Synthesis and reaction mechanism of Ti3SiC2 ternary compound by carbothermal reduction of TiO2 and SiO2 powder mixtures

The present study aims to investigate synthesis of Ti₃SiC₂ from TiO₂ and SiO₂ powder mixtures by carbothermal reduction method. Equilibrium TiO₂–SiO₂–C ternary phase diagram was used to predict the conditions for the formation of Ti₃SiC₂ at 1800 K under Ar atmosphere. A reactant mixture with a TiO₂:SiO₂ molar ratio of 1.5 and a C content of 68.75 mol% (26.86 wt%) was initially selected among the thermodynamically favorable reactant compositions for the experimental studies. Two different C sources, graphite flakes and pyrolytic C coating, were used to synthesize Ti₃SiC₂ at 1800 K under Ar atmosphere. When graphite flakes were used, the products contained a trace amount of Ti₃SiC₂ phase along with major TiC and minor SiC phases. Whereas, pyrolytic C coating on the oxide particles resulted in the products with much higher Ti₃SiC₂ contents owing to the close contact between the reactants. Optimal C concentration for the C coated oxide mixtures with a TiO₂:SiO₂ molar ratio of 1.5 was determined to be 30.05 wt% under the experimental conditions studied. Ti₃SiC₂ content of the products obtained from this reactant was observed to increase with reaction time to 31 wt% at 75 min beyond which it gradually decreased. XRD studies indicated that the product with the highest ternary carbide content also contained TiC and a trace amount of SiC. SEM-EDS analyses showed that this sample essentially consisted of spherical fine TiC particles and Ti₃SiC₂ nanolaminates. Equilibrium thermodynamic analysis of the TiO₂–SiO₂–C system suggested that the reaction of solid Ti₂O₃ with SiO and CO gases may play a dominant role in the formation of 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.     

Formation of Ti3SiC2 interphase coating on SiCf/SiC composite by electrophoretic deposition

To improve the oxidation resistance of SiC composites at high temperature, the feasibility of using Ti₃SiC₂ coated via electrophoretic deposition (EPD) as a SiC fiber reinforced SiC composite interphase material was studied. Through fiber pullout, Ti₃SiC₂, due to its lamellar structure, has the possibility of improving the fracture toughness of SiC_f/SiC composites. In this study, Ti₃SiC₂ coating was produced by EPD on SiC fiber; using Ti₃SiC₂‐coated SiC fabric, SiC_f/SiC composite was fabricated by hot pressing. Platelet Ti₃SiC₂ powder pulverized into nanoparticles through high‐energy wet ball milling was uniformly coated on the SiC fiber in a direction in which the basal plane of the particles was parallel to the fiber. In a 3‐point bending test of the SiC_f/SiC composite using Ti₃SiC₂‐coated SiC fabric, the SiC_f/SiC composite exhibited brittle fracture behavior, but an abrupt slope change in the strength‐displacement curve was observed during loading due to the Ti₃SiC₂ interphase. On the fracture surface, delamination between each layer of SiC fabric was observed.     

Synthesis and microstructure of the Ti3SiC2 in SiC matrix grown by chemical vapor deposition

Ti₃SiC₂ + SiC and TiC + SiC were deposited on graphite substrate at 1300–1600 °C by chemical vapor deposition with TiCl₄, SiCl₄, C₃H₈, H₂ as reactive gases. Process parameters such as temperature, pressure, concentration of C₃H₈ were varied to study their effects on the phases and microstructure of the deposited layers. The results show that binary phases of Ti₃SiC₂ + SiC are formed at temperature less than 1400 °C. For temperature above 1500 °C, TiC + SiC phases are formed. Increase of the process pressure causes the disappearance of Ti₃SiC₂ and the formation of TiC. The surface morphology of Ti₃SiC₂ shows a plate-like structure. The hardness of Ti₃SiC₂ + SiC and TiC + SiC is HV4251 and HV4612 respectively for a load of 10 g.     

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.     

In-situ fabrication of laminated SiC/TiSi2 and SiC/Ti3SiC2 ceramics by liquid silicon infiltration

The laminated silicon carbide/titanium silicon (SiC/TiSi₂) and silicon carbide/titanium silicon carbide (SiC/Ti₃SiC₂) ceramics were successfully designed and fabricated by liquid silicon (Si) infiltration. When the thickness of TiC layer was 150 and 450?µm, the TiSi₂ and Ti₃SiC₂ phases were the main products in the TiC layer, respectively. The as-fabricated structural unit of laminated SiC/Ti₃SiC₂ ceramics consisted of five layers of functionally graded materials, which has multiscale layered structure containing macro-layered structure and nano layered structure. The generation of hierarchical structure was attributed to the diffusion of Ti elements and in-situ formation of TiSi₂ and Ti₃SiC₂. The growth direction of Ti₃SiC₂ was anisotropic, thus providing more paths for the crack propagation via deflection, branching, and delamination during fracture process. However, the crack propagation inside the Ti₃SiC₂ phase included the pull out, bridging, lamination, deflection, and fracture of the single layer, which are the energy absorption and damage tolerance mechanisms of the Ti₃SiC₂ phase.     

