Application of pulse discharge sintering (PDS) technique to rapid synthesis of Ti3SiC2 from Ti/Si/C powders

To synthesize Ti₃SiC₂ samples, pulse discharge sintering (PDS) technique was utilized to sinter elemental powders of Ti/Si/C with stoichiometric and off-stoichiometric ratios in a temperature range of 1200–1500 °C. The results showed that high purity Ti₃SiC₂ could not be obtained from the Ti/Si/C powder with molar ratio of 3:1:2, and Ti₃SiC₂ preferred to form at relatively low sintering temperature for a short time. When 5Ti/2Si/3C and 3Ti/1.5Si/2C powders were sintered for 15 min, the TiC content was respectively decreased to 6.4 and 10 wt.% at 1250–1300 °C. The corresponding relative density of the samples sintered from 5Ti/2Si/3C powder was calculated to be as high as 99% at the temperature above 1300 °C. It is suggested that low-temperature rapid synthesis of Ti₃SiC₂ would be possible through the PDS technique, provided that the composition of the starting powders should be adjusted to be off-stoichiometric ratio from 3:1:2.     

Synthesis of single-phase Ti3SiC2 powder

In this study, free 2Ti/2Si/3TiC powder mixture was heated at high temperatures in vacuum, in order to reveal the possibility for the synthesis of high Ti₃SiC₂ content powder. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used for the evaluation of phase identities and the morphology of the powder after different treatments. Results showed that almost single phase Ti₃SiC₂ powder (99.3 wt.%) can be synthesized by heat treatment with free 2Ti/2Si/3TiC powders in vacuum at 1210°C for about 3 h. The nucleation and growth of Ti₃SiC₂ within TiC particles was observed. The typical appearance of the formed Ti₃SiC₂ is equiaxed with particle size of 2–4 μm. Effects of temperature and heating time on the morphology and the particle sizes of the synthesized Ti₃SiC₂ powders are not obvious.     

Preparation and characterization of Ti3SiC2 powder

Pressureless sintering in vacuum was applied to synthesize Ti₃SiC₂ from elemental powders of Ti, Si and C. Based on the phase compositions and purities of the products obtained by X-ray diffraction, the elemental powders composition and sintering condition were optimized. It was found that the sample sintered at 1450 °C for 240 min from a mixture of 3Ti/1.75Si/2C (molar ratio) contained Ti₃SiC₂ with the volume fraction as high as 93%. It was proposed that loss of Si through gaseous vaporization and contamination of C might be the main obstacles against obtaining high-purity material by this way.     

Effect of Al2O3 on mechanical properties of Ti3SiC2/Al2O3 composite

The effect of Al₂O₃ on mechanical properties of Ti₃SiC₂/Al₂O₃ composite fabricated by SPS was studied systematically. The results show that the hardness of the Ti₃SiC₂/Al₂O₃ composite can reach 10.28 GPa, 50% higher than that of pure Ti₃SiC₂. However, slight decrease in the other mechanical properties was observed with Al₂O₃ addition higher than 5–10 vol.%, which is believed to be due to the agglomeration of Al₂O₃ in the composite.     

Surface strengthening of Ti3SiC2 through magnetron sputtering Cu and subsequent annealing

Magnetron sputtering deposition Cu and subsequent annealing in the temperature range of 900–1100 °C for 30–60 min were conducted with the motivation to modify the surface hardness of Ti₃SiC₂. Owing to the formation of TiC following the reaction Ti₃SiC₂ + 3Cu → 3TiC_0.67 + Cu₃Si, the surface hardness was enhanced from 5.08 GPa to a maximum 9.65 GPa. In addition, the surface hardness was dependent on the relative amount of TiC, which was related to Cu film thickness, heat treatment temperatures and durations of annealing. Furthermore, after annealing at 1000 °C for 30 min the Cu-coated Ti₃SiC₂ has lower wear rate and lower COF at the running-in stage compared with Ti₃SiC₂ substrate. The reaction was triggered by the inward diffusion of Cu along the grain boundaries and defects of Ti₃SiC₂. At low temperature and short annealing time, i.e. 900 or 1000 °C for 30 min, Cu diffused inward Ti₃SiC₂ and accumulated at the trigonal junctions first. At higher temperature of 1100 °C or prolonging the annealing time to 60 min, considerable amount of Cu diffused to Ti₃SiC₂ and filled up the grain boundaries leaving a mesh structure.     

