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.     

High-performance B4C matrix composites fabricated from the B4C–Si–CeO2 system via reactive hot pressing

Boron carbide (B₄C) matrix composites had the advantages of high hardness, high melting point and low density. However, due to the low relative density and poor fracture toughness of B₄C, its comprehensive properties were limited in engineering applications. In this work, in order to improve the comprehensive properties of B₄C composites, B₄C–SiC–SiB₆–CeB₆ composites were designed and fabricated via reactive hot pressing at 2050 °C and 20 MPa with B₄C matrix and novel additives (Double doping of Si and CeO₂) as raw materials. The effects of additive CeO₂ content on the microstructures and mechanical properties of composite were investigated, and reaction mechanisms of B₄C, Si and CeO₂ at different temperatures were studied in detail. The work showed that liquid phase Si and SiB₆ greatly improved the densification of composites. CeB₆ played an indispensable role in the formation of SiC–SiB₆ agglomerate structure, increasing strength and supplementing toughness. When the content of CeO₂ was 6 wt%, the relative density, hardness, flexural strength and fracture toughness reached to 99.7%, 34.9 GPa, 461.46 MPa and 5.57 MPa m^1/2, respectively. Our strategy benefited from the formation of two liquid phases and SiC–SiB₆ agglomerate structure, showing great potential in promoting sintering and improving fracture toughness.     

B4C–TiB2 composites fabricated by hot pressing TiC–B mixtures: The effect of B excess

Previous research have reported that B₄C–TiB₂ composites could be prepared by the reactive sintering of TiC–B powder mixtures. However, due to spontaneous oxidation of raw powders, using TiC–B powder mixtures with a B/TiC molar ratio of 6: 1 introduced an intermediate phase of C during the sintering process, which deteriorated the hardness of the composites. In this report, the effects of B excess on the phase composition, microstructure, and mechanical properties of B₄C–TiB₂ composites fabricated by reactive hot pressing TiC–B powder mixtures were investigated. XRD and Raman spectra confirmed that lattice expansion occurred in B-rich boron carbide and B_xC–TiB₂ (x > 4) composites were obtained. The increasing B content improved the hardness and fracture toughness but decreased the flexural strength of B_xC–TiB₂ (x > 4) composites. When the molar ratio of B/TiC increased from 6.6:1 to 7.8:1, the Vickers hardness and the fracture toughness of the composites were enhanced from 26.7 GPa and 4.53 MPa m^1/2 to 30.4 GPa and 5.78 MPa m^1/2, respectively. The improved hardness was attributed to the microstructural improvement, while the toughening mechanism was crack deflection, crack bridging and crack branching.     

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.     

Microstructure evolution and performance of B4C–NdB6 composites fabricated by in situ hot pressing

B₄C–NdB₆ composites were fabricated by in situ hot pressing at different temperatures (1950–2150°C) with B₄C and Nd₂O₃ (2–4 wt%) as raw materials. The microstructure evolution of the composites with sintering temperature and Nd₂O₃ content was studied in detail, and the influence of pressure on the sintering of B₄C with different contents of Nd₂O₃ was also investigated. The performance of the fabricated composites was researched and the toughening mechanism was discussed. The results indicate that Nd₂O₃ can react with B₄C to form the thin-sheet intermediate products (Nd(BO₂)₃, Nd₂CO₅) first, which then transform to band-shaped NdB₆. Pressure can reduce the distance of B₄C and Nd₂O₃, accelerating the mass transfer and contributing to the formation of NdB₆. NdB₆ and intermediate products are first in agglomerate structure at 1950°C, and then the agglomerates are broken to form dispersive micron and submicron NdB₆ at 2000°C by the synergistic function of pressure, diffusion at high temperature, and liquid phase sintering. NdB₆ can enhance the densification owing to the bonding function. Excessive Nd₂O₃ content leads to residual pores, and excessive temperature (2150°C) results in the coarsening of phases. The coexistence of transgranular and intergranular fracture of NdB₆ promote the fracture toughness.     