Effects of Si source and high gravity on combustion synthesis of Ti3SiC2 in air

Abstract

Combustion synthesis of Ti₃SiC₂ was carried out in air with Si₃N₄, SiC, and Si as Si sources respectively, and the effect of Si source on the phase composition of the products was investigated. With Si₃N₄ as Si source, the major product was TiC_xN_1?x and no Ti₃SiC₂ was synthesised. When SiC and Si were used, Ti₃SiC₂ was synthesised. Such effect of Si source is thought to be connected with the formation mechanism of Ti₃SiC₂, where the presence of a Ti–Si melt is required. The combustion synthesis was also performed under high gravity condition instead of common gravity. The apparent density of the product prepared under high gravity was ～60% higher than that obtained under normal gravity. It is proposed that, the high gravity can facilitate the permeation of Ti–Si melt and enlarge the interface between the melt and carbide phases, which is helpful for the formation of Ti₃SiC₂.     

Interface structure and wetting behaviour of Cu/Ti3SiC2 system

Wetting behaviour of a Cu/Ti₃SiC₂ system was investigated by the sessile drop technique under a vacuum atmosphere. Contact angles between Cu and Ti₃SiC₂ changed from 95 to 15° as temperatures increased from 1089 to 1270°C. Two distinct reaction layers consisting of different contents of Cu, TiC_x, Ti₃SiC₂ and Cu_xSi_y intermetallics were formed at the interface of Cu and Ti₃SiC₂. The formation of the interface layers contributes to the improvement of the wettability of the system. The dissolution of Si from theTi₃SiC₂ into the molten Cu at high temperature plays a dominant role in the wetting behaviour of Cu/Ti₃SiC₂ systems.     

Microstructure and mechanical properties of in-situ hot pressed (TiB2 + SiC)/Ti3SiC2 composites with tunable TiB2 content

Without impurity phases detected, fully dense (TiB₂?+?SiC)/Ti₃SiC₂ composites have been successfully synthesised by in-situ reaction hot pressing. The effect of TiB₂ content on phase composite, sintering properties, microstructure, and mechanical properties of the composites were thoroughly investigated. With TiB₂ content increasing from 0 to 50?vol.-%, the flexural strength increases first and then decreases, whereas fracture toughness, hardness and modulus show a linear increase. The maximum strength of 826?MPa was obtained at 20?vol.-% TiB₂. On the whole, the (TiB₂?+?SiC)/Ti₃SiC₂ composites exhibit a superior comprehensive mechanical properties superior to other reported Ti₃SiC₂-based composites reinforced by singular reinforcement. The significant strengthening and toughening effect induced by the in-situ incorporated TiB₂ can be ascribed to the unique properties of TiB₂ and the synergistic action of many mechanisms including particle reinforcement, pulling out of grains, crack deflection and grain refinement strengthening.     

Joining of SiCf/SiC using a layered Ti3SiC2-SiCw and TiC gradient filler

A layered filler consisting of Ti₃SiC₂-SiC whiskers and TiC transition layer was used to join SiC_f/SiC. The effects of SiC_w reinforcement in Ti₃SiC₂ filler were examined after joining at 1400 or 1500 °C in terms of the microstructural evolution, joining strength, and oxidation/chemical resistances. The TiC transition layer formed by an in-situ reaction of Ti coating resulted in a decrease in thermal expansion mismatch between SiC_f/SiC and Ti₃SiC₂, revealing a sound joint without cracks formation. However, SiC_f/SiC joint without TiC layer showed formation of cracks and low joining strength. The incorporation of SiC_w in Ti₃SiC₂ filler showed an increase in joining strength, oxidation, and chemical etching resistance due to the strengthening effect. The Ti₃SiC₂ filler containing 10 wt.% SiC_w along with the formation of TiC was the optimal condition for joining of SiC_f/SiC at 1400 °C, showing the highest joining strength of 198 MPa as well as improved oxidation and chemical resistance.     