Al alloy/Ti3SiC2 composites fabricated by pressureless infiltration with melt-spun Al alloy ribbons

Al alloy/Ti₃SiC₂ composites with compressive strengths ranging from 743 to 932 MPa have been successfully fabricated by a new two-step pressureless infiltration method. 6061 Al alloy ribbons prepared by melt spinning were employed as the Al alloy matrix for melt infiltration. Shifts in phase constitution and reaction mechanisms of Ti₃SiC₂ preforms in molten Al at 950 °C were investigated, and the compression performance of Al alloy/Ti₃SiC₂ composites was tested. The Vickers hardness of the composites was enhanced to a maximum of 751 HV by increasing the Al content.     

In situ reaction synthesis and characterization of Ti3Si(Al)C2/SiC composites

The reaction route, microstructure, and properties of Ti₃Si(Al)C₂/SiC composites with 5–30 vol.% SiC content prepared by in situ hot pressing/solid–liquid reaction synthesis process are investigated. In contrast to monolithic Ti₃Si(Al)C₂, the SiC particle-reinforced composites exhibit higher elastic modulus, Vickers hardness, fracture toughness, improved wear, and oxidation resistance, but have a slight loss in flexural strength. The improvement in the properties is mainly ascribed to the contribution of SiC particles, and the strength degradation is due to the residual tensile stresses in the matrix.     

Impurity control in pressureless reactive synthesis of pure Ti3SiC2 bulk from elemental powders

The impurity control in pressureless reactive synthesis of pure Ti₃SiC₂ from elemental powders is reported. Ti₃SiC₂ bulk samples were prepared by sintering compacts of ball-mixed elemental powders at 1500 °C for 2 h in lidded alumina crucibles under Ar atmosphere. Undesirable TiC impurity was successfully eliminated from the synthesized product. Product with desired phase constituent can be fabricated by preparing samples according to phase diagram data. Keeping away from the phase fields that involve TiC is a vital way to obtain pure Ti₃SiC₂ without containing the undesirable TiC. The key for successful impurity control in the sintering process is the conservation of mass in the reactants.     

Effect of liquid reaction on the synthesis of Ti3SiC2 powder

Synthesis of Ti₃SiC₂ powder was carried out by heat treating powder mixtures of Si, TiC and coarse Ti (−150 μm) in a temperature range of 1000–1400 °C. The phase content of Ti₃SiC₂ in the synthesized powder was improved to 99% when heat treated at 1400 °C for 4 h. Ti–Si liquid reaction was found to occur above the binary eutectic temperature, and this liquid reaction is believed to have assisted the synthesis reaction of Ti₃SiC₂.     

Effect of the starting materials on the reaction synthesis of Ti3SiC2

Ternary carbide of titanium and silicon was produced via mechanical milling and following heat treatment. Effects of the starting materials, milling time and heat treatment temperature were studied. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were utilized to evaluate the structural and morphological evolutions of the ball-milled and annealed powders. Results showed that the ball milling of TiO–Si–C as the starting materials failed to synthesize Ti₃SiC₂. Additionally, ball milling the elemental powders for shorter milling times resulted in the activation of the powders. However, after longer milling times, Ti–TiC nanocomposite was obtained. Furthermore, during annealing the milled powders, Ti₃SiC₂–TiC nanocomposite with the mean grain size of 16 nm was synthesized. After 20 h of milling, a very fine microstructure with narrow size of distribution and spheroid particles was achieved.     

