Gas-solid displacement reactions in the Ti–W–C system

Displacement reactions between binary and ternary ceramics in the Ti–W–C system and reactive gaseous atmospheres are investigated in this work. Specifically, WC and 50:50 wt% TiC:WC solid solution powders were exposed to flowing hydrogen gas, or equilibrated against an excess of titanium in the presence of iodine, to form metallic tungsten and TiC solid products. In the case of pure WC reacting with hydrogen, transformation to metallic tungsten occurred as a result of removal of chemically bound carbon as gaseous hydrocarbons. In the case of pure WC reacting with titanium iodide vapors, transformation was accompanied by the appearance of TiC as a solid product formed at the gas-solid interface. In the case of 50:50 wt% TiC:WC solid solution powders, hydrogen was generally found to be an ineffective displacing reagent, whereas reaction with titanium iodide vapors was observed to proceed virtually to completion, resulting in a two phase product mixture comprising metallic tungsten and TiC. For the latter case, a variety of microstructures could be observed within a given batch, including tungsten platelets and/or lamellae in a TiC matrix, or coarse tungsten grains interspersed with TiC grains. These morphological variations are speculated to arise from compositional variation in the starting material and the occurrence of local rapid coarsening along fast diffusion pathways within reacting agglomerates and polycrystalline primary particles. The observed reaction products and relative efficacy of gaseous reagents to promote displacement reactions in the Ti–W–C system are rationalized on the basis of thermodynamic predictions. The reaction between 50:50 wt% TiC:WC solid solution powders and titanium iodide vapors constitutes the first known report of an internal displacement reaction proceeding via gaseous intermediates in a nonoxide ceramic system.     

Sintering and mechanical behavior of SiC and WC co-added TiC-based composites densified by hot-pressing

In this investigation, the individual and synergetic influences of the SiC whiskers and WC particles on the various features of TiC were studied. Fully dense specimens were secured when 40 vol% SiC additive was added to the TiC and TiC-WC systems. The nucleation and growth of the new SiC grains were found as the two main mechanisms positively affecting the sinterability of TiC. Although WC particles were completely dissolved into the TiC matrix in the TiC-WC system, they were entrapped in the newly grown SiC grains in the TiC-WC-SiC system, contributing to strengthening of the specimen. The highest values of flexural strength (590 MPa) and Vickers hardness (2525 HV_0.5 kg) were attained for the sample codoped with SiC whiskers and WC particles.     

Migration of Intergranular Liquid Films and Formation of Core-Shell Grains in Sintered TiC–Ni Bonded to WC–Ni

When TiC–20 wt% Ni powder mixtures are sintered at 1400°C, relatively large TiC grains possibly containing some Ni form with near-equilibrium shapes. When these specimens are heat-treated again at 1400°C in contact with sintered WC–20 wt% Ni pieces, the liquid films between the TiC grains in the contact region migrate against their increasing curvatures, forming (Ti,W)C solid solution behind them. These migrating liquid films reverse their directions on further heat-treatment. As in other alloys, this liquid film migration must be driven by the coherency strain energy produced by W diffusion at the surface of the dissolving TiC grains. Shells of (Ti,W)C solid solution also form around the cores of TiC grains near the contact region, and this process is probably driven by both coherency strain energy and free energy of mixing. At some contact regions, (Ti,W)C precipitates nucleate and grow, probably driven mainly by the free energy of mixing. In powder mixtures, the formation of core-shell grains is expected to be driven by the coherency strain energy, the free energy of mixing, and the capillary effect.     

