Microstructure and mechanical properties of carbon-precursor-added B4C and B4C−SiC ceramics subjected to pressureless sintering

Organic-carbon-precursor-added B₄C and B₄C–SiC ceramics were subjected to pressureless sintering at various temperatures. The carbon precursor increased the densification of the B₄C and B₄C–SiC ceramics sintered at 2200 °C to 95.6 % and 99.1 % theoretical density (T.D.), respectively. The pyrolytic carbon content of the B₄C–SiC composite decreased with increasing SiC content. The graphitization degree of pyrolytic carbon decreased slightly with the amount of carbon precursor and content of SiC. The 95 wt. % B₄C–5 wt. % SiC composite added with 7.5 wt. % carbon precursor and sintered at 2200 °C outperformed the other B₄C–SiC composites, and its sintered density, flexural strength, Young’s modulus, and microhardness were 98.6 % T.D., 879 MPa, 415 GPa, and 28.5 GPa, respectively. These values were higher than those of composites prepared via pressureless sintering and comparable to those of composites fabricated via hot pressing and/or using metal or oxide additives.     

Toughening of super-hard ultra-fine grained B4C densified by spark-plasma sintering via SiC addition

Toughening of super-hard B₄C ceramics with ultra-fine grained microstructures via the addition of SiC (15 wt.%) or the simultaneous addition of SiC (15 wt.%) and graphite (2 wt.%) is reported. The ultra-fine grained B₄C–SiC and B₄C–SiC–C composites prepared by spark-plasma sintering from powder mixtures subjected to high-energy co-ball-milling are found to be remarkably tougher (i.e., ～65% and 50%) than the pure B₄C ceramic with a coarsened microstructure. Crack bridging by the homogenously dispersed SiC grains can give an explanation for the improvement in toughness. Also, the addition of SiC to the B₄C matrix was found to change the fracture mode from purely transgranular to a mixture of intergranular and transgranular fracture. This is derived from the weakness of the B₄C–SiC interfaces due to the existence of residual thermo-elastic stresses. It was also found that despite SiC is softer than B₄C, the B₄C–SiC are yet extremely hard if densified appropriately, with the hardness even reaching 36 GPa.     

Effects of SiC on the microstructures and mechanical properties of B4C–SiC–rGO composites prepared using spark plasma sintering

In this study, B₄C–SiC–rGO composites with different SiC contents were prepared by spark plasma sintering at 1800 °C for 5 min under a uniaxial pressure of 50 MPa. The effects of SiC on the microstructures and mechanical properties of the B₄C–SiC–rGO composites were investigated. The optimal values for flexural strength (545.25 ± 23 MPa) and fracture toughness (5.72 ± 0.13 MPa·m^1/2) were obtained simultaneously when 15 wt.% SiC was added to 5 wt.%–GO reinforced B₄C composites (BS15G5). It was found that SiC and rGO inhibited the grain growth of B₄C and improved the mechanical properties of the B₄C–SiC–rGO composites. The clear and narrow grain boundaries of rGO–B₄C and rGO–SiC, as well as the semi-coherent B₄C–SiC interface, indicated strong interface compatibility. The twin structures of SiC and B₄C observed in the composites improved their fracture toughness. Crack deflection and crack bridging caused by the SiC grains as well as rGO bridging and rGO pull-out were observed on the crack propagation path.     

Si/B/C/N/Al precursor-derived ceramics: Synthesis,high temperature behaviour and oxidation resistance

The Si/B/C/N/H polymer T2(1), [B(C₂H₄Si(CH₃)NH)₃]_n, was reacted with different amounts of H₃Al·NMe₃ to produce three organometallic precursors for Si/B/C/N/Al ceramics. These precursors were transformed into ceramic materials by thermolysis at 1400 °C. The ceramic yield varied from 63% for the Al-poor polymer (3.6 wt.% Al) to 71% for the Al-rich precursor (9.2 wt.% Al). The as-thermolysed ceramics contained nano-sized SiC crystals. Heat treatment at 1800 °C led to the formation of a microstructure composed of crystalline SiC, Si₃N₄, AlN(+SiC) and a BNC_x phase. At 2000 °C, nitrogen-containing phases (partly) decomposed in a nitrogen or argon atmosphere. The high temperature stability was not clearly related to the aluminium concentration within the samples. The oxidation behaviour was analysed at 1100, 1300, and 1500 °C. The addition of aluminium significantly improved the oxide scale quality with respect to adhesion, cracking and bubble formation compared to Al-free Si(/B)/C/N ceramics. Scale growth rates on Si/B/C/N/Al ceramics at 1500 °C were comparable with CVD–SiC and CVD–Si₃N₄, which makes these materials promising candidates for high-temperature applications in oxidizing environments.     