Al对等离子放电烧结法合成Ti3SiC2的影响研究

以元素为原料，Al为助剂，采用等离子放电烧结(SPS)工艺合成Ti3SiC2块体材料，通过X射线衍射分析和对SPS过程参数的研究表明：适量A1能促进Ti3SiC2的反应合成，提高合成材料的纯度，但Al也会使Ti3SiC2的热稳定性降低。     

Effect of Ti5Si3 on wear properties of Ti3Si(Al)C2

Near-fully dense Ti₃Si(Al)C₂/Ti₅Si₃ composites were synthesized by in situ hot pressing/solid–liquid reaction process under a pressure of 30 MPa in a flowing Ar atmosphere at 1580 °C for 60 min. Compared to monolithic Ti₃Si(Al)C₂, Ti₃Si(Al)C₂/Ti₅Si₃ composites exhibit higher hardness and improved wear resistance, but a slight loss in flexural strength (about 26% lower than Ti₃Si(Al)C₂ matrix). In addition, Ti₃Si(Al)C₂/Ti₅Si₃ composites maintain a high fracture toughness (K_IC = 5.69–6.79 MPa m^1/2). The Ti₃Si(Al)C₂/30 vol.%Ti₅Si₃ composite shows the highest Vickers hardness (68% higher than that of Ti₃Si(Al)C₂) and best wear resistance (the wear resistance increases by 2 orders of magnitude). The improved properties are mainly ascribed to the contribution of hard Ti₅Si₃ particles, and the strength degradation is mainly due to the lower Young's modulus and strength of Ti₅Si₃.     

Si-rich pressureless sintering of the gelcasted Ti3SiC2 bulk ceramic

The Si-rich pressureless sintering was used to fabricate the Ti₃SiC₂ bulk ceramic. The results show that the optimized Ti₃SiC₂ suspension could be prepared at the absolute value of zeta potential, pH level, PAA-NH₄ dosage, and solid loading of 62.1 mV, 11, 2.0 wt%, and 50 vol%, respectively. The channels existing in the Si-free sintered body facilitated the reactants and products to diffuse to the interior and out of the Ti₃SiC₂ matrix, thereby forming the porous reaction layer of TiC-Ti₃SiC₂. The co-effects of the channels and the reaction layer of TiC-Ti₃SiC₂ severely lowered mechanical properties of the Si-free sintered Ti₃SiC₂ ceramic. On the contrary, the Si-rich sintering method isolated the volatile carbon and established a closed Si-rich atmosphere to sinter the green Ti₃SiC₂ cylinder. The porosity, density, fracture toughness, hardness, and flexural strength of the Si-rich sintered Ti₃SiC₂ ceramic reached 0.74 vol%, 4.36 g/cm³, 5.49 MPa·m^1/2, 4.03 GPa, and 383 MPa, respectively.     

Rapid synthesis of Ti3AlC2/TiB2 composites by the spark plasma sintering (SPS) technique

Dense Ti₃AlC₂/TiB₂ composites were successfully fabricated from B₄C/TiC/Ti/Al powders by spark plasma sintering (SPS). The microstructure, flexural strength and fracture toughness of the composites were investigated. The experimental results indicate that the Vickers hardness increased with the increase in TiB₂ content. The maximum flexural strength (700 ± 10 MPa) and fracture toughness (7.0 ± 0.2 MPa m^1/2) were achieved through addition of 10 vol.% TiB₂, however, a slight decrease in the other mechanical properties was observed with TiB₂ addition higher than 10 vol.%, which is believed to be due to TiB₂ agglomeration.     

Carbon atmosphere effect on Ti3SiC2 based composites made from TiC/Si powders

The effect of carbon activity and CO pressure in the furnace atmosphere is investigated with respect to the phase reactions during heat treatment of TiC/Si powders. Special attention is given to the production and decomposition of Ti₃SiC₂. Samples were heated in graphite and alumina furnaces, connected to a dilatometer which enabled in situ analysis of the phase reactions. The phase compositions of the heat treated samples were determined by X-ray diffraction. The reducing atmosphere of the graphite furnace enhanced the reactivity of the starting powder and enabled phase reactions to take place at a lower temperature than in the alumina furnace. TiSi₂ and SiC phases formed at temperatures below the melting point of Si and were continuously consumed at higher temperatures. Ti₃SiC₂ formed at the melting point of Si regardless of furnace atmosphere. No decomposition of the Ti₃SiC₂ was observed in either furnace.     

Reactive synthesis for porous Ti3AlC2 ceramics through TiH2, Al and graphite powders

Porous Ti₃AlC₂ ceramics were fabricated by reactive synthesis. The process of fabrication involved five steps: (i) the pyrolysis of stearic acid at 450 °C; (ii) the decomposition of TiH₂ at 700 °C, which leads to the conversion of TiH₂ to Ti; (iii) the solid–liquid chemical reaction of solid Ti and molten Al at 800–1000 °C, which converts the mixture to Ti–Al compounds; (iv) the newly synthesized Ti–Al compounds that react with surplus Ti and graphite to form ternary carbides and TiC at 1100–1200 °C; and (v) reactive synthesized ternary carbides and TiC that yield porous Ti₃AlC₂ at 1300 °C.     

