Titanium diboride–silicon carbide–boron carbide ceramics with super‐high hardness and strength

Triplex particulate composites composed of boride and carbide ceramics were found to have high strength, hardness, and fracture toughness values. Two compositions consisting of 70:15:15 and 1:1:1 volume ratios of TiB_2, SiC, and B₄C were produced from commercially available powders by hot‐pressing. The 70:15:15 ceramic exhibited a strength of ~1.3 GPa, while the 1:1:1 ceramic had a strength of ~0.9 GPa. These strengths are comparable to super‐strong Y₂O₃‐PSZ and β‐SiAlON based composites. The Vickers’ hardness values of these ceramics were ~32 GPa for indent loads of 9.8 N. Hardness increased as indentation load decreased. The 1:1:1 ceramic had a hardness of ~53 GPa at an indentation load of 0.49 N, higher than values reported for so‐called “super‐hard” ceramics, and comparable to c‐BN.     

Microstructural Effects on the Mechanical Properties of SiC‐15 vol% TiB2 Particulate‐Reinforced Ceramic Composites

The microstructures and mechanical properties were studied for two different SiC ceramics containing 15 vol% of TiB₂ particulates. The first was prepared from commercially available spray‐dried granules and the second by blending individual SiC and TiB₂ powders. The average TiB₂ particle sizes were 2.7 μm for the ceramic prepared from blended powders, which had a uniform distribution of TiB₂, and 2.3 μm for the ceramic prepared from spray‐dried granules, which had a nonuniform distribution of TiB₂ agglomerates. Although the two ceramics had hardness values of 26 GPa, the other properties were different. For example, the fracture toughness was 4.3 MPa·m^1/2 for the ceramic prepared from blended powders compared to 3.1 MPa·m^1/2 for the ceramic prepared from spray‐dried granules. In contrast, the Weibull modulus for the ceramic prepared from spray‐dried granules was 21 compared to 12 for the other. Calculations predicted spontaneous microcracking in the ceramic prepared from spray‐dried granules, which was confirmed by analysis of the microstructure. The presence of microcracks accounted for the higher Weibull modulus, but lower flexural strength, Young's modulus and fracture toughness for the ceramic prepared from spray‐dried granules.     

A high strength alumina-silicon carbide-boron carbide triplex ceramic

A ceramic particulate composite composed of oxide, and carbide ceramics was found to have high strength, hardness, and fracture toughness values. A composition consisting of Al₂O₃ with 15 vol% SiC and 15 vol% B₄C additions was produced by hot-pressing at 1650 °C for 30 min, with full density reached after ~5 min at temperature. Both WB and WB₂ were observed, with the W source presumably an impurity from WC milling media, and Al₁₈B₄O₃₃ was also detected following densification. Strength was ~880 MPa, which is greater than values reported for comparable composites of Al₂O₃ containing 30 vol% SiC or B₄C. Vickers hardness was ~21 GPa, and fracture toughness was ~4.5 MPa m^½, comparable to values reported for the binary mixtures. The calculated critical flaw size of the material was similar to the size of the SiC/B₄C clusters and microcracking at grain boundaries. The latter resulting from thermal expansion mismatch between the Al₂O₃ matrix and SiC/B₄C reinforcing phases.     

Densification,microstructure, and mechanical properties of ZrC–SiC ceramics

ZrC–SiC ceramics were fabricated by high-energy ball milling and reactive hot pressing of ZrH₂, carbon black, and varying amounts of SiC. The ceramics were composed of nominally pure ZrC containing 0 to 30 vol% SiC particles. The relative density increased as SiC content increased, from 96.8% for nominally pure ZrC to 99.3% for ZrC-30 vol% SiC. As SiC content increased from 0 to 30 vol%, Young's modulus increased from 404 ± 11 to 420 ± 9 GPa and Vickers hardness increased from 18.5 ± 0.7 to 23.0 ± 0.5 GPa due to a combination of the higher relative density of ceramics with higher SiC content and the higher Young's modulus and hardness of SiC compared to ZrC. Flexure strength was 308 ± 11 MPa for pure ZrC, but increased to 576 ± 49 MPa for a SiC content of 30 vol%. Fracture toughness was 2.3 ± 0.2 MPa·m^1/2 for pure ZrC and increased to about 3.0 ± 0.1 MPa·m^1/2 for compositions containing SiC additions. The combination of high-energy ball milling and reactive hot pressing was able to produce ZrC–SiC ceramics with sub-micron grain sizes and high relative densities with higher strengths than previously reported for similar materials.     

