles, as the bcc phase was selectively dissolved from the cores. Annealing of the Fe@Pd core-shell particles at 800 °C led to the formation of fcc Fe-Pd solid solution. Acid treatment of the Fe-Pd alloys formed by annealing of the core-shell particles allowed selectively dissolving iron from the bcc Fe-based phase (Fe(Pd) solid solution), while the fcc Fe-rich Fe-Pd solid solution remained stable (resistant to acid corrosion). It was demonstrated that the phase composition and the Fe/Pd ratio in the alloys (phases) can be tailored by applying annealing and/or acid treatment to the as-synthesized Fe@Pd core-shell particles.

Core-Shell Particle Reinforcements-A New Trend in the Design and Development of Metal Matrix Composites.

Metal matrix composites (MMCs) are a constantly developing class of materials. Simultaneously achieving a high strength and a high ductility is a challenging task in the design of MMCs. This article aims to highlight a recent trend: the development of MMCs reinforced with particles of core-shell structure. The core-shell particles can be synthesized in situ upon a partial transformation of metal (alloy) particles introduced into a metal matrix. MMCs containing core-shell particles with cores of different compositions (metallic, intermetallic, glassy alloy, high-entropy alloy, metal-ceramic) are currently studied. For metal core-intermetallic shell particle-reinforced composites, the property gain by the core-shell approach is strengthening achieved without a loss in ductility. The propagation of cracks formed in the brittle intermetallic shell is hindered by both the metal matrix and the metal core, which constitutes a key advantage of the metal core-intermetallic shell particles over monolithic particles of intermetallic compounds for reinforcing purposes. The challenges of making a direct comparison between the core-shell particle-reinforced MMCs and MMCs of other microstructures and future research directions are discussed.

Detonation Spraying of Hydroxyapatite on a Titanium Alloy Implant.

Hydroxyapatite (HA), the major mineral component of tooth enamel and natural bones, is a good candidate for bone tissue engineering. Synthetic HA is used for making coatings on metallic implants intended for medical applications. A HA coating renders the implant biocompatible and osteoinductive. In addition, it improves fixation and the overall performance of the implanted object. In the present work, HA coatings were deposited on a medical titanium alloy implant with mesh geometry and a developed surface by detonation spraying. The feedstock powder was HA obtained by the dry mechanochemical method. Single-phase HA coatings were obtained. The coatings were formed not only on the surfaces normal to the particle flow direction, but also on the sides of the mesh elements. Despite partial melting of the powder, no decomposition of HA occurred. This work demonstrates the prospects of detonation spraying for the production of HA coatings on metallic implants with complex geometries.

Structure and Phase Composition of a W-Ta-Mo-Nb-V-Cr-Zr-Ti Alloy Obtained by Ball Milling and Spark Plasma Sintering.

In this paper, the structural characteristics of a W-Ta-Mo-Nb-V-Cr-Zr-Ti non-equiatomic refractory metal alloy obtained by spark plasma sintering (SPS) of a high-energy ball-milled powder mixture are reported. High-energy ball milling resulted in the formation of particle agglomerates ranging from several tens to several hundreds of micrometers. These agglomerates were composed of micrometer and submicrometer particles. It was found that, during ball milling, a solid solution of A2 structure formed. The grains of the sintered material ranged from fractions of a micrometer to several micrometers. During SPS, the phase transformations in the alloy led to the formation of a Laves phase of C15 structure and ZrO and ZrO2 nanoparticles. The microhardness of the ball-milled alloy and sintered material was found to be 9.28 GPa ± 1.31 GPa and 8.95 GPa ± 0.42 GPa, respectively. The influence of the processing conditions on the structure, phase composition, and microhardness of the alloy is discussed.

Combustion of Titanium-Carbon Black High-Energy Ball-Milled Mixtures in Nitrogen: Formation of Titanium Carbonitrides at Atmospheric Pressure.

In this work, titanium carbonitrides were synthesized by self-propagating high-temperature synthesis (SHS) in nitrogen. For the first time, the synthesis of titanium carbonitrides by combustion was realized in nitrogen at atmospheric pressure. The synthesis was carried out by subjecting high-energy ball-milled titanium-carbon black powder mixtures to combustion in a nitrogen atmosphere. The influence of the ball milling time on the phase composition of the products of SHS conducted in the Ti+0.3C reaction mixture was studied. It was found that the titanium-carbon black mixtures need to be milled for a certain period of time for the combustion synthesis to yield a single-phase carbonitride product.

Interaction of a Ti⁻Cu Alloy with Carbon: Synthesis of Composites and Model Experiments.

Titanium carbide (TiC), is the most thermodynamically stable compound in the Ti-C-Cu system, which makes it a suitable reinforcement phase for copper matrix composites. In this work, the interaction of a Ti-Cu alloy with different forms of carbon was investigated to trace the structural evolution leading to the formation of in-situ TiC-Cu composite structures. The reaction mixtures were prepared from Ti25Cu75 alloy ribbons and carbon black or nanodiamonds to test the possibilities of obtaining fine particles of TiC using ball milling and Spark Plasma Sintering (SPS). It was found that the behavior of the reaction mixtures during ball milling depends on the nature of the carbon source. Model experiments were conducted to observe the outcomes of the diffusion processes at the alloy/carbon interface. It was found that titanium atoms diffuse to the alloy/graphite interface and react with carbon forming a titanium carbide layer, but carbon does not diffuse into the alloy. The diffusion experiments as well as the synthesis by ball milling and SPS indicated that the distribution of TiC particles in the composite structures obtained via reactive solid-state processing of Ti25Cu75+C follows the distribution of carbon particles in the reaction mixtures. This justifies the use of carbon sources that have fine particles to prepare the reaction mixtures as well as efficient dispersion of the carbon component in the alloy-carbon mixture when the goal is to synthesize fine particles of TiC in the copper matrix.