Morphology evolution of TiC-based cermets via different sintering schedules

Solid state sintering, liquid phase and cooling stages play different roles in determining the final morphology and composition of cermets, especially the well-known core-rim structure. In this work, TiC-(5–25 wt%)WC-11Mo₂C-18(Ni-Co) cermets were prepared and sintered by different sintering schedules. Morphology evolution and rim phase composition during sintering from 1250 °C to 1600 °C were investigated. Effects of sintering stages on the final morphology of cermets were also studied. It was shown that submicron (Ti, W, Mo)C grains tend to precipitate in binder during the cooling for cermets with high WC content. After the formation of outer rims during liquid sintering stage, interface reaction began to take effect between the rims and core. Coreless (Ti_0.76, W_0.13, Mo_0.11)C ceramic grains would be formed under high temperature (1600 °C) for TiC cermets with 25% WC. Long time sintering at solid state favored the formation of black core-thick inner rim and bright core-grey rim phases, while cooling near the melting point could result in submicron bright particles. This study provided not only a better view of the formation of rim-core structure but also an easier way to control the final morphology of cermets via reasonable changing the sintering cycle.     

Effect of Ti addition on the wetting and brazing of Sn0.3Ag0.7Cu filler on SiC ceramic

The wetting behavior of Sn0.3Ag0.7Cu (SAC) filler with the addition of Ti on SiC ceramic was investigated using sessile drop method. SiC/SiC was brazed by SAC-Ti filler with different Ti content at 1223 K (950°C) for 10 minutes. The wettability of SAC-Ti filler on SiC was significantly enhanced with the addition of Ti. The contact angle decreased at first and then increased with increasing Ti content. The lowest contact angle of 9° was obtained with SAC-1.5Ti (wt%) filler. When Ti content further increased to 2.0 wt%, the contact angle increased, due to the intense reaction of Ti–Sn. The reaction between Ti and SiC controlled the wetting behavior of SAC-Ti on the SiC substrate and the reaction products such as TiC and Ti₅Si₃ were formed. The wetting of SAC-Ti on SiC was reaction-controlled. Interfacial reaction products TiC and Ti₅Si₃ were observed. The wetting activation energy in spreading stage was calculated to be 129.3 kJ/mol. Completely filled SiC/SiC joints were obtained using the filler with Ti content higher than 0.5 wt%. The fillet height increased firstly then decreased with mounting Ti content. The shear strength of joints increased first with the addition of Ti then decreased with Ti content increasing to 2.0 wt%. The highest shear strength of 35.7 MPa was obtained with SAC-1.5 Ti (wt%) filler.     

Tungsten carbide – Titanium carbide composite preparation by arc plasma melting and its characterization

WC-TiC composite with six different values of TiC in the range 1–15?wt% was prepared by arc plasma (Ar) melting. Characterizations of the in situ melt-cast composite as well as its powder by XRD, FESM, TEM, SAED and EDS show the composite to consist of related carbide, sub-carbide and mixed carbide phases [WC, W₂C, TiC, TiC_0.981 /TiC_1-x, TiWC₂ /(Ti,W)C] besides presence of minor phases such as carbon (graphite), W, and TiO₂ in traces in few cases. The composite exhibits high hardness and a maximum value of 3650?±?75 VHN is observed in the case of WC-12 (WC+15?wt% TiC) sample. Improved hardness is attributed to the presence of phases like TiC, TiC_0.981 /TiC_1-x and TiWC₂/(Ti,W)C. While total pore volume of open pores in the composite (measured by BET method) lies in the range 0.0002–0.0097?cm³?/g. TEM study of the microstructures shows absence of meso and macro pores in the samples. In the light of these findings, the composite may be called zero porosity material for practical usage. Young's modulus for different compositions of the composite shows significantly high values in the range of 540–703?GPa. Simultaneous improvement in hardness and Young's modulus value of the composite may be attributed both to growth of new mixed carbide phases of W and Ti as stated above and porosity free nature of the samples. The new composite has good scope for use in cast cutting tools, grinding wheels, bullet-proof vests, etc.     