Study on the toughening mechanism of in-situ synthesis (TixZr1−x)B2 in solid-state sintered SiC composite ceramics

High-dense SiC-(Ti_xZr_1?x)B₂ composite ceramics were fabricated by in-situ synthesis of (Ti_xZr_1?x)B₂ solid solution using solid-state spark plasma sintering (SPS). 64 vol% SiC, 20 vol% ZrB₂, 15 vol% TiB₂, and 1 vol% graphite powders are chosen as raw materials. The composite ceramics has the relative density of 99.97 %, the Vickers hardness of 24.71 GPa, the flexure strength of 435 MPa and the fracture toughness of 8.05 MPa ? m^1/2. Compared with the single-phase SiC ceramics and SiC-TiB₂ composite ceramics, the fracture toughness of SiC-(Ti_xZr_1?x)B₂ composite ceramics increased by 242.6 % and 53.6 %, respectively. A shell-core structure is found in the SiC-(Ti_xZr_1?x)B₂ composite ceramics, in which (Ti_xZr_1?x)B₂ solid solution is the core and fine SiC grain is the shell. The results show that the toughening effect of solid-state sintered SiC-(Ti_xZr_1?x)B₂ composite ceramics is attributed to the shell-core structure.     

Dense and core-rim structured B4C-TiB2 ceramics with Mo-Co-WC additive

B₄C-TiB₂ ceramics (TiB₂ ranging 5~70 vol%) with Mo-Co-WC as the sintering additive were prepared by spark plasma sintering. In comparison with B₄C-TiB₂ without additive, the enhanced densification was evident in the sintered specimen with Mo-Co-WC additive. Core-rim structured grain was observed around TiB₂ grains. The interface of the rim between TiB₂ and B₄C phases demonstrated different feature: the inner borderline of the rim exhibited a smooth feature, whereas a sharp curved grain boundary was observed between the rim and the B₄C grain. The formation mechanism is discussed: the epitaxial growth of (Ti,Mo,W)B₂ rim around the TiB₂ core may occur as a result of the solid solution and dissolution-precipitation between TiB₂ phase and the sintering additive. It was revealed that the fracture toughness increased as the content of TiB₂ content increased, alongside the decreased hardness. B₄C-30 vol% TiB₂ specimen demonstrated the optimal combination of mechanical properties, reaching Vickers hardness of 24.3 GPa and fracture toughness of 3.33 MPa·m^1/2.     

Hot-pressing and characterization of TiB2–SiC composites with different amounts of BN additive

This research aimed to study the influence of different amounts of hBN additive on the mechanical properties and microstructure of TiB₂-15 vol% SiC samples. All ceramics, containing 0, 3.5, and 7 vol% hBN, were sintered at 2000 °C using a hot-pressing route and reached their near full densities. Thanks to two different chemical reactions among the SiC reinforcement and the TiB₂ surface oxides (B₂O₃ and TiO₂), the in-situ phases of SiO₂ and TiC were generated over the sintering process. The intergranular mode was identified as the predominant fracture type in all three composite samples. The hBN additive could contribute to grain refining of composites so that the sample containing 7 vol% hBN reached the finest microstructure. Finally, the highest Vickers hardness of 25.4 HV_0.5 kg and flexural strength of 776 MPa were attained for the TiB₂–SiC and TiB₂–SiC-7 vol% hBN samples, respectively.     

Silicon carbide–titanium diboride ceramic composites

The effect of TiB₂ content on mechanical properties of silicon carbide–titanium diboride ceramic composites was studied. The hardness of the ceramics decreased from 27.8 GPa for nominally pure SiC to 24.4 GPa for nominally pure TiB₂. In contrast, fracture toughness of the ceramics increased from 2.1 MPa m^1/2 for SiC to ～6 MPa m^1/2 for SiC with TiB₂ contents of 40 vol.% or higher. Flexure strengths were measured for three composites containing 15, 20, and 40 vol.% TiB₂ and analyzed using a two parameter Weibull analysis. The Weibull modulus increased from 12 for 15 vol.% TiB₂ to 17 for 20 and 40 vol.% TiB₂. Microstructural analysis revealed microcracking in the ceramics containing 20 and 40 vol.% TiB₂. The ceramic containing 40 vol.% TiB₂ had the best combination of properties with a fracture toughness of 6.2 MPa m^1/2, hardness of 25.3 GPa, Weibull modulus of 17, and a strength of 423 MPa.     