Preparation of novel carborane-containing boron carbide precursor and its derived ceramic hollow microsphere

High melting point and hardness of boron carbide make it extremely difficult to be directly prepared as hollow microsphere. However, precursor derived method is an effective approach to prepare ceramic materials with complex shape. Therefore, in this work a novel boron carbide precursor, poly[1,7-bis(4-chlorophenyl)-m-carborane] (P4CB), was synthesized. The ceramic yield of the precursor P4CB reached as high as 90.25% at 900 °C in nitrogen. Oxidation of P4CB in air was barely observed below 500 °C, and a passive oxidation was exhibited beyond 700 °C. The P4CB/PAN slurry was prepared and coated on a polyoxymethylene (POM) ball substrate. After air crosslinking, substrate decomposition and heat-treatment at 1100 °C in Ar atmosphere, boron carbide hollow microsphere with diameter of approximate 1.34 mm and average shell thickness of 30 μm was finally obtained. The novel precursor could be also utilized to fabricate boron carbide ceramics with different shapes due to its high ceramic yield.     

Mechanical properties and microstructure evolution of pressureless-sintered B4C–SiC ceramic composite with CeO2 additive

Boron carbide ceramic composites (B₄C)-silicon carbide (SiC) with the cerium oxide (CeO₂) additive, which was varied from 0 wt% to 9 wt%, were prepared by pressureless sintering at 2150 °C for 60 min. The effect of CeO₂ additive content on the microstructure and mechanical properties of the B₄C–SiC ceramic composites was investigated in detail. In-situ synthesised cerium hexaboride (CeB₆) was identified in the B₄C–SiC ceramic composites. B-rich transition zones (such as B_38.22C₆, B_51.02C_1.82) were formed between the B₄C and CeB₆ grains, which introduced local lattice distortion to increase the sintering driving force. The thermal conductivity coefficient of CeB₆ was higher than that of B₄C, which benefited the delivery of heat quantity and helped achieve a highly dense and uniform sintered body. When the CeO₂ additive was excessively increased (more than 5 wt%), the CeB₆ grains had a large grain size and exhibited an increase in the amount of generated carbon monoxide (CO) gas, which led to an increase in the porosity of the B₄C–SiC ceramic composites and decrease in the mechanical properties. The optimum values of the relative density, Vickers hardness, flexural strength, and fracture toughness of the B₄C–SiC ceramic composite with 5 wt% CeO₂ additive were 96.42%, 32.21 GPa, 380 MPa, and 4.32 MPa m^1/2, respectively.     

Microstructure and properties of a graphene platelets toughened boron carbide composite ceramic by spark plasma sintering

A kind of B₄C/SiC composite ceramic toughened by graphene platelets and Al was fabricated by spark plasma sintering. The effects of graphene platelets and Al on densification, microstructure and mechanical properties were studied. The sintering temperature was decreased about 125–300?°C with the addition of 3–10?wt% Al. Al can also improve fracture toughness but decrease hardness. The B₄C/SiC composite ceramic with 3?wt%Al and 1.5?wt% graphene platelets sintered at 1825?°C for 5?min had the optimal performances. It was fully densified, and the Vickers hardness and fracture toughness were 30.09?±?0.39?GPa and 5.88?±?0.49?MPa?m^1/2, respectively. The fracture toughness was 25.6% higher than that of the composite without graphene platelets. The toughening mechanism of graphene platelets was also studied. Pulling-out of graphene platelets, crack deflection, bridging and branching contributed to the toughness enhancement of the B₄C-based ceramic.     

Tribological properties of SiC-B4C ceramics under dry sliding condition

SiC-B₄C ceramic composites with different ratios of SiC to B₄C were produced. The relative density, mechanical properties, initial surface characteristics, dry sliding tribological properties against SiC ball and worn surface characteristics of the SiC-B₄C ceramics were studied. Results of dry sliding tribological tests showed that, 40 wt. % SiC-60 wt. % B₄C ceramic composite had the best tribological properties in SiC-B₄C ceramic composites. A relief structure with height difference of 10−30 nm between B₄C grains and SiC grains is formed after dry sliding. This relief structure, on the one hand, can reduce real contact area on interface, decreasing adhesion effect, and on the other hand, can fix or trap the wear pieces formed on sliding interface during the dry sliding process, reducing the abrasive wear. However, there is a limit to the beneficial influence of decreased adhesion effect and reduced abrasive wear, and an optimum proportion of relief structure. Pores can also fix or trap some wear pieces, reducing the abrasive wear. Under the condition of strong bonding between SiC grains and B₄C grains, the SiC-B₄C ceramic composites with higher porosity can obtain better tribological properties. In addition, it is observed by AFM that the depth of scratch on B₄C grains is shallower than that on SiC grains. Hence, it is demonstrated by micro scale measurement that the wear rate of B₄C is lower than that of SiC in this study.     