Microstructure and mechanical properties of TiB2–B4C ceramics fabricated by hot-pressing

In this study, TiB₂–B₄C composite ceramics were prepared using Y₂O₃ and Al₂O₃ as the sintering aids. Different contents of B₄C were added to seek promoted comprehensive mechanical properties of the composites. The mixed powders were sintered at 1850 °C under a uniaxial loading of 30 MPa for 2 h via hot-pressing. Through the measurement of XRD, SEM and related mechanical properties, the influence of B₄C content on the microstructure and mechanical properties of TiB₂–B₄C composites ceramics was discussed. The experimental results show that TiB₂–B₄C composite ceramics exhibit excellent mechanical properties, which can be attributed to the dense microstructure and fine grain size. In addition, TiB₂–B₄C composite ceramic shows a relatively high comprehensive properties when the addition amount of B₄C is 20 wt%. The relative density, Vickers hardness, fracture toughness and flexural strength are measured to be 99.61%, 27.63 ± 1.73 GPa, 4.77 ± 0.06 MPa m^1/2, 612.5 ± 28.78 MPa, respectively.     

High toughness TiB2–Al2O3 composite ceramics produced by reactive hot pressing with fusible components

A manufacturing method of high toughness TiB₂–Al₂O₃ ceramic composites by reactive hot pressing via exothermic reactions with Al, B₂O₃, C and TiB₂ has been developed. The usage of fusible initial components (Al and B₂O₃) in the hot pressing procedure allowed forming dense ceramics with homogeneous fine structure at 1900°C and 20 MPa (after 8 min exposure) without any grinding of the initial powders. The hot pressed TiB₂–Al₂O₃ composites exhibit the fracture toughness of 9 MPa m^1/2, which is much higher than that of both single phase TiB₂ (6 MPa m^1/2) and Al₂O₃ (4 MPa m^1/2) ceramics.     

Wear resistance of αSiC–TiB2 composites prepared by reactive sintering

The relative wear resistance of αSiC–TiB₂ composites prepared by reactive sintering was investigated on a pin on flat tribometer, in air and in presence of water. Experimental results show that the composite materials are less worn than monolithic SiC. The wear mechanisms in air and water are identified.In air, a protective oxidised debris layer is formed on the composites, whereas roller formation was observed with SiC. In water, the surface of the composites is polished, whereas SiC is worn by fragile ruptures (cleavages).     

Densification of MCMB–SiC composites via two-step hot pressing

Mesocarbon microbead–SiC (MCMB–SiC) composites with 30 wt% MCMBs were densified using a two-step hot pressing method. Based on the pyrolysis of the initial MCMB powders, the effects of the pressing schedule on densification were investigated and the optimal first-step pressing temperature was determined. To reveal the influence of temperature on their microstructures, the raw MCMB powders were heat-treated at different temperatures in the range 400–1400 °C. The morphologies and degrees of carbonisation at different temperatures were additionally studied. The results showed that densification was mainly affected by the micro-gaps in the lamellar structure formed during the pyrolysis of the MCMBs. When the samples were first hot-pressed at a lower temperature and then at a higher temperature, the densification pressure required was effectively decreased. Furthermore, when the samples were first pressed at an appropriate temperature, the relative density of the composites was improved to a rather high value of 98.6%. The two-step hot pressing method was effective in fabricating dense C–SiC composites with high C content.     

Mechanical properties and deformation mechanisms of B4C–TiB2 eutectic composites

Samples of B₄C–TiB₂ eutectic are laser processed to produce composites with varying microstructural scales. The eutectic materials exhibit both load dependent and load independent hardness regimes with a transition occurring between 4 and 5 N indentation load. The load-independent hardness of eutectics with a microstructural scale smaller than 1 μm is about 31 GPa, and the indentation fracture toughness (5–10 N indenter load) of the eutectics is 2.47–4.76 MPa m^1/2. Indentation-induced cracks are deflected by TiB₂ lamellae, and indentation-induced spallation is reduced in the B₄C–TiB₂ eutectic compared to monolithic B₄C. Indentation-induced amorphization in monolithic B₄C and the B₄C phase of the eutectic is detected using Raman spectroscopy. Sub-surface damage is observed using TEM, including microcracking and amorphization damage in B₄C and B₄C–TiB₂ eutectics. Dislocations are observed in the TiB₂ phase of eutectics with an interlamellar spacing of 1.9 μm.     