High-strength TiB2-B4C composite ceramics sintered by spark plasma sintering

Spark plasma sintering (SPS) is an advanced sintering technique because of its fast sintering speed and short dwelling time. In this study, TiB₂, Y₂O₃, Al₂O₃, and different contents of B₄C were used as the raw materials to synthesize TiB₂-B₄C composites ceramics at 1850°C under a uniaxial loading of 48 MPa for 10 min via SPS in vacuum. The influence of different B₄C content on the microstructure and mechanical properties of TiB₂-B₄C composites ceramics are explored. The experimental results show that TiB₂-B₄C composite ceramic achieves relatively good comprehensive properties and exceptionally excellent flexural strength when the addition amount of B₄C reaches 10 wt.%. Its relative density, Vickers hardness, fracture toughness, and flexural strength reach to 99.20%, 24.65 ± .66 GPa, 3.16 MPa·m^1/2, 730.65 ± 74.11 MPa, respectively.     

Effect of TiB2 particles on microstructure and mechanical properties of B4C–TiB2 ceramics prepared by hot pressing

B₄C-20 wt% TiB₂ ceramics were fabricated by hot pressing B₄C and ball-milled TiB₂ powder mixtures. The effects of the TiB₂ particle size on the microstructure and mechanical properties were investigated. The results showed that the TiB₂ particle size played an important role in the mechanical properties of the B₄C–TiB₂ ceramics. In addition, SiO₂ introduced by ball milling was beneficial for densification but detrimental to the mechanical properties of the B₄C–TiB₂ ceramics. The typical values of relative density, hardness, flexural strength, and fracture toughness of the ceramics were 99.20%, 35.22 GPa, 765 MPa, and 7.69 MPa m^1/2, respectively. The toughening mechanisms of the B₄C–TiB₂ ceramics were explained by crack deflection and crack branching. In this study, the effects of high pressure and temperature caused liquefying SiO₂ to migrate to the surface of B₄C–TiB₂ and react with diffused carbon source in the graphite foil to form a 30 μm thick SiC layered structure, which improved the high-temperature oxidation resistance of the material. The unique SiC layered structure overcame the insufficient oxidation resistance of B₄C and TiB₂, thereby improving the oxidation resistance of the ceramics under high-temperature service conditions.     

Effects of TiN content on the properties of hot pressed TiB2–SiC ceramics

This research intended to study the impacts of different contents of the TiN additive on the mechanical properties and microstructural features of the TiB₂–SiC-based composites. Three different samples of TiB₂-15 vol% SiC- x vol% TiN (x = 0, 3.5, and 7) were produced by hot-pressing at 2000 °C under 35 MPa for 120 min. Thanks to advancement of some reactions among the TiB₂ surface oxides and the SiC reinforcement, two in-situ phases of TiC and SiO₂ were produced during the sintering. Nevertheless, the TiN incorporation resulted in generating another in-situ compound (TiC_0.3N_0.7) in the relevant as-sintered ceramics. Moreover, introducing TiN significantly refined the microstructure of the composites, leading to higher mechanical characteristics. Finally, the highest flexural strength (781 MPa) and Vickers hardness (27.1 GPa) values were attained for the sample introduced by 7 vol% TiN.     

Synthesis and properties of conductive B4C ceramic composites with TiB2 grain network

High electrical resistance and low fracture toughness of B₄C ceramics are 2 of the primary challenges for further machining of B₄C ceramics. This report illustrates that these 2 challenges can be overcome simultaneously using core‐shell B₄C‐TiB₂&TiC powder composites, which were prepared by molten‐salt method using B₄C (10 ± 0.6 μm) and Ti powders as raw materials without co‐ball milling. Finally, the near completely dense (98%) B₄C‐TiB₂ interlayer ceramic composites were successfully fabricated by subsequent pulsed electric current sintering (PECS). The uniform conductive coating on the surface of B₄C particles improved the mass transport by electro‐migration in PECS and thus enhanced the sinterability of the composites at a comparatively low temperature of 1700°C. The mechanical, electrical and thermal properties of the ceramic composites were investigated. The interconnected conductive TiB₂ phase at the grain boundary of B₄C significantly improved the properties of B₄C‐TiB₂ ceramic composites: in the case of B₄C‐29.8 vol% TiB₂ composite, the fracture toughness of 4.38 MPa·m^1/2, the electrical conductivity of 4.06 × 10⁵ S/m, and a high thermal conductivity of 33 W/mK were achieved.     