Fabrication of Porous Materials by Spark Plasma Sintering: A Review.

Spark plasma sintering (SPS), a sintering method that uses the action of pulsed direct current and pressure, has received a lot of attention due to its capability of exerting control over the microstructure of the sintered material and flexibility in terms of the heating rate and heating mode. Historically, SPS was developed in search of ways to preserve a fine-grained structure of the sintered material while eliminating porosity and reaching a high relative density. These goals have, therefore, been pursued in the majority of studies on the behavior of materials during SPS. Recently, the potential of SPS for the fabrication of porous materials has been recognized. This article is the first review to focus on the achievements in this area. The major approaches to the formation of porous materials by SPS are described: partial densification of powders (under low pressures, in pressureless sintering processes or at low temperatures), sintering of hollow particles/spheres, sintering of porous particles, and sintering with removable space holders or pore formers. In the case of conductive materials processed by SPS using the first approach, the formation of inter-particle contacts may be associated with local melting and non-conventional mechanisms of mass transfer. Studies of the morphology and microstructure of the inter-particle contacts as well as modeling of the processes occurring at the inter-particle contacts help gain insights into the physics of the initial stage of SPS. For pre-consolidated specimens, an SPS device can be used as a furnace to heat the materials at a high rate, which can also be beneficial for controlling the formation of porous structures. In sintering with space holders, SPS processing allows controlling the structure of the pore walls. In this article, using the literature data and our own research results, we have discussed the formation and structure of porous metals, intermetallics, ceramics, and carbon materials obtained by SPS.

Formation of Aluminum Particles with Shell Morphology during Pressureless Spark Plasma Sintering of Fe-Al Mixtures: Current-Related or Kirkendall Effect?

A need to deeper understand the influence of electric current on the structure and properties of metallic materials consolidated by Spark Plasma Sintering (SPS) stimulates research on inter-particle interactions, bonding and necking processes in low-pressure or pressureless conditions as favoring technique-specific local effects when electric current passes through the underdeveloped inter-particle contacts. Until now, inter-particle interactions during pressureless SPS have been studied mainly for particles of the same material. In this work, we focused on the interactions between particles of dissimilar materials in mixtures of micrometer-sized Fe and Al powders forming porous compacts during pressureless SPS at 500-650 °C. Due to the chemical interaction between Al and Fe, necks of conventional shape did not form between the dissimilar particles. At the early interaction stages, the Al particles acquired shell morphology. It was shown that this morphology change was not related to the influence of electric current but was due to the Kirkendall effect in the Fe-Al system and particle rearrangement in a porous compact. No experimental evidence of melting or melt ejection during pressureless SPS of the Fe-Al mixtures or Fe and Al powders sintered separately was observed. Porous FeAl-based compacts could be obtained from Fe-40at.%Al mixtures by pressureless SPS at 650 °C.

Outside Mainstream Electronic Databases: Review of Studies Conducted in the USSR and Post-Soviet Countries on Electric Current-Assisted Consolidation of Powder Materials.

This paper reviews research articles published in the former USSR and post-soviet countries on the consolidation of powder materials using electric current that passes through the powder sample and/or a conductive die-punch set-up. Having been published in Russian, many of the reviewed papers are not included in the mainstream electronic databases of the scientific articles and thus are not known to the scientific community. The present review is aimed at filling this information gap. In the paper, the electric current-assisted sintering techniques based on high- and low-voltage approaches are presented. The main results of the theoretical modeling of the processes of electromagnetic field-assisted consolidation of powder materials are discussed. Sintering experiments and related equipment are described and the major experimental results are analyzed. Sintering conditions required to achieve the desired properties of the sintered materials are provided for selected material systems. Tooling materials used in the electric current-assisted consolidation set-ups are also described.

Crystallization of Ti33Cu67 metallic glass under high-current density electrical pulses.

We have studied the phase and structure evolution of the Ti33Cu67 amorphous alloy subjected to electrical pulses of high current density. By varying the pulse parameters, different stages of crystallization could be observed in the samples. Partial polymorphic nanocrystallization resulting in the formation of 5- to 8-nm crystallites of the TiCu2 intermetallic in the residual amorphous matrix occurred when the maximum current density reached 9.7·108 A m-2 and the pulse duration was 140 µs, though the calculated temperature increase due to Joule heating was not enough to reach the crystallization temperature of the alloy. Samples subjected to higher current densities and higher values of the evolved Joule heat per unit mass fully crystallized and contained the Ti2Cu3 and TiCu3 phases. A common feature of the crystallized ribbons was their non-uniform microstructure with regions that experienced local melting and rapid solidification.PACS: 81; 81.05.Bx; 81.05.Kf.

Properties of Cu-based nanocomposites produced by mechanically-activated self-propagating high-temperature synthesis and spark-plasma sintering.

One of the possible reasons for low conductivity of in-situ produced dispersion strengthened copper matrix composites may be the incompleteness of the reaction between the initial reactants that remain in a state of solid solutions in the copper matrix. We report in-situ synthesis of TiB2-Cu composites starting from the powder mixtures with the limited content of copper ensuring a high probability of contact between the particles of titanium and boron and, as a result, their full conversion into the TiB2 phase. The nanoparticles were formed in a self-propagating mode in the ball milled Ti-B-Cu powder mixture corresponding to 57 vol.% TiB2-Cu composition. Afterwards, the system was "diluted" with the required amount of the copper matrix using subsequent ball milling. Highly conductive 4.5 vol.% TiB2-Cu composites showing 82-87% IACS (International Annealed Copper Standard) conductivity were obtained by Spark Plasma Sintering (SPS) of the powders.