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.     

C/SiC–ZrB2–ZrC composites fabricated by reactive melt infiltration with ZrSi2 alloy

C/SiC–ZrB₂–ZrC composites were prepared by reactive melt infiltration (RMI) combined with vacuum pressure impregnation (VPI) method. B₄C–C was first introduced into C/SiC composites with a porosity of about 30% by impregnating the mixture of B₄C and phenol formaldehyde resin, followed by pyrolysis at 900 °C. The molten ZrSi₂ alloy was then infiltrated into the porous C/SiC–B₄C–C to obtain C/SiC–ZrB₂–ZrC composites. The flexural strength was tested. The ablation behavior was investigated under an oxyacetylene torch flame. It has been found that the C/SiC–ZrB₂–ZrC showed a high flexural strength and an excellent ablation resistance. The reactions between ZrSi₂ alloy and B₄C–C were studied, and a model based on these reactions was built up to describe the formation mechanism of the matrix.     

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.     

Microstructure and mechanical properties of C/C–SiC composites fabricated by a rapid processing method

C/C–SiC composite was fabricated with time efficiency and low cost by a two-step process. A quasi 3D carbon-fiber-felt was firstly densified to C/C composite in 2–5 h by a thermal gradient CVI method based on precursor of kerosene. Then, the C/C composite of different porosities was reactively infiltrated with Si for 40 min to obtain C/C–SiC composite. The influence of the porosity of the C/C composite on the microstructure and mechanical properties of the C/C–SiC composite was investigated. The results show that the density of the C/C–SiC composite increases from 2.0 g/cm³ to 2.3 g/cm³ while its porosity decreases from 5.8% to 1.7% with the increasing porosity of the C/C composite. Moreover, the porosity of the C/C composite affects both the amounts of β-SiC, Si phases and the mechanical properties of the C/C–SiC composite. The flexural strength and modulus of the C/C–SiC composite are much higher than those of the C/C composite. The C/C–SiC composite from the C/C composite of 19.7% porosity has the highest flexural strength and modulus, which are 132 MPa and 14.4 GPa, respectively.     

Microstructure and mechanical properties of WB2–B4C composites fabricated by boro/carbothermal reduction and SPS

The phase composition, microstructure, and mechanical properties of the WB₂–B₄C composites fabricated by a combination of boro/carbothermal reduction and spark plasma sintering (SPS) method with WO₃, B₄C, and graphite as raw materials were investigated in this study. The experimental results showed that the relative density of the as-sintered WB₂–B₄C composites was ∼93.1% and ∼99.5%, respectively, after being SPS sintered at 1600°C under the applied load of 30 MPa for 10 min. Scanning electron microscope analysis showed that a network structure with WB₂ grains surrounded by B₄C grains was observed after sintering. Analyses of high-resolution TEM showed semi-coherent interface and lattice distortion transition region between WB₂ and B₄C grains. The Vickers hardness of WB₂–B₄C composite increased to 22.3 ± 0.9 GPa at 9.8 N owing to the fully dense, solid solution of C, and three-dimensional network structure. Moreover, the fracture toughness and flexural strength of WB₂–B₄C composite reach 6.04 ± 0.81 MPa m^1/2 and 750 ± 80 MPa, respectively, which could be attributed to the semi-coherent interface between WB₂ and B₄C grains.     

Multidimensional nano-graphite constructed TiB2–SiC–B4C composite ceramics with the integration of mechanical and electromagnetic properties

The goal of this study is to create structure-functional integrated ceramic matrix composites with high structural strength and electromagnetic absorbing properties. The multidimensional nano-graphite (1-Dimensional rod-like nano-graphite, 0-Dimensional dispersive nano-graphite, and 2-Dimensional lamellar nano-graphite) were employed to construct TiB₂–SiC–B₄C composites via high-energy ball milling, vacuum filtration, and reactive SPS sintering. The microstructure of multidimensional nano-graphite was investigated using XRD and HRTEM and determined to be a crystal-amorphous coexisting. Furthermore, solid solution reaction and interfacial evolution are confirmed as the primary influence on the microstructure of TiB₂–SiC–B₄C composite. A significant improvement occurs on the flexural strength (647.6 MPa) and bending toughness (5.1 MPa m^1/2). Meanwhile, the multi-dimensional nano-graphite gives the TiB₂–SiC–B₄C composite the loss ability of electromagnetic waves, and the matching thickness of the 10 vol% sample is 2.4 mm and the absorption range is 10.4–11.3 GHz.     

