Ultrafine-grained B6O–diamond composites with superb mechanical properties

We report here the high-pressure and high-temperature (HPHT) synthesis of well-sintered B₆O–diamond composites from B₆O and carbon black nanopowders. The carbon black was transformed into diamond nanograins at HPHT conditions, and simultaneously formed high-strength B₆O–diamond interfaces. The ultrafine B₆O and diamond nanograins and the high-strength B₆O–diamond interfaces synergistically construct excellent mechanical properties for the synthesized composites. The B₆O–diamond composites possess a hardness (avg. 52 GPa) comparable to that of polycrystalline diamond (40–60 GPa), whereas the fracture toughness (avg. 7.2 MPa m^1/2) is increased several times compared to previously synthesized polycrystalline B₆O ceramics (1.7–3.1 MPa m^1/2) and B₆O-based composites (3–4 MPa m^1/2). Fracture behavior analysis demonstrates that the main toughening mechanisms in this B₆O–diamond composite are nanotwin toughening, crack deflection, and crack bridging.     

Enhancement mechanical properties of in-situ preparated B4C-based composites with small amount of (Ti3SiC2+Si)

B₄C-based composites were synthesized by spark plasma sintering using B₄C、Ti₃SiC₂、Si as starting materials. The effects of sintering temperature and second phase content on mechanical performance and microstructure of composites were studied. Full dense B₄C-based composites were obtained at a low sintering temperature of 1800 °C. The B₄C-based composite with 10 wt% (TiB₂+SiC) shows excellent mechanical properties: the Vickers hardness, fracture toughness, and flexural strength are 33 GPa, 8 MPa m^1/2, 569 MPa, respectively. High hardness and flexural strength were attributed to the high relative density and grain refinement, the high fracture toughness was owing to the crack deflection and uniform distribution of the second phase.     

Investigation of the density and microstructure homogeneity of square-shaped B4C-ZrB2 composites produced by spark plasma sintering method

Square-shaped monolithic B₄C and B₄C-ZrB₂ composites were produced by spark plasma sintering (SPS) method to investigate the effect of 5, 10, 15 vol% ZrB₂ addition on the densification, mechanical and microstructural properties of boron carbide. The relative density of B₄C increased with the increasing volume fraction of ZrB₂ and density differences in different regions of the sample narrowed down. Homogeneous density distribution and microstructure were accomplished with the increasing holding time from 7 to 20 min for the B₄C-15 vol% ZrB₂ composites, and the highest overall relative density was achieved as 99.23%. The hardness and fracture toughness of composites were enhanced with the addition of ZrB₂ compared to monolithic B₄C. The enhancement in fracture toughness was observed due to the crack deflection, crack bridging and crack branching mechanisms. The B₄C-15 vol% ZrB₂ composite exhibited the combination of superior properties (hardness of 33.08 GPa, Vickers indentation fracture toughness of 3.82 MPa.m^1/2).     

Hard and tough ultrafine-grained B4C-cBN composites prepared by high-pressure sintering

Tough and hard ultrafine-grained B₄C-cBN composites were firstly fabricated by high-pressure sintering mixed B₄C and cBN nanopowders at 6 GPa and 1700 °C. The phase transition from cBN to hBN is avoided by high pressure during the sintering process. The effects of the cBN content on the densification and mechanical properties of B₄C-cBN composites were evaluated. The results indicated that the hardness of the as-fabricated composites increased gradually with the increase of cBN content. The composite composed of 50 wt.% cBN exhibited excellent comprehensive mechanical properties with relative density of 98.6 %, density of 2.9 g/cm³, Vickers hardness of 36.2 GPa and fracture toughness of 6.7 MPa·m^1/2. The introduction of superhard cBN maintained the lightweight and high hardness while enhancing the fracture toughness of the B₄C. The main toughening mechanisms were crack bridging, crack deflection and pull-out of homogeneously dispersed cBN grains.     

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.     