Effect of WC content on microstructure and mechanical properties of Ni3Al-bonded cermets

The effect of WC content on microstructure and mechanical properties of the TiC–Ni₃Al system cermets was investigated. Ni₃Al-bonded cermets showed a core–rim structure with carbide particle coupled with rim embedded in Ni₃Al binder. With WC content increasing, TiC grains were refined and the white rim became complete and got thicker gradually. Interface between core and rim showed a completely coherent relationship. The rim enriched in W constituted an ideal coherence between hard phase and Ni₃Al binder phase. With WC content increasing, the densification of cermets was enhanced, and hardness and TRS were increased firstly and then reduced, reaching peak values 90.9 HRA (HV₃₀ 15 GPa) and 1629 MPa, respectively in cermet N5 (25 wt% WC). Similarly, fracture toughness got a peak value (11.6 MPa m^1/2), at the composition with 20 wt% WC.     

Novel (Zr,Ti)B2-(Zr,Ti)C-SiC ceramics via reactive hot pressing

Fully dense (Zr, Ti)B₂-(Zr, Ti)C-SiC ceramics were prepared by reactive hot-pressing using ZrB₂, TiC, and SiC as the initial materials for the first time. Effects of SiC addition on the microstructure evolution and mechanical properties were reported. The in-situ reaction between ZrB₂ and TiC as well as the SiC addition leads to the grain refinement. Besides, elongated (Zr, Ti)B₂ plate-like grains are obtained due to the occurrence of a transient liquid phase, which leads to the crack deflection in the matrix effectively. Mechanical properties are improved significantly due to grain-refinement and solid solution strengthening, and plate-like grains toughening effects. The ZrB₂-10 mol%TiC composite with 10 mol% SiC additional exhibits good comprehensive mechanical properties of the hardness of 20.2 GPa, the flexural strength of 803 MPa, and the fracture toughness of 5.7 MPa m^1/2.     

Microstructure and mechanical property of SiC whisker coating modified C/C composite/Ti2AlNb alloy dissimilar joints prepared by transient liquid phase diffusion bonding

SiC whisker coating was prepared on the surface of C/C composite successfully by CVD, and transient liquid phase (TLP) diffusion bonding was employed to realize the joining of SiC whisker coating modified C/C composite and Ti₂AlNb alloy using Ti–Ni–Nb foils as interlayer. The microstructure, shear strength and fracture behavior were investigated by scanning electron microscopy (SEM) with energy dispersive X-ray spectrometer (EDS), X-ray diffraction (XRD) and universal testing machine. The results show that SiC has good compatibility with C/C composite, and gradient interface formed between SiC-modified C/C composite and Ti₂AlNb alloy. When the bonding experiment was carried out under bonding temperature of 1040 °C and holding time of 30min with 5 MPa pressure in vacuum, the joints formed well and no obvious defects can be observed. The typical microstructure of joints is C/C composite/SiC + TiC/Ti–Ni compounds + Ti–Ni–Nb solid solutions/residual Nb/diffusion reaction layer/Ti₂AlNb alloy. With the increasing of bonding temperature, the thickness of joining area increased due to sufficient element diffusion. However, when bonding temperature is elevated to 1060 °C, some defects such as cracks and slag inclusions exist in the interface layer between interlayer and Ti₂AlNb. The joints with maximum average shear strength of 32.06 MPa are bonded at 1040 °C for 30min. C, SiC and TiC can be found on the fracture surface of joints bonded at 1040 °C which indicated that fracture occurred at the interface layer adjacent SiC layer.     

Spark plasma sintering of WC-based cermets/titanium and vanadium added composites: A comparative study on the microstructure and mechanical properties

In an attempt to develop the composition and properties of W₂C-(W,Ti)C-TiC and WC-WC_1-x-VC-V super hardmetals, spark plasma sintering (SPS) method was implemented. WC powders were mixed separately with 10?wt% Ti and 10?wt% V in a high energy mixer mill and sintering processes were performed at temperatures of 2150 and 2000?°C, respectively. XRD investigations revealed the formations of TiC and (Ti,W)C as the reaction products in WC-10?wt% Ti composite. Moreover, the interfacial reaction between WC and V led to the formation of WC1-x and VC compounds. A higher bending strength (613?±?25?MPa) and fracture toughness (4.1?±?0.58?MPa?m^1/2) were obtained for WC-10?wt% V samples compared to WC-10?wt% Ti, While the WC-10?wt% Ti composite showed a higher value of hardness (3128?±?42 Vickers) in comparison to WC-10?wt% V (2632?±?39 Vickers), which can act as a super hard cermet.     