Superhard single-phase (Ti,Cr)B2 ceramics

A nominally pure and dense (Ti_0.9Cr_0.1)B₂ ceramic was produced by spark plasma sintering of powders synthesized by boro/carbothermal reduction of oxides. The synthesized powders were a single phase and had an average particle of 0.4 ± 0.1 μm and an oxygen content of 1.2 wt%. Average Vickers hardness values of the resulting ceramics increased from 25.9 ± 0.8 GPa at a load of 9.81 N, to 46.3 ± 0.8 GPa at a load of 0.49 N. Compared to the nominally pure TiB₂ ceramic obtained under the same processing conditions, the (Ti_0.9Cr_0.1)B₂ ceramic had higher values under the same load due to the finer average grain size (2.4 ± 1.0 μm), higher relative density, and solid solution hardening. The results indicated that the Cr addition promoted densification, suppressed grain growth, and improved the hardness of TiB₂ ceramics. This is the first report for dense and single-phase (Ti,Cr)B₂ ceramics as superhard materials.     

Microstructures and mechanical properties of B4C–SiC and B4C–SiC–TiB2 ceramic composites fabricated by hot pressing

Boron carbide (B₄C) ceramic composites with excellent mechanical properties were fabricated by hot-pressing using B₄C, silicon carbide (SiC), titanium boride (TiB₂), and magnesium aluminum silicate (MAS) as raw materials. The influences of SiC and TiB₂ content on the microstructural evolution and mechanical properties of the composites were systematically investigated. The mechanism by which MAS promotes the sintering process of composites was also investigated. MAS exists in composites in the form of amorphous phase. It can effectively remove the oxide layer from the surface of ceramic particles during the high temperature sintering process. The typical values of relative density, hardness, bending strength, and fracture toughness of B₄C–SiC–TiB₂ composites are 99.6%, 32.61 GPa, 434 MPa, and 6.20 MPa m^1/2, respectively. Based on the microstructure observations and finite element modeling, the operative toughening mechanism is mainly attributed to the crack deflection along the grain boundary, which results from the residual stress field generated by the thermal expansion mismatch between B₄C and TiB₂ phase.     

Preparation of TiB2–SiC composites toughened with interlocking microstructure by self-assembled TiB2 plates

The spark plasma sintering (SPS) technique was found to effectively improve the mechanical properties of TiB₂–SiC ceramic by forming a unique interlocking structure. This study investigated the phase transition process of the hexagonal micro-platelets TiB₂ powders with self-assembled structure during the molten-salt-mediated carbothermal reduction and its effect on promoting the mechanical properties of TiB₂-based ceramics. It was found that the SPS approach ensured a highly densified TiB₂–SiC ceramics with enhanced Vickers hardness of 21.0 ± 1.3 GPa and fracture resistance of 7.8 ± 0.3 MPa m^1/2. The performance enhancement of the resultant TiB₂–SiC composite was attributed to the interlocking structure from the original anisotropic TiB₂ powders, which could effectively absorb the energy and facilitate the crack deflection.     

B4C‒TiB2 composite with modified microstructure and enhanced properties from optimal size coupling of raw powders

B₄C‒15 vol% TiB₂ composites were fabricated by in situ reactive spark plasma sintering with B₄C, TiC, and amorphous B powders as the raw materials. The size coupling of initial B₄C and TiC particles was optimized based on the reaction mechanism to derive B₄C‒TiB₂ composites with enhanced microstructure and properties. During the reactive sintering, fine B₄C–TiB₂ particles were firstly formed by an in situ reaction between TiC and B. Then, large B₄C particles tended to grow at the cost of small B₄C particles. The in situ TiB₂ grains gradually grew up and interconnect, distributing around the large B₄C grains to form an intergranular TiB₂ network. The results showed that the B₄C‒15 vol% TiB₂ composite prepared from 3.12 μm B₄C powder and 0.80 μm TiC powder had the optimal comprehensive properties, with a relative density of 99.50%, a Vickers hardness of 31.84 GPa, a flexural strength of 780 MPa, a fracture toughness of 5.77 MPa·m^1/2, as well as an electrical resistivity of 3.01 × 10⁻² Ω·cm.     