Synthesis of SiBNC-Al ceramics with different aluminum contents via polymer-derived method

This study reports the synthesis of three types of aluminium (Al)-modified polyborosilazane ceramic precursors (PBSAZ) from C₈H₁₉Al/HSiCl₃/HMDZ/BCl₃ and their thermal conversion to SiBNC-Al ceramics at 1000°C. FT-IR, nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA) are used to characterize the structures and properties of the PBSAZ. PBSAZ is found to be built up of the Si─N─B framework, with Al successfully introduced into the ceramic network structures. The ceramic yield is 63.5 wt.% for the Al-poor polymers (PBSAZ-5) and 65.1 wt.% for the Al-rich polymers (PBSAZ-1). The high-temperature cracking behavior and the crystal phase structures of the ceramics were characterized by XRD and Raman, which revealed that SiBNC-Al ceramics contained Si₄N₃, SiC, and AlN (+SiC) crystals after heat treatment at 1600°C. The oxidation behavior of SiBNC and SiBNC-Al ceramics at 1500°C shows that the introduction of Al improves the quality of the oxide layer, effectively suppresses the oxide layer cracking phenomenon, and reduces gas bubble generation.     

Processing of silicon carbide–boron carbide–aluminium composites

The aim of this work was to shed light on the wetting mechanism in the SiC–B₄C–Al system and to explore processing routes that enable infiltration of Al alloys into these ceramic powder mixtures without the formation of the deleterious reaction product Al₄C₃. For this purpose, powder mixtures consisting of SiC and pre-treated B₄C were pressureless infiltrated with Al alloys at relatively low temperatures under an inert gas atmosphere. Depending on the characteristics of the starting powders fully infiltrated composites were achieved in the temperature range of 935–1420 °C. It was observed that addition of pre-treated B₄C to SiC enabled complete infiltration of the ～0.6 cm thick preforms. The bulk density of all produced composites was >98% of the X-ray density. By controlling the surface chemistry and particle size of the starting powders as well as the processing conditions, the wetting behaviour and reaction kinetics of this system could be tailored so as to render fully dense SiC–B₄C–Al composites devoid of Al₄C₃.     

Geometrical morphology optimisation of laser drilling in B4C ceramic: From plate to hollow microsphere

Boron carbide (B₄C) ceramic plates with 400-µm thickness and hollow microspheres were used for hole machining study with a fibre laser. The diameter, hole circularity, taper angle, and recast layer were evaluated as functions of processing parameters such as the peak power and the ablation time. Scanning electron microscope (SEM) was used to observe surface morphologies of drilled materials and the attached energy-dispersive spectrometer was used for elemental analyses of recast layers around holes. Based on the results of characterisations, holes on front side were found to have a larger diameter but a worse circularity than those on back side under different conditions. The taper angle was steady near 1.8° with the increase in laser parameter values. To obtain holes on B₄C ceramic with relatively good quality, the peak power and the ablation time should be controlled to be about 40 W and in 5–10 ms. In addition, compared with previous reports, superior holes drilled on B₄C hollow microspheres with a better circularity and smooth layer on the inner wall can be obtained.     

Electromagnetic wave absorption properties of hot-pressed Si3N4-SiC ceramic nanocomposites

High-density Si₃N₄-SiC ceramic nanocomposites have exceptional mechanical properties, but little is known about their electromagnetic wave absorption (EMA) capabilities. In this paper, the effects of sintering temperature and starting material compositions on the dielectric and EMA properties of hot-pressed Si₃N₄-SiC ceramic nanocomposites were investigated. The real and imaginary permittivities of Si₃N₄-SiC ceramic nanocomposites increase with increasing sintering temperature or SiC content, particularly at the sintering temperature of 1850°C and SiC content of 50 wt.%. This is primarily due to the improvement of interfacial and defect polarizations, which is caused by the doping of nitrogen into the SiC nanocrystals during the solution-precipitation process. The real and imaginary permittivities of Si₃N₄-SiC ceramic nanocomposites show decreasing trends as sintering aid content increases. Si₃N₄-SiC ceramic composites have both good EMA and mechanical properties when they are sintered at 1850°C with 30 wt.% SiC and 5–8 wt.% sintering aids. The minimum reflection loss and maximum flexural strength reach -58 dB and 586 MPa, respectively. Materials with multilayered structural designs have both strong and broad EMA properties.     