Spark plasma sintering of boron nitride micron tubes reinforced boron carbide ceramics with excellent mechanical property

In this paper, the novel boron nitride micron tubes (BNMTs) were used to reinforce commercial boron carbide (B₄C) ceramics prepared via spark plasma sintering technology. The effects of the sintering parameters, sintering temperature, the holding time, and the BNMTs content on the microstructure and mechanical properties of B₄C/BNMTs composite ceramics were studied. The results indicated that adding a proper amount of BNMTs could inhibit the grain growth of B₄C and improve the fracture toughness of the B₄C/BNMTs composite ceramics. The prepared composite ceramic sample with 5 wt% BNMTs at 1850°C, 8 min and 30 MPa displayed the best mechanical properties. The relative density, hardness, fracture toughness, and bending strength of the samples were 99.7% ± .1%, 35.62 ± .43 GPa, 6.23 ± .2 MPa m^1/2, and 517 ± 7.8 MPa, respectively. Therein, the corresponding value of hardness, fracture toughness, and bending strength was increased by 10.3%, 43.59%, and 61.5%, respectively, than that of the B₄C/BNMTs composite ceramic without BNMTs. It was proved that the high interface binding energy and bridging effect between boron carbide and BNMTs were the toughening principle of BNMTs.     

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.     

The improvement mechanism of mechanical properties of B4C ceramics by constructing core–shell powders

B₄C ceramics have been widely used in armor plate and cutting tools due to their high hardness. However, their poor sintering performance and low fracture toughness have limited their extended applications. In order to solve these problems, B₄C@TiB₂ composite powders with core–shell structure were prepared by a sol–gel method using B₄C and TiCl₄ as raw materials and then sintered by spark plasma sintering. The composite powders were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The mechanical properties of B₄C ceramics were tested by indentation and three-point bending methods. The results showed that the B₄C@TiB₂ composite powders exhibited a tight core–shell structure, and the chemical bonds on the surface were mainly B–C and B–Ti bonds. When the molar ratio of B₄C:TiCl₄ was 2:1, the relative density and bulk density of B₄C ceramics reached 96.2% and 2.92 g/cm³, respectively. Because of the good sintering performance of the B₄C@TiB₂ composite powders, the Vickers hardness and fracture toughness reached 26.6 GPa and 5.22 MPa m^1/2, respectively. The bending strength reached a maximum of 570 MPa. The excellent fracture toughness can be attributed to crack deflection, crack branching, and the residual thermal stress of the core–shell structure.     

Microstructure and mechanical behaviour of transient liquid phase spark plasma sintered B4C–SiC–TiB2 composites from a B4C–TiSi2 system

Almost fully-dense B₄C–SiC–TiB₂ composites with a high combination of strength and toughness were prepared through in situ reactive spark plasma sintering using B₄C and TiSi₂ as raw materials. The densification, microstructure, mechanical properties, reaction, and toughening mechanisms were explored. TiSi₂ was confirmed as a reactive sintering additive to promote densification via transient liquid-phase sintering. Specifically, Si formed via the reaction between B₄C and TiSi₂ that served as a transient component contributed to densification when it melted and then reacted with C to yield more SiC. Toughening mechanisms, including crack deflection, branching and bridging, could be observed due to the residual stresses induced by the thermoelastic mismatches. Particularly, the introduced SiC–TiB₂ agglomerates composed of interlocked SiC and TiB₂ played a critical role in improving toughness. Accordingly, the B₄C–SiC–TiB₂ composite created with B₄C-16 wt% TiSi₂ achieved excellent mechanical performance, containing a Vickers hardness of 33.5 GPa, a flexural strength of 608.7 MPa and a fracture toughness of 6.43 MPa m^1/2.     