Effects of SiC amount and morphology on the properties of TiB2-based composites sintered by hot-pressing

This investigation intended to assess the influence of SiC morphology on the sinterability and physical-mechanical features of TiB₂-SiC composites. For this aim, different volume percentages of SiC particles and SiC whiskers were introduced to TiB₂ samples hot-pressed at 1950 °C for 2 h under an external pressure of 25 MPa. The characterization of as-sintered specimens was carried out using X-ray diffraction, optical microscopy, and scanning electron microscopy. The relative density studies revealed that SiC_w had a more significant impact on the sinterability of TiB₂-based composites. The XRD investigation confirmed the production of an in-situ TiC phase during the hot-pressing; however, some peaks related to the graphitized carbon also appeared in the patterns of SiC_w-doped ceramics. The addition of 25 vol% SiC_p halved the average grain size of TiB₂ while introducing the same content of SiC_w decreased this value by just around 20%. Finally, the highest Vickers hardness and fracture toughness were obtained for the sample reinforced with 25 vol% SiC_w, standing at 29.3 GPa and 6.1 MPa m^1/2, respectively.     

Development of spark plasma sintered conductive SiC–TiB2 composites for electrical discharge machining applications

Highly dense electrically conductive silicon carbide (SiC)–(0, 10, 20, and 30 vol%) titanium boride (TiB₂) composites with 10 vol% of Y₂O₃–AlN additives were fabricated at a relatively low temperature of 1800°C by spark plasma sintering in nitrogen atmosphere. Phase analysis of sintered composites reveals suppressed β→α phase transformation due to low sintering temperature, nitride additives, and nitrogen sintering atmosphere. With increase in TiB₂ content, hardness increased from 20.6 to 23.7 GPa and fracture toughness increased from 3.6 to 5.5 MPa m^1/2. The electrical conductivity increased to a remarkable 2.72 × 10³ (Ω cm)^–1 for SiC–30 vol% TiB₂ composites due to large amount of conductive reinforcement, additive composition, and sintering in nitrogen atmosphere. The successful electrical discharge machining illustrates potential of the sintered SiC–TiB₂ composites toward extending the application regime of conventional SiC-based ceramics.     

High hardness and high fracture toughness B4C-diamond ceramics obtained by high-pressure sintering

The B₄C-diamond composite with high hardness and toughness was first prepared by high-pressure sintering of B₄C and diamond powders at 5 GPa and 1600 °C. The effect of the diamond fraction on the densification, microstructure and mechanical properties of B₄C-diamond composite were investigated. The results indicated that the hardness of the as-prepared composite ceramics increased gradually with the increase in diamond content. The composite having 40 vol% diamond exhibited excellent comprehensive mechanical properties with a relative density of 98.3%, a density of 2.86 g/cm³, Vickers hardness of 39.8 GPa and fracture toughness of 8.1 MPa·m^1/2. The use of superhard diamond enhanced the fracture toughness of the B₄C while maintaining its lightweight and high hardness. The main toughening mechanisms were crack bridging, crack deflection and pull-out of homogeneously dispersed diamond grains. Superhard second phase dispersion high-pressure sintering provides a new technical route to improve the properties of advanced composites.     

Influence of TiB2 content on the properties of TiC–SiCw composites

The impact of various volume percentages of TiB₂ additive (0, 10, 20, and 30) on the microstructure, relative density (RD), Vickers hardness, flexural strength, and thermal conductivity of as-sintered TiC-10 vol% SiC_w-based composite samples were scrutinized. All four samples were sintered using the SPS method under the following circumstances; sintering temperature of 1900 °C, dwell time of 7 min, and external pressure of 40 MPa. The best relative density of 98.73% was achieved for the sample with no TiB₂ additive, indicating the negative effect of TiB₂ additive on the RD and formation of porosity. The microstructural observations and XRD results confirmed the chemical interaction of TiO₂ and B₂O₃ oxide layers and SiC_w and in-situ formation of the TiSi brittle phase and TiC. The most significant values of flexural strength (511 MPa) and hardness (27.67 GPa) were related to TiC-10 vol% SiC_w and TiC-10 vol% SiC_w-30 vol% TiB₂ samples, respectively. On the contrary, the specimens with 30 vol% and 10 vol% TiB₂ as additive presented the poorest qualities of flexural strength (234 MPa) and Vickers hardness (22.12 GPa). Finally, the influence of the TiB₂ content on the thermal conductivity was evaluated, indicating the positive impact of this secondary phase on this characteristic, so with adding 30 vol% TiB₂ to TiC-10 vol% SiC_w, a thermal conductivity of 30.7 W/m.K was obtained.