Reactive hot pressing of ZrB2–ZrCx ultra-high temperature ceramic composites with the addition of SiC particulate

Starting with non-stoichiometric Zr–B₄C powder mixture ZrB₂–ZrC matrix composites with SiC particulate addition have been made. It was found that variable amounts (5–25 vol%) of SiC could be incorporated and reactively hot pressed (RHPed) to relative densities of 97–99% at 1400–1500 °C. This technique has the potential to fabricate ZrB₂-based matrices at low temperatures with a variety of reinforcements whose composition and volume fraction are not limited by stoichiometric considerations. The hardness of the composites is in the range of 17–22 GPa.     

Synthesis and performance of TiB2–B4C composites by high pressure of TiC–B mixture

TiB₂–B₄C composites were in situ synthesized and consolidated by high pressure synthesis method from a mixture of TiC and B powders at the pressure and temperature of 5.0 GPa and 1500℃-1900℃. The phase composition, microstructure, density, hardness, thermal conductivity, and electrical resistivity of TiB₂–B₄C composites were analyzed. As the increase in the synthesis temperature, the products were TiB₂ and B₄C phases and that crystallinity improved. TiB₂–B₄C composites were dense without obvious pores. TiB₂–B₄C composites synthesized at 1800℃ obtained the optimized performance, including the relative density of 98.2%, the Vickers hardness of 31.7 ± 1.2 GPa with the load of 9.8 N, the thermal conductivity of 30.3 ± 0.7 W/(m K), and the electrical resistivity of 3.3 × 10⁻³ Ω cm, respectively. The grain size of the TiB₂–B₄C composites changed with the increase in synthesis temperature, leading to the changes in hardness, thermal conductivity, and electrical resistivity.     

Mechanical properties of B4C–CrB2 binary eutectic composites prepared by arc-melting

B₄C–CrB₂ composites were prepared by arc-melting using B₄C and CrB₂ powders as raw materials. The eutectic composition of B₄C–CrB₂ system was 30B₄C–70CrB₂ (mol%) with a labyrinth-like irregularly layered eutectic microstructure, composed of B₄C phase about 1–2 μm in thickness dispersing in CrB₂ matrix, much smaller than raw powders. The interface of the eutectic composite was well bonded, and there were edge dislocations at the interface to alleviate the interface mismatch. The eutectic temperature of B₄C–CrB₂ composites was approximately 2200 K. At the eutectic composition, the B₄C–CrB₂ composites showed the maximum Vickers hardness (24.6 GPa) and fracture toughness (4.3 MPa m^1/2) at room temperature.     

ZrB2–SiC composites prepared by reactive pulsed electric current sintering

Fully densified ZrB₂–20 vol% SiC composites were produced by reactive pulsed electric current sintering (PECS) of a powder mixture containing ZrH₂, B, SiC and B₄C within a total thermal cycle time of only 50 min. During the combined synthesis and sintering process, the ZrH₂ powder decomposed gradually from ZrH₂ into ZrH_m and finally metal Zr that reacted with elemental B to form the ZrB₂ matrix. Reducing the ZrH₂ particle size by attritor milling significantly enhanced densification and allowed initiation of self-propagating high temperature synthesis (SHS) during PECS. The PECS grades exhibited a slightly textured structure, with ≤17% of the ZrB₂ grains oriented with their (0 0 1) planes perpendicular to the direction of pressure and DC current. Because of the ZrB₂ grain orientation, anisotropic mechanical properties were observed. Ceramics prepared from attritor milled powders and PECS with a pressure applied after 5 min upon reaching 1900 °C achieved excellent flexural strengths of 901–937 MPa. The hardness and fracture toughness were respectively 19.7–19.8 GPa and 4.0–4.7 MPa m^1/2 in the direction parallel and 20.2–21.3 GPa and 3.8–3.9 MPa m^1/2 in the direction perpendicular to the applied pressure.