Effect of sintering temperature and Ho2O3 on the properties of TiO2-based varistors

In this study, a series of TiO₂-based ceramics doped with different contents of Ho₂O₃ in the range of 0–0.6?mol% are prepared by means of a conventional solid-state reaction method. Phase composition, microstructure and element distribution are studied by use of X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) separately. The influence of sintering temperature and Ho₂O₃ on the properties of samples is explored. The results show that the breakdown voltage decreases continuously while both the nonlinear coefficient and the relative dielectric constant ascend firstly and then descend with the sintering temperature increasing. Meanwhile, the relative dielectric constant and nonlinear coefficient of samples firstly ascend and then descend with the increasing of Ho₂O₃. Although the minimum breakdown voltage (3.3?V/mm) is obtained when sample is sintered at 1450?°C, the sample doped with 0.45?mol% Ho₂O₃ sintered at 1400?°C exhibits high comprehensive electrical properties, with breakdown voltage of 6?V/mm, the nonlinear coefficient of 5.5 and the relative dielectric constant of 1.88?×?10⁵.     

Effects of Al2O3 addition on the sintering behavior and microwave dielectric properties of CaSiO3 ceramics

The effects of Al₂O₃ addition on the densification, structure and microwave dielectric properties of CaSiO₃ ceramics have been investigated. The Al₂O₃ addition results in the presence of two distinct phases, e.g. Ca₂Al₂SiO₇ and CaAl₂Si₂O₈, which can restrict the growth of CaSiO₃ grains by surrounding their boundaries and also improve the bulk density of CaSiO₃-Al₂O₃ ceramics. However, excessive addition (≥2 wt%) of Al₂O₃ undermines the microwave dielectric properties of the title ceramics since the derived phases of Ca₂Al₂SiO₇ and CaAl₂Si₂O₈ have poor quality factor. The optimum amount of Al₂O₃ addition is found to be 1 wt%, and the derived CaSiO₃-Al₂O₃ ceramic sintered at 1250 °C presents improved microwave dielectric properties of ?_r = 6.66 and Q × f = 24,626 GHz, which is much better than those of pure CaSiO₃ ceramic sintered at 1340 °C (Q × f = 13,109 GHz).     

Phase analysis and wear behavior of in-situ spark plasma sintered Ti3SiC2

In-situ synthesis of dense near-single phase Ti₃SiC₂ ceramics from 3Ti/SiC/C/0.15Al starting powder using spark plasma sintering (SPS) at 1250 °C is reported. Systematic analysis of the phase development over a range of sintering temperatures (1050–1450 °C) suggested that solid state reactions between intermediate TiC and Ti₅Si₃ phases lead to the formations of Ti₃SiC₂. The effect of starting powder composition on phase development after SPS at 1150 °C was also investigated using three distinct compositions (3Ti/SiC/C, 2Ti/SiC/TiC, and Ti/Si/2TiC). The results indicate that the starting powder compositions, with higher amounts of intermediate phase such as TiC, favor the formation of Ti₃SiC₂ at relatively lower sintering temperature. Detailed analysis of wear behavior indicated that samples with higher percentage of TiC, present either as an intermediate phase or a product of Ti₃SiC₂ decomposition, exhibited higher microhardness and better wear resistance compared to near single phase Ti₃SiC₂.     

Material removal and surface damage in EDM of Ti3SiC2 ceramic

Material removal and surface damage of Ti₃SiC₂ ceramic during electrical discharge machining (EDM) were investigated. Melting and decomposition were found to be the main material removal mechanisms during the machining process. Material removal rate was enhanced acceleratively with increasing discharge current, i_e, working voltage, u_i, but increased deceleratively with pulse duration, t_e. Microcracks in the surface and loose grains in the subsurface resulted from thermal shock were confirmed, and the surface damage in Ti₃SiC₂ ceramic led to a degradation of both strength and reliability.