Search Results (15)

The reactive spark plasma sintering (R-SPS) method was compared in this work with the two-step SHS–SPS route, based on the combination of the self-propagating high-temperature synthesis (SHS) with the SPS process, for the fabrication of dense (Hf_0.2Mo_0.2Ti_0.2Ta_0.2Nb_0.2)B₂–SiC and (Hf_0.2Mo_0.2Ti_0.2Ta_0.2Zr_0.2)B₂–SiC ceramics. A multiphase and inhomogeneous product, containing various borides, was obtained at 2000 °C/20 min by R-SPS from transition metals, B₄C, and Si. In contrast, if the same precursors were first reacted by SHS and then processed by SPS under the optimized condition of 1800 °C/20 min, the desired ceramics were successfully attained. The resulting sintered samples possessed relative densities above 97% and displayed uniform microstructures with residual oxide content <2.4 wt.%. The presence of SiC made the sintering temperature milder, i.e., 150 °C below that needed by the corresponding additive-free system. The fracture toughness was also markedly improved, particularly when considering the Nb-containing system processed at 1800 °C/20 min, whereas the fracture toughness progressively decreased (from 7.35 to 5.36 MPa m^1/2) as the SPS conditions became more severe. SiC addition was found to inhibit the volatilization of metal oxides like MoO₃ formed during oxidation experiments, thus avoiding mass loss in the ceramics. The benefits above also likely took advantage of the fact that the two composite constituents were synthesized in parallel, according to the SHS–SPS approach, rather than being produced separately and combined subsequently, so that strong interfaces between them were formed. Full article

A novel solid-phase synthetic approach was developed to produce a mineral-like composite ceramic based on strontium titanate (SrTiO₃) and yttrium titanate (Y₂Ti₂O₇) matrices for immobilizing radionuclides such as ⁹⁰Sr and its daughter product ⁹⁰Y, as well as lanthanides and actinides, via reactive spark plasma sintering technology (SPS-RS). Using XRD, SEM, and EDS analyses, the sintering kinetics of the initial mixed oxide reactants of composition Y_xSr_1–1.5xTiO₃ (x = 0.2, 0.4, 0.6 and 1) and structure-phase changes in the ceramics under SPS-RS conditions were investigated as a function of Y³⁺ content. In addition, a detailed study of phase transformation kinetics over time as a function of the heating temperature of the initial components (SrCO₃, TiO₂, and Y₂O₃) was conducted via in situ synchrotron XRD heating experiments. The composite ceramic achieved relatively high physicomechanical properties, including relative density between 4.92–4.64 g/cm³, Vickers microhardness of 500–800 HV, and compressive strength ranging from 95.5–272.4 MPa. An evaluation of hydrolytic stability and leaching rates of Sr²⁺ and Y³⁺ from the matrices was performed, demonstrating rates did not exceed 10⁻⁵–10⁻⁶ g·cm⁻²·day⁻¹ in compliance with GOST R 50926-96 and ANSI/ANS 16.1 standards. The leaching mechanism of these components was studied, including the calculation of solution penetration depth in the ceramic bulk and ion diffusion coefficients in the solution. These findings show great promise for radioactive waste conditioning technologies and the manufacturing of radioisotope products. Full article

This research introduces a method to enhance the biocompatibility of bioinert Al₂O₃-based ceramics by incorporating calcium phosphates (hydroxyapatite (HAp) and tricalcium phosphate (TCP)) into alumina via spark plasma sintering-reactive sintering (SPS-RS). TGA/DTG/DTA and XRD revealed phase formation of HAp and TCP and determined the main temperature points of solid-phase reactions occurring in situ during the sintering of the CaO-CaHPO₄ mixture within the volume of Al₂O₃ under SPS-RS conditions in the range of 900–1200 °C. SEM, EDX, low temperature, and nitrogen physisorption were used to monitor changes in the morphology, structure, and elemental composition of bioceramics. Structural meso- and macroporosity, with a mean mesopore size of 10 nm, were revealed in the ceramic volume, while sintering temperature was shown to play a destructive role towards the porous inorganic framework. The physico-chemical characterization demonstrated increased relative density (up to 95.1%), compressive strength (640 MPa and above), and Vickers microhardness (up to 700 HV) depending on the HAp and TCP content and sintering temperature. Four bioceramic samples with different contents of HAP (20 and 50 wt.%) were bio-tested in in vivo models. The samples were implanted into the soft tissues under the superficial fascia of the thorax of a laboratory animal (a New Zealand White rabbit, female) in the area of the trapezius muscle and the broadest muscle of the back. Based on the results of the assessment of the surrounding tissue reaction, the absence of specific inflammation, necrosis, and tumor formation in the tissues during the implantation period of 90 days was proven. Microbial tests and dynamics of Pseudomonas aeruginosa bacterial film formation on bioceramic surfaces were studied with respect to HAp content (20 and 50 wt.%) and holding time (18, 24, and 48 h) in the feed medium. Full article