Effect of carbon content on electrical,thermal, and mechanical properties of porous SiC ceramics with B4C and C additives

The electrical, thermal, and mechanical properties of porous SiC ceramics with B₄C-C additives were investigated as functions of C content and sintering temperature. The electrical resistivity of porous SiC ceramics decreased with increases in C content and sintering temperature. A minimal electrical resistivity of 4.6 × 10^?2 Ω·cm was obtained in porous SiC ceramics with 1 wt% B₄C and 10 wt% C. The thermal conductivity and flexural strength increased with increasing sintering temperature and showed maxima at 4 wt% C addition when sintered at 2000 °C and 2100 °C. The thermal conductivity and flexural strength of porous SiC ceramics can be tuned independently from the porosity by controlling C content and sintering temperature. Typical electrical resistivity, thermal conductivity, and flexural strength of porous SiC ceramics with 1 wt% B₄C-4 wt% C sintered at 2100 °C were 1.3 × 10^?1 Ω·cm, 76.0 W/(m·K), and 110.3 MPa, respectively.     

Microstructure of laser cladded carbide reinforced Inconel 625 alloy for turbine blade application

Inconel 625 - WC metal matrix composite is a very promising material for high temperature applications. In this study, microstructure investigation and phase composition of a mixture between Inconel 625 and fine tungsten carbide (φ≈0.64 µm) was performed by means of XRD, SEM with EDS and TEM with EDS. Two powder mixtures were prepared: 20 wt% of WC and 30 wt% of WC and deposited on Inconel 625 substrate by laser cladding obtaining a crack and pore free material. The high temperature of the process resulted in partial dissolution of WC in Inconel 625 matrix. In sample containing 30 wt% of WC appearance of topologically close-packed (TCP) phases was observed at grain boundaries. WC, W2C, NbC, W₆C_2.54 and (W,Cr,Ni)₂₃C₆ were detected by XRD. Angular residual carbides and spherical oxide precipitates were visible in both types of samples. Processes occurring during laser action were explained.     

Microstructure and mechanical properties of (Zr,Ti)B2–SiC composites obtained by pressureless sintering of ZrB2–SiC–TiO2 powder mixtures

Multiphase ceramics have been highlighted due to the combination of different properties. This work proposes to obtain the multiphase composite of (Zr,Ti)B₂–SiC based on the mixture of ZrB₂, SiC, and TiO₂ sintered without pressure. The effect of TiO₂ addition on solid solution formation with ZrB₂, densification, microstructure, and mechanical properties was investigated. For this, 2.0 wt% TiO₂ was added to ZrB₂–SiC composites with 10–30 vol% SiC and processed by reactive pressureless sintering at 2050 °C with a 2 h holding time. Sinterability, crystalline phases, microstructure, Vickers hardness, and indentation fracture toughness of these composites were analyzed and compared to the non-doped ZrB₂–SiC samples. The XRD analysis and EDS elemental map images indicated the incorporation of Ti atoms into the ZrB₂ crystalline structure with solid solution generation of (Zr,Ti)B₂. The addition of TiO₂ resulted in matrix grain size refinement and a predominant intergranular fracture mode. The relative densities were not significantly modified with the TiO₂ addition, though a higher weight loss was detected after the sample sintering process. The composites doped with TiO₂ showed an increase in fracture toughness but exhibited a slightly lower Vickers hardness compared to composites without TiO₂ addition.     