B4C-based hard and tough ceramics densified via spark plasma sintering using a novel Mg2Si sintering aid

Full-dense B₄C-based ceramics with excellent mechanical properties were fabricated using spark plasma sintering with Mg₂Si as a sintering aid at a low temperature of 1675 °C while applying a uniaxial pressure of 50 MPa. The effect of Mg₂Si addition on the densification behaviours, mechanical properties and microstructure of as-sintered ceramics were investigated. Not only did the formation of ultra-fine grained SiC using the in-situ reaction effectively inhibit the growth of B₄C grains, but it also contributed to the strength and toughness of the resultant ceramics. Additionally, microalloying Mg imparted more metal bonding characteristics to the B₄C matrix, thereby improving their ductility. The results indicate that the composite containing 7 wt% Mg₂Si had excellent mechanical properties, including a light weight of 2.54 g/cm³, Vickers hardness of 34.3 GPa, fracture toughness of 5.09 MPa m^1/2 and flexural strength of 574 MPa.     

Fabrication and characterization of FAST sintered micro/nano boron carbide composites with enhanced fracture toughness

Toughening of boron carbide (B₄C) without hardness degradation, was achieved by hierarchical structures consisting of B₄C micro-grains, titanium diboride (TiB₂) grains, and graphitic phases along B₄C grain boundaries. Such hierarchical structures were uniquely achieved by co-sintering of B₄C micro-powder and carbon-rich B₄C nano-powder, in situ formation of TiB₂, and by utilizing the short sintering time of field-assisted sintering technology. Toughening mechanisms observed after micro-indentation include crack deflection and delamination of graphite platelets, micro-crack toughening and crack deflection/bridging by TiB₂ grains. Fracture toughness enhancement was achieved while maintaining hardness: 4.65 ± 0.49 MPa m^1/2 fracture toughness and 31.88 ± 1.85 GPa hardness for a micro/nano B₄C-TiB₂ composite (15 vol% TiB₂ and 15 vol% B₄C nano-powders) vs. 2.98 ± 0.24 MPa m^1/2 and 32.46 ± 1.67 GPa for a reference micro B₄C sample. In future, macro-scale mechanical testing will be conducted to further evaluate how these micro-scale hierarchical structures can be translated to macro-scale mechanical properties.     

Microstructure and mechanical properties of boron carbide/graphene nanoplatelets composites fabricated by hot pressing

In this study, boron carbide (B₄C)-graphene nanoplatelets (GNPs) composites, with enhanced strength and toughness, were fabricated by hot pressing at 1950 °C under a pressure of 30 MPa for 1 h. Microstructure analysis revealed that the GNPs are homogenously dispersed within the B₄C matrix. Raman spectroscopy and electron microscopy showed the orientation of the GNPs in the composites. The effects of the amount of GNPs on the microstructure and mechanical properties of the composites were also investigated. The optimal mechanical properties were achieved using 1 wt% GNPs. The relative density, Vickers hardness, flexure strength, and fracture toughness of the B₄C-GNPs composite ceramic were found to be 99.12%, 32.8 GPa, 508 MPa, and 4.66 MPa m^1/2, respectively. The main toughening mechanisms included crack deflection in three dimensions, GNPs pull-out, and crack bridging. The curled and semi-wrapped GNPs encapsulated individual B₄C grains to resist GNPs pull-out and to deflect propagating cracks.     

Effect of manganese addition on sintering behavior and mechanical properties of alumina toughened zirconia

The effect of MnO₂ additives on the sintering behavior and mechanical properties of alumina-toughened zirconia (ATZ, with 10 vol% alumina) composites was investigated by incorporating different amounts of MnO₂ (0, 0.5, 1.0, and 1.5 wt%) and sintering at various temperatures ranging from 1300 to 1450 °C. The addition of MnO₂ up to 1.0 wt% improved the sintered density, hardness, flexural strength, and fracture toughness of the composite. However, the addition of 1.5 wt% MnO₂ degraded the relative density, hardness, and flexural strength of the composite due to the transformation of the ZrO₂ phase from tetragonal to monoclinic and grain coarsening. Optimal results were obtained with 1.0 wt% MnO₂ and sintering at 1450 °C, which improved the mechanical properties (hardness: 13.5 GPa, flexural strength: 1.2 GPa, fracture toughness: 8.5 MPa m^1/2) and lowered the sintering temperature compared to the conventional sintering temperature of ATZ composites (1550 °C). Thus, the ATZ composite doped with MnO₂ is a promising material for structural engineering ceramics owing to its improved mechanical properties and lower sintering temperature.     