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. Full article

W-Si-C composites with high relative densities and good mechanical and wear properties were successfully prepared by spark plasma sintering. The influence of SiC content on the relative density, microstructure, mechanical properties and wear characteristics was investigated. The results indicated that the reaction between SiC and W at their interface produced W₂C and W₅Si₃. SiC also reacted with oxygen impurities at the W grain boundary to form SiO₂. The purification of the grain boundaries of W was carried out by SiO₂ synthesis. Reactive sintering reduces the free energy of the system and facilitates the densification process of W-Si-C composites. This results in a significant increase in the relative density of W-Si-C composites, which reaches a maximum of 98.12%, higher than the 94.32% of pure tungsten. The hardness significantly increases from 4.33 GPa to 8.40 GPa when the SiC content is 2 wt% compared to pure tungsten due to the generation of the hard ceramic phase and the increase in relative density. The wear resistance of the W-Si-C composites was significantly improved with little SiC addition. The wear rate significantly decreased from 313.27 × 10⁻³ mm³/N·m of pure tungsten to 5.71 × 10⁻³ mm³/N·m of W-0.5 wt% SiC. SEM analyses revealed that the dominant wear mechanism of pure tungsten was attributed to fatigue wear, while that of W-Si-C composites was due to abrasive wear. Full article

The present work reports the direct production of a high-entropy (HE) intermetallic CoNi_0.3Fe_0.3Cr_0.15Al material with a B2 structure from mechanically activated elemental powder mixtures. Fast and efficient combustion synthesis (CS), spark plasma sintering (SPS), and reactive SPS (RSPS) methods were used to synthesize the HE powders and bulks. The formation of the main B2 phase along with some amounts of secondary BCC and FCC phases are reported, and L12 intermetallic (CS scheme) and BCC based on Cr (CS + SPS and RSPS schemes at 1000 °C) were observed in all samples. The interaction between the components during heating to 1600 °C of the mechanically activated mixtures and CS powders has been studied. It has been shown that the formation of the CoNi_0.3Fe_0.3Cr_0.15Al phase occurs at 1370 °C through the formation of intermediate intermetallic phases (Al₉Me₂, AlCo, AlNi₃) and their solid solutions, which coincidences well with thermodynamic calculations and solubility diagrams. Compression tests at room and elevated temperatures showed that the alloy obtained by the RSPS method has enhanced mechanical properties (σ_p = 2.79 GPa, σ_0.2 = 1.82 GPa, ε = 11.5% at 400 °C) that surpass many known alloys in this system. High mechanical properties at elevated temperatures are provided by the B2 ordered phase due to the presence of impurity atoms and defects in the lattice. Full article

We present a new reactive spark plasma sintering (RSPS) technique for synthesizing the rhombohedral Ca${}_{14}$Si${}_{19}$ phase. The RSPS approach reduces the synthesis time from several weeks to a few minutes. The RSPS was found to be sufficient for obtaining a high level of purity of the Ca${}_{14}$Si${}_{19}$ under a pressure of 100 MPa for a dwell period of 5 min at a temperature of 900 ${}^{\circ }$C. From electrical resistivity measurements, we were able to determine the energy band gap of Ca${}_{14}$Si${}_{19}$ to $E_{\mathrm{g}}=0.145\left(15\right)$ eV. The Seebeck coefficient shows Ca${}_{14}$Si${}_{19}$ as a p-type semiconductor at room temperature. It becomes n-type with increasing temperature pointing to significant bipolar and conduction band contributions due to the narrow bandgap of the compound. Full article