High temperature strength of silicon carbide sintered with 1 wt.% aluminum nitride and lutetium oxide

A heat-resistant SiC ceramic was developed from submicron β-SiC powders using a small amount (1 wt.%) of AlN–Lu₂O₃ additives at a molar ratio of 60:40. Observation of the ceramic using high-resolution transmission electron microscopy (HRTEM) showed a lack of amorphous films in both homophase (SiC–SiC) boundaries and junction areas. The junction phase consisted of Lu–Si–O elements, and the homophase boundaries contained Lu, Al, O, and N atoms as segregates. The ceramic maintained its room temperature (RT) strength up to 1600 °C. The flexural strength of the ceramic was 630 MPa and 633 MPa at RT and 1600 °C, respectively.     

Chemical process and solid solution formation in reactive hot pressed ZrB2–SiC ceramics doped with W

ZrB₂–SiC doped with W was prepared from a mixture of Zr, Si, B₄C and W via reactive hot pressing. The fully dense ZrB₂–SiC–WB–ZrC ceramic was obtained at 1900°C for 60 min under 30?MPa in an argon atmosphere. Reaction path and solid solution characteristics of the starting powders were studied through a series of pressureless heat treatment at temperatures between 700 and 1500°C. The solid solution phases of (Zr, W)B₂, (W, Zr)B and (Zr, W)C were formed directly by reactions between the precursors. Homogeneous distribution of solute atoms in solution and the solid solubilities were also studied.     

High-temperature oxidation induced layering process for Si–C–B–N ceramic fibers with SiC nanograins

High-temperature oxidation resistance is important for Si–C–B–N ceramic fibers when reinforcing ceramic matrix composites with superior reliability and faulting tolerance. At present, few studies have investigated on the high-temperature oxidation behavior of Si–C–B–N fibers, limiting their further applications. In this work, we analyzed the high-temperature oxidation process of Si–C–B–N ceramic fibers with SiC nanograins (SiBCN-SiCn fibers) at 1000–1500 °C in air. SiBCN-SiCn fibers stated to be oxidized at 1000 °C, with the formation of thin oxide layer. After oxidizing at 1300 °C, obvious oxide layer that mainly consisted of amorphous SiO₂ could be detected. Further oxidizing at 1500 °C caused the thickness increment of oxide layer, which could inhibit the oxidation products (CO, N₂) to release away from the fibers. The remained CO and N₂ may react with SiC nanograins to form SiO₂ and graphite-like g-C₃N₄, causing the formation of additional transition layer. Our finding may support useful information for the applications of SiBCN-SiCn fibers under harsh environment.     

Densification behaviour and mechanical properties of B4C–SiC intergranular/intragranular nanocomposites fabricated through spark plasma sintering assisted by mechanochemistry

High-performance B₄C–SiC nanocomposites with intergranular/intragranular structure were fabricated through spark plasma sintering assisted by mechanochemistry with B₄C, Si and graphite powders as raw materials. Given their unique densification behaviour, two sudden shrinkages in the densification curve were observed at two very narrow temperature ranges (1000–1040 °C and 1600–1700 °C). The first sudden shrinkage was attributed to the volume change in SiC resulting from disorder–order transformation of the SiC crystal structure. The other sudden shrinkage was attributed to the accelerated densification rate resulting from the disorder–order transformation of the crystal structure. The high sintering activity of the synthesised powders could be utilised sufficiently because of the high heating rate, so dense B₄C–SiC nanocomposites were obtained at 1700 °C. In addition, the combination of high heating rate and the disordered feature of the synthesised powders prompted the formation of intergranular/intragranular structure (some SiC particles were homogeneously dispersed amongst B₄C grains and some nanosized B₄C and SiC particles were embedded into B₄C grains), which could effectively improve the fracture toughness of the composites. The relative density, Vickers hardness and fracture toughness of the samples sintered at 1800 °C reached 99.2±0.4%, 35.8±0.9 GPa and 6.8±0.2 MPa m^1/2, respectively. Spark plasma sintering assisted by mechanochemistry is a superior and reasonable route for preparing B₄C–SiC composites.     