Triplet carbide composites of TiC,WC, and SiC

In this study, the influence of adding 0, 10, 20, and 30 vol% SiC_w on the microstructure and physical-mechanical properties (relative density (RD), flexural strength, and Vickers hardness) of TiC-3 wt% WC_n was investigated. All designed samples were spark plasma sintered under the same conditions: sintering temperature of 1900 °C, external pressure of 40 MPa, and dwell time of 7 min. Microstructural evaluation and relative density calculation revealed that the additives were dispersed homogeneously in the TiC matrix. Based on the Archimedes principles, RD values of >100% were measured for the composite samples with 20 and 30 vol% SiC_w, due to not accounting the formation of non-stoichiometric TiC and (Ti,W)C phases in the calculations. On the contrary, the lowest RD was related to the sample with 10 vol% SiC_w. On the other hand, the most significant values of Vickers hardness (28.6 GPa) and flexural strength (694 MPa) were obtained for TiC-3 wt% WC_n and TiC-3 wt% WC_n-20 vol% SiC_w composite samples, respectively.     

Influence of silicon carbide addition on the microstructural development of hot pressed zirconium and titanium diborides

The influences of adding SiC on the microstructure and densification behavior of ZrB₂ and TiB₂ ceramics, hot pressed at 1850 °C for 60 min under 20 MPa, were investigated. The sintered samples were characterized by SEM, EDS and XRD methods. A fully dense TiB₂-based ceramic was obtained by adding 30 vol% SiC. The grain size of ZrB₂ or TiB₂ matrices in the final microstructures decreased with increasing SiC content. The XRD analyses, microstructural characterization as well as thermodynamical calculations proved the in-situ formation of TiC in the SiC reinforced TiB₂-based composites. The interfaces between ZrB₂ and SiC grains in the SiC reinforced ZrB₂-based composites were free of any impurities or tertiary interfacial phases such as ZrC. This result was consistent with the X-ray diffraction pattern and thermodynamics.     

Wetting and interfacial behavior of Al–Ti/4H–SiC system:A combined study of experiment and DFT simulation

Wetting and interfacial behavior of molten Al-(10, 20, 30, 40) at.%Ti alloys on C-terminated 4H–SiC at 1500 and 1550 °C were investigated experimentally, and theoretical bonding strength, structure stability and electronic structure of interfacial reaction products/C-terminated 4H–SiC interfaces were evaluated by first-principle calculations. The wetting experiments show that the Al–Ti/SiC systems present excellent wettability with contact angle of less than 15° except the Al–40Ti/SiC system performed at 1500 °C × 30 min. The SEM-EDS and TEM analyses demonstrate that the reaction products are mainly composed of Al₄C₃, TiC, Ti₃SiC₂, Ti₅Si₃C_X and τ phase, and their formation and evolution can be mainly affected by the Ti concentration in the Al–Ti alloys and wetting temperature. Moreover, the calculated results show that the SiC/C-terminated TiC interface presents the highest work of separation and its electronic property reveals that the localization of electrons and formation of covalent bond between interfacial C atoms lead to the excellent bonding strength of SiC/TiC interface.     

Microstructure evolution and characteristic of Ti(C,N)-based cermets prepared by in situ carbothermal reduction in TiO2

Ti(C,N)-based cermets were prepared by in situ carbothermal reduction in TiO₂ and subsequent liquid phase sintering under vacuum. The prepared cermets were examined using XRD, SEM, TEM, and EDX. During solid-state sintering, fine TiC particles were formed through the carbothermal reduction in TiO₂. A great number of (Ti,W,Mo)C complete solid solutions containing more W and Mo subsequently formed through the counter diffusion of the fine TiC and carbides. The majority of the coarse TiN particles in the raw powders remained undissolved. During liquid phase sintering, Ti-based carbonitride complex solid solutions with less W or Mo precipitated on the coarse TiN particles and fine (Ti,W,Mo)C particles, resulting in black core/gray rim structures and white core/gray rim structures, respectively. Moreover, small amounts of Ti-based carbonitride complex solid solutions precipitated directly from the liquid binder phase in some areas enriched in W and Mo during the cooling stage after sintering, resulting in coreless grains. Ultimately, after being sintered at 1400°C for 1 hour, the present cermets were characterized with white core/gray rim grains, black core/gray rim grains and a few gray grains. In addition, the interfaces between the black core/gray rim grains and binder phase were atomically smooth, exhibiting a orientation relationship with a perfect coherency state.     