A nucleation method based on a composite of uranium dioxide (UO₂) and graphene is presented by in situ synthesis, and the relevant mechanism and fuel properties are investigated. UO₂–graphene composite fuel powders containing graphene volume (2%, 4%, 6%, and 8%) were prepared using a nucleation method through the reactive deposition of uranyl nitrate and aqueous ammonia on graphene by controlling the reaction parameters. The composite fuel pellets were prepared using spark plasma sintering (SPS). The results showed that the uniformity of UO₂–graphene powder prepared by in situ synthesis reached up to 96.39%. An analysis on the relevant phase structure showed that only UO₂ and graphene existed in the sintered pellets at 1723 K, graphene and UO₂ were not destroyed during the reaction, and the pellet densities for the in-situ synthesis were 95.56%TD, 95.32%TD, 95.08%TD, and 94.76%TD for graphene contents of 2%, 4%, 6%, and 8%, respectively. The thermal conductivities of pellets at 293 K increased by 12.27%, 20.13%, 27.47%, and 34.13%, and by 18.36%, 35.00%, 47.07%, and 58.93% at 1273 K for 2%, 4%, 6%, and 8% graphene contents, respectively. The performance of graphene in the fuel was superior at high temperatures, which overcame shortcomings due to the low thermal conductivity of UO₂ at high temperatures. SEM results showed that the grain sizes of the pellets prepared by synthesis in situ were 10–30 μm, and there was no obvious pore at the grain boundary because the grains were closely bound. The graphene was uniformly coated by UO₂, and the thermal conductivity of the pellets improved upon the formation of a bridging heat conduction network. Full article

Metal–ceramic composites are obtained via ex-situ or in-situ routes. The in-situ route implies the synthesis of reinforcement in the presence of a matrix and is often regarded as providing more flexibility to the microstructure design of composites than the ex-situ route. Spark plasma sintering (SPS) is an advanced sintering method that allows fast consolidation of various powder materials up to full or nearly full density. In reactive SPS, the synthesis and consolidation are combined in a single processing step, which corresponds to the in-situ route. In this article, we discuss the peculiarities of synthesis of ceramic reinforcements in metallic matrices during SPS with a particular consideration of reactant/matrix mutual chemistry. The formation of carbide reinforcements in Cu, Al, and Ni matrices is given attention with examples elaborated in the authors’ own research. Factors determining the suitability of reactive SPS for manufacturing of composites from a matrix/reactants system and features of the structural evolution of the reaction mixture during sintering are discussed. Full article

MAX phases are an advanced class of ceramics based on ternary carbides or nitrides that combine some of the ceramic and metallic properties, which make them potential candidate materials for many engineering applications under severe conditions. The present work reports the successful synthesis of nearly single bulk Ti₂AlN MAX phase (>98% purity) through solid-state reaction and from a Ti and AlN powder mixture in a molar ratio of 2:1 as starting materials. The mixture of Ti and AlN powders was subjected to reactive spark plasma sintering (SPS) under 30 MPa at 1200 °C and 1300 °C for 10 min in a vacuum atmosphere. It was found that the massive formation of Al₂O₃ particles at the grain boundaries during sintering inhibits the development of the Ti₂AlN MAX phase in the outer zone of the samples. The effect of sintering temperature on the microstructure and mechanical properties of the Ti₂AlN MAX phase was investigated and discussed. Full article