Ti3SiC2 friction material prepared by novel method of infiltration sintering

Titanium silicon carbide (Ti₃SiC₂) is a remarkable friction material for its combination of the best properties of metals and ceramics. The high purity Ti₃SiC₂ ceramic has been prepared by infiltration sintering (IS), and the effect of a small amount of Si on Ti₃SiC₂ ceramic formation was investigated. The results show that the purity of Ti₃SiC₂ ceramic could be increased significantly and the sintering time for Ti₃SiC₂ could be decreased remarkably when proper amount of Si was added in the starting mixture. The Ti₃SiC₂ sintered compact with a purity of 99.2?wt-% and a relative density of 97% was obtained by the IS from a starting mixture composed of n(Ti):n(Si):n(TiC)?=?1:0.3:2 at 1500°C with holding time of 2/3?h.     

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.     

Oxidation behavior and kinetics of in situ (TiB2 + TiC)/Ti3SiC2 composites in air

The isothermal oxidation behavior of in situ (TiB₂ + TiC)/Ti₃SiC₂ composite ceramics with different TiB₂ content has been investigated at 900-1200 °C in air for exposure times up to 20 h by means of X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and energy dispersive spectroscopy. The oxidation of (TiB₂ + TiC)/Ti₃SiC₂ composites follows a parabolic rate law. With the increase in TiB₂ content, the oxidation weight gain, thickness of the oxidation scale, and parabolic rate constant decrease dramatically, which suggests that the incorporation of TiB₂ greatly improves the oxidation resistance of the composites. With the increase in oxidation temperature, the enhancement effect becomes more pronounced. Due to the incorporation of TiB₂, the oxidation scale of (TiB₂ + TiC)/Ti₃SiC₂ composites is generally composed of an outer layer of coarse-grained TiO₂ and an inner layer of amorphous boron silicate and fine-grained TiO₂. Only the dense inner layer formed on the surface acts as a diffusion barrier, retarding the inward diffusion of O, and consequently contributing to the improved oxidation resistance of the (TiB₂ + TiC)/Ti₃SiC₂ composites.     

Reaction mechanism in Ti–SiC–C powder mixture during pulse discharge sintering

During pulse discharge sintering (PDS) of Ti/SiC/C powder mixture, combustion synthesis reactions occurred at heating rates above 20 °C/min. With an increase in heating rate, combustion synthesis occurred at higher temperatures. The essential of this combustion reaction is the liquid reaction between Ti and formed Ti₅Si₃. The exothermic TiC formation during PDS process promotes this liquid reaction. We have found that the combustion reactions alone did not finish the formation reactions for Ti₃SiC₂, and further heating following the combustion reactions is necessary for the synthesis process of Ti₃SiC₂.     

Residual thermal stress of SiC/Ti3SiC2/SiC joints calculation and relaxed by postannealing

Residual thermal stresses in SiC/Ti₃SiC₂/SiC joining couples were calculated by Raman spectra and simulated by finite element analysis, and then relaxed successfully by postannealing. The results showed that the thermal residual stress between Ti₃SiC₂ and SiC was about on the order of 1 GPa when cooling from 1300°C to 25°C. The thermal residual stresses can be relaxed by the recovery of structure disorders during postannealing. When the SiC/Ti₃SiC₂/SiC joints postannealed at 900°C, the bending strength reached 156.9 ± 13.5 MPa, which was almost twice of the as‐obtained SiC/Ti₃SiC₂/SiC joints. Furthermore, the failure occurred at the SiC matrix suggested that both the flexural strength of joining layer and interface were higher than the SiC matrix.     

In-situ formation of Ti3SiC2 interphase in SiCf/SiC composites by molten salt synthesis

Titanium silicon carbide (Ti₃SiC₂) film was synthesized by molten salt synthesis route of titanium and silicon powder based on polymer-derived SiC fibre substrate. The pre-deposited pyrolytic carbon (PyC) coating on the fibre was utilized as the template and a reactant for Ti₃SiC₂ film. The morphology, microstructure and composition of the film product were characterized. Two Ti₃SiC₂ layers form the whole film, where the Ti₃SiC₂ grains have different features. The synthesis mechanism has been discussed from the thickness of PyC and the batching ratio of mixed powder respectively. Finally, the obtained Ti₃SiC₂ film was utilized as interphase to prepare the SiC fibre reinforced SiC matrix composites (SiC_f/Ti₃SiC₂/SiC composites). The flexural strength (σ_F) and fracture toughness (K_IC) of the SiC_f/Ti₃SiC₂/SiC composite is 460 ± 20 MPa and 16.8 ± 2.4 MPa?m^1/2 respectively.     