Carbon contents design and characterization of gradient cemented carbonitrides with nano-TiN addition

Gradient cemented carbonitrides with brittle cubic phase depleted in the surface layer were prepared in the paper. This gradient material is believed to be a promising composite used as the substrate of a coated insert for machining operation. The formation of gradient layers stems from nitrogen decomposition. In this paper, nano-TiN was introduced as a nitrogen supplier, and besides it functioned as a grain growth inhibitor of (Ti,W)C cubic phase. The microstructure, fracture morphology, mechanical and magnetic properties of the gradient cemented carbonitrides with carbon contents from 6.04wt% to 6.34 wt% were investigated systematically. The results show that lattice parameters of (Ti,W)C in the transit zone increase due to more Ti solid solution when the gradient layer thickens. (Ti,W)C grains in the inner bulk are refined effectively by nano-TiN. Intergranular fracture along WC grain, transgranular fracture of (Ti,W)C grains, and the tearing of binder are found in the bulk of the gradient cemented carbonitride. When cracks encounter the gradient layer, they grow from new origins and a macroscopic boundary is formed between the gradient layer and the bulk. The transverse rupture strength is promoted with the carbon contents increased, and its stability is also increased. Additionally, the microhardness of the gradient cemented carbonitride is correlated closely with the Ti and Co distribution.     

Electrical resistivity of silicon carbide ceramics sintered with 1 wt% aluminum nitride and rare earth oxide

The influence of additive composition on the electrical resistivity of hot-pressed liquid-phase sintered (LPS)-SiC was investigated using AlN–RE₂O₃ (RE = Sc, Nd, Eu, Gd, Ho, Er, Lu) mixtures at a molar ratio of 60:40. It was found that all specimens could be sintered to densities >95% of the theoretical density by adding 5 wt% in situ-synthesized nano-sized SiC and 1 wt% AlN–RE₂O₃ additives. Six out of seven SiC ceramics showed very low electrical resistivity on the order of 10^?4 Ω m. This low electrical resistivity was attributed to the growth of nitrogen-doped SiC grains and the confinement of non-conducting RE-containing phases in the junction areas. The SiC ceramics sintered with AlN–Lu₂O₃ showed a relatively high electrical resistivity (～10^?2 Ω m) due to its lower carrier density (～10¹⁷ cm^?3), which was caused by the growth of faceted grains and the resulting weak interface between SiC grains.     

Synthesis,microstructure, and mechanical properties of WC–TiC–Co ceramic composites

A ceramic composite constituting the formula 78 wt% WC–16 wt% TiC–6 wt% Co denoted as the 78WC–16TiC–6Co ceramic composite was fabricated using a powder metallurgy process, by utilising commercially available WC and Co powders, and laboratory produced TiC powders. TiC powders were produced from machining chips of Grade 4 Titanium. Five different procedures were followed for the manufacturing process by altering the amount of the binding agent (stearic acid) and/or compacting pressure and/or sintering regime (temperature and time) and/or mixing process (dry mixing and mechanical alloying). Characterisation investigations conducted on the sintered samples revealed that stearic acid as the binding agent resulted in the decrease of the relative density while mechanical alloying (MA) induced finer microstructures. The 78WC–16TiC–6Co composites manufactured from commercially available and laboratory produced TiC powders using similar process procedures (including MA) exhibited similar characteristics in terms of relative density, hardness, and wear performance.