The traditional solid-state reaction method was employed to synthesize bulk calcium cobaltite (Ca349/Ca₃Co₄O₉) ceramics via ball milling the precursor mixture. The samples were compacted using conventional sintering (CS) and spark plasma sintering (SPS) at 850, 900, and 950 °C. The X-ray diffraction (XRD) pattern indicates the presence of the Ca349 phase for samples sintered at 850 and 900 °C. In addition, SPS fosters higher densification (81.18%) than conventional sintering (50.76%) at elevated sintering temperatures. The thermo-gravimetric analysis (TGA) and differential thermal analysis (DTA) performed on the precursor mixture reported a weight loss of ~25.23% at a temperature range of 600–820 °C. This current work aims to analyze the electrical properties (Seebeck coefficient (s), electrical resistivity (ρ), and power factor) of sintered samples as a function of temperature (35–500 °C). It demonstrates that the change in sintering temperature (conventional sintering) did not evince any significant change in the Seebeck coefficient (113–142 μV/K). However, it reported a low resistivity of 153–132 μΩ-m and a better power factor (82–146.4 μW/mK²) at 900 °C. On the contrary, the SPS sintered samples recorded a higher Seebeck coefficient of 121–181 μV/K at 900 °C. Correspondingly, the samples sintered at 950 °C delineated a low resistivity of 145–158 μΩ-m and a better power factor (97–152 μW/mK²). Full article

The article presents an original way of getting porous and mechanically strong CaSiO₃-HAp ceramics, which is highly desirable for bone-ceramic implants in bone restoration surgery. The method combines wet and solid-phase approaches of inorganic synthesis: sol-gel (template) technology to produce the amorphous xonotlite (Ca₆Si₆O₁₇·2OH) as the raw material, followed by its spark plasma sintering–reactive synthesis (SPS-RS) into ceramics. Formation of both crystalline wollastonite (CaSiO₃) and hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) occurs “in situ” under SPS conditions, which is the main novelty of the method, due to combining the solid-phase transitions of the amorphous xonotlite with the chemical reaction within the powder mixture between CaO and CaHPO₄. Formation of pristine HAp and its composite derivative with wollastonite was studied by means of TGA and XRD with the temperatures of the “in situ” interactions also determined. A facile route to tailor a macroporous structure is suggested, with polymer (siloxane-acrylate latex) and carbon (fibers and powder) fillers being used as the pore-forming templates. Microbial tests were carried out to reveal the morphological features of the bacterial film Pseudomonas aeruginosa that formed on the surface of the ceramics, depending on the content of HAp (0, 20, and 50 wt%). Full article

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. Full article

This paper reports about a new synthesis method for preparing Mg₂Si in an efficient way. The intermetallic Mg₂Si-phase forms gradually from a mixture of Mg and Si fine powder during exposure to hydrogen atmosphere, which reacts in a vacuum vessel at 350 °C. The resulting powder has the same particle size (100 µm) compared with commercial Mg₂Si powder, but higher reactivity due to large surface area from particulate morphology. Both types of powders were compacted by spark plasma sintering (SPS) experiments at 627, 602, 597, and 400 °C for 600 s with a compaction pressure of 80 MPa. The thermoelectric characterization was performed with low and high temperature gradients of ΔT = 10 K up to 600 K. The results confirmed a Seebeck coefficient of −0.14 mV/K for specimens sintered from both powders. The small difference in total performance between purchased and produced power is considered to be due to the effect of impurities. The best values were obtained for n-type Mg₂Si doped with 3% Bi yielding a Seebeck coefficient of −0.2 mV/K, ZT = 0.45) and electric output power of more than 6 µW. Full article

A wider utilization of ultra high temperature ceramics (UHTC) materials strongly depends on the availability of efficient techniques for their fabrication as dense bodies. Based on recent results reported in the literature, it is possible to state that Spark Plasma Sintering (SPS) technology offers a useful contribution in this direction. Along these lines, the use of two different SPS-based processing routes for the preparation of massive UHTCs is examined in this work. One method, the so-called reactive SPS (R-SPS), consists of the synthesis and densification of the material in a single step. Alternatively, the ceramic powders are first synthesized by Self-propagating High-temperature Synthesis (SHS) and then sintered by SPS. The obtained results evidenced that R-SPS method is preferable for the preparation of dense monolithic products, while the sintering of SHS powders requires relatively milder conditions when considering binary composites. The different kinetic mechanisms involved during R-SPS of the monolithic and composite systems, i.e., combustion-like or gradual solid-diffusion, respectively, provides a possible explanation. An important role is also played by the SHS process, particularly for the preparation of composite powders, since stronger interfaces are established between the ceramic constituents formed in situ, thus favoring diffusion processes during the subsequent SPS step. Full article