Improvement of oxidation resistance of unidirectional Cf/SiO2 composites by the addition of SiCp

Unidirectional carbon fiber reinforced fused silica composites (uni-C_f/SiO₂) with addition of different contents of SiC particle (SiC_p) were prepared by slurry infiltrating and hot-pressing. The model of oxygen infiltrating into the composite was supposed according to the characterization of fiber/matrix interface observed by transmission electronic microscope (TEM). The oxidation process of the composite was analyzed by thermo-gravimetry and differential scanning calorimeter (TG-DSC) method and the oxidation resistance was evaluated by the residual flexural strength and the fracture surface of the composite after heat treatment at elevated temperatures method. The results showed that the oxidation of carbon fiber started at 480 °C and ended at 800 °C and the oxidation of SiC_p started at above 1000 °C in the composite. The addition of 20 wt.% SiC_p had a better oxidation resistance. According to the characterization of fiber/matrix interface observed by TEM, gaps existed at the fiber/matrix interface which resulted from the CTE mismatch of carbon fiber and SiO₂ matrix. While the CTE mismatch between SiC_p and SiO₂ matrix could also result in the pre-existing gaps in the matrix. The oxygen penetrated along the gaps and simultaneously reacted with carbon fiber ends and SiC_p, which filled the gaps at the fiber/matrix interface and the pre-existing gaps in the matrix and subsequently prevented oxygen from infiltrating inward.     

High-temperature hydrogenation behaviour of bulk titanium silicon carbide

Thermal stability of Ti₃SiC₂ was investigated at 1200–1400°C in hydrogen atmosphere for 3 hours. The hydrogenation mechanism was clarified by a combination of X-ray diffraction, scanning electron microscope, Raman spectroscopy and first principles calculation. At 1200°C, a dense and uniform TiSi₂ layer formed on the sample surface, which originated from both the preferable lose of silicon from the Ti₃SiC₂ substrate and the dissociation of Ti₃SiC₂. As temperature increased to 1300°C, TiSi₂ layer began to scale off and presented laminated Ti₃SiC₂ grains beneath this layer, which indicated preferential hydrogenation occurred along the basal planes. This phenomenon was ascribed to the fact that the introduction of H interstitial atom weakened the combination between titanium and silicon interface layer, which was confirmed by first principles calculations. In addition, the formation of TiSi₂ owing to the dissociation of Ti₃SiC₂ caused the volume expansion after hydrogenation, resulting in that majority of TiSi₂ layer spelled off at 1400°C.     

Joining of Ti-coated monolithic SiC using a SiCw/Ti3SiC2 filler by electric field-assisted sintering

Monolithic SiC, for the first time, was successfully joined using a SiC whisker-reinforced Ti₃SiC₂ composite (SiC_w/Ti₃SiC₂) filler via electric field-assisted sintering technique. A thin Ti coating layer was formed on the SiC surface to minimize the residual stress at the joint interface by transforming it into a TiC gradient layer. After optimizing process parameters, a joint strength higher than 250 MPa was obtained, which is higher than the other values reported in the literature. Failure occurred at the SiC base rather than the joining interface because of the improved joint strength by the incorporation of SiC_w. The addition up to 15 wt. % SiC_w in the filler layer improved the joint strength by various strengthening mechanisms. On the other hand, the joint strength was lower with 20 wt. % SiC_w addition, indicating the importance of thermal expansion mismatch between SiC_w and Ti₃SiC₂ to obtain a sound SiC joint.     

Joining of SiC monoliths using a thin MAX phase tape and the elimination of joining layer by solid-state diffusion

This paper reports the joining of SiC monoliths using a thin MAX phase tape filler, such as Ti₃AlC₂ and Ti₃SiC₂, and the subsequent phenomena leading to the elimination of the joining layer via solid-state diffusion of the MAX phase into the SiC base material, particularly with the decomposition of the Ti₃AlC₂ filler. The base SiC monolith, showing?≥?99% density, was fabricated by hot pressing SiC powder after adding 5?wt. % Al₂O₃-Y₂O₃ sintering additive. A butt-joint configuration was prepared and joined by hot pressing under a pressure of 3.5?MPa. The effects of the experimental parameters, including the type and thickness of the joining filler, temperature as well as the holding time, were examined carefully in terms of the microstructure, phase evolution and joining strength. The joining interface could be eliminated from the SiC base when the SiC monoliths were joined at 1900?°C using a thin Ti₃AlC₂ tape, showing a high joining strength ～300?MPa. Moreover, fracture during the mechanical test occurred mainly at the base material rather than the joining interface, indicating excellent joining properties. These findings highlight the elimination of the joining interlayer, which might be ideal for practical applications because the absence of a joining filler helped preserve the excellent SiC mechanical properties of the joint.