Single-source-precursor synthesis and high-temperature evolution of a boron-containing SiC/HfC ceramic nano/micro composite

A boron-containing SiHfC(N,O) amorphous ceramic was synthesized upon pyrolysis of a single-source-precursor at 1000 °C in Ar atmosphere. The high-temperature microstructural evolution of the ceramic at high temperatures was studied using X-ray powder diffraction, Raman spectroscopy, solid-state nuclear magnetic resonance spectroscopy and transmission electron microscopy. The results show that the ceramic consists of an SiHfC(N,O)-based amorphous matrix and finely dispersed sp²-hybridized boron-containing carbon (i.e. B_yC). High temperature annealing of B_yC/SiHfC(N,O) leads to the precipitation of HfC_xN_1-x nanoparticles as well as to β-SiC crystallization. After annealing at temperatures beyond 1900 °C, HfB₂ formation was observed. The incorporation of boron into SiHfC(N,O) leads to an increase of its sintering activity, consequently providing dense materials possessing improved mechanical properties as compared to those of boron-free SiC/HfC. Thus, hardness and elastic modulus values up to 25.7 ± 5.3 and 344.7 ± 43.0 GPa, respectively, were measured for the dense monolithic SiC/HfC_xN_1-x/HfB₂/C ceramic nano/micro composite.     

Polymer‐Derived SiC/B4C/C Nanocomposites: Structural Evolution and Crystallization Behavior

Structural evolution and crystallization behavior between 600°C and 1450°C during the preparation of bulk SiC/B₄C/C nanocomposites by the pyrolysis of CB‐PSA preceramic were investigated. The CB‐PSA preceramic converts into carbon‐rich Si–B–C ceramics up to 800°C. Structural evolution and crystallization of Si–B–C materials could be controlled by adjusting the pyrolytic temperature. The Si–B–C ceramics are amorphous between 800°C and 1000°C. Phase separation and crystallization begin at 1100°C. The crystallization of β‐SiC takes place at 1100°C and B₄C nanocrystallites generate at 1300°C. The sizes of β‐SiC and B₄C nanocrystals increase with the pyrolytic temperature rising. In addition, the boron‐doping effect on structural evolution was studied by comparing the crystallization and graphitization behavior of Si–B–C ceramics and the corresponding Si–C materials. Boron is helpful for the growth of β‐SiC nanocrystals and the graphitization, but harmful for the nucleation of β‐SiC crystallites.     

Transition metal diboride-silicon carbide-boron carbide ceramics with super-high hardness and strength

Three phase boride and carbide ceramics were found to have remarkably high hardness values. Six different compositions were produced by hot pressing ternary mixtures of Group IVB transition metal diborides, SiC, and B₄C. Vickers’ hardness at 9.8 N was ~31 GPa for a ceramic containing 70 vol% TiB₂, 15 vol% SiC, and 15 vol% B₄C, increasing to ~33 GPa for a ceramic containing equal volume fractions of the three constituents. Hardness values for the ceramics containing ZrB₂ and HfB₂ were ~30% and 20% lower than the corresponding TiB₂ containing ceramics, respectively. Hardness values also increased as indentation load decreased due to the indentation size effect. At an indentation load of 0.49 N, the hardness of the previously reported ceramic containing equal volume fractions of TiB₂, SiC and B₄C was ~54 GPa, the highest of the ceramics in the present study and higher than the hardness values reported for so-called “superhard” ceramics at comparable indentation loads. The previously reported ceramic containing 70 vol% TiB₂, 15 vol% SiC, and 15 vol% B₄C also displayed the highest flexural strength of ~1.3 GPa and fracture toughness of 5.7 MPa·m^1/2, decreasing to ~0.9 GPa and 4.5 MPa·m^1/2 for a ceramic containing equal volume fractions of the constituents.     

Air-sintered silicon (Si)-bonded silicon carbide (SiC) hollow fiber membranes for oil/water separation

In this work we evaluated the effect of adding Si as sintering additive into SiC for producing air-sintered hollow fiber membranes. According to crystallographic analyses, SiC and Si were converted to SiO₂ after sintering at 1350 °C. The addition of 30 wt% of Si into SiC ceramic material promoted the binding of SiC particles and improved the membrane mechanical resistance to 42.25 ± 3.39 MPa after air sintering at 1350 °C. The produced asymmetric ceramic membrane presented a packed pore-network and micro-voids with pore sizes of 1.73 and 5.29 μm, respectively. The filtration of an oil/water emulsion enabled oil retention 98.75 ± 0.95 %. Cake formation was the main fouling occurrence and membrane regeneration with equivalent oil retention and similar steady sate flux was achieved after water cleaning under ultrasound irradiation. Thus, the use of Si as air-sintering aid was favorable for producing Si-bonded SiC hollow fiber membranes with suitable application for oil/water separation.