In situ reaction and solid solution induced hardening in (Ti,Zr)B2-(Zr,Ti)C composites

(Ti,Zr)B₂ - (Zr,Ti)C ceramics were synthesized by reactive hot-pressing and solid solution coupling effect using ZrB₂ and TiC powders as starting materials. Effects of sintering temperature on phase relations, microstructure and mechanical properties were reported. The equimolar ZrB₂ and TiC reactants ensured a complete in situ reaction to form (Ti,Zr)B₂ and (Zr,Ti)C solid solutions. The (Ti,Zr)B₂ - (Zr,Ti)C composite sintered at 1750°C was fully densified, and exhibited a high hardness of 29.1 GPa due to fine-grain hardening and solid solution hardening. The optimized comprehensive mechanical properties such as a hardness of 27.9 GPa, a strength of 705 MPa and an indentation fracture toughness of 5.3 MPa m^1/2 were achieved in (Ti,Zr)B₂ - (Zr,Ti)C composites sintered at 1800°C for 1 hour.     

Performance of B4C/CeB6 composites fabricated via hot pressing under different processes

In this work, CeO₂ sintering additive reinforced B₄C ceramic composites were prepared by hot-pressing reaction sintering under different processes of low temperature–long holding time (1980°C, 30 MPa, 3 h, 4 wt% CeO₂) and high temperature–short holding time (2050°C, 30 MPa, .5 h, 4 wt% and 6 wt% CeO₂). The effect of sintering process and CeO₂ content on the microstructure and mechanical properties of B₄C-CeB₆ composites were investigated. The existed impurities in the obtained composites were also analyzed. Results show that CeO₂ is an active sintering additive. CeB₆ is formed by the reaction between CeO₂, B₄C and C in sintering process. The densification of B₄C ceramics is enhanced, and the grains can be refined by the formed CeB₆, which promotes the strength. The thermal expansion coefficient mismatch, crack deflection, and fracture mode change caused by the in situ formed CeB₆ improve the toughness. The process of low temperature–long holding time is more suitable for playing the role of CeO₂ additive in sintering of B₄C, under which condition the relative density, flexural strength, fracture toughness, and hardness reach 99%, 417 MPa, 5.32 MPa·m^1/2, and 30.66 GPa, respectively. The impurities in the composites are the kinds of Ti-contained, C-O-Mg-Ca-contained, C-O-Ca-S-contained, and Si-contained impurities.     

Nanoindentation and TEM investigation of spark plasma sintered TiB2–SiC composite

The impact of adding 20 vol% SiC on the properties of TiB₂ was studied in this research. The spark plasma sintering (SPS) process was used as the preparation technique at 1850 °C, the resulted composite was characterized using X-ray diffraction (XRD), field emission electron probe micro analyzer, transmission electron microscopy (TEM), field emission scanning electron microscopy, energy dispersive X-ray analysis, and nanoindentation. The prepared composite presented a relative density of ～98.5%. XRD and TEM results confirmed the in-situ formation of graphite; no in-situ TiC could be detected in the final microstructure of the composite. Forming a low melting point compound between SiO₂ and B₂O₃ oxides lead to the creation of wet interfaces between the ingredients. In terms of mechanical properties, the composite possessed Vickers hardness of 21.6 ± 2.2 GPa, flexural strength of 616 ± 28 MPa, fracture toughness of 5.3 ± 1.2 MPa m^1/2, and elastic modulus of 498 ± 12 GPa. According to the microstructural images, crack deflection, crack branching, crack arresting, crack bridging, and grain breaking events were found to be the main toughening mechanisms in this ceramic. In addition, the nanoindentation investigation indicated the role of SiC addition in improving the elastic modulus, hardness, and wear resistance of the prepared composite.     

Effect of particle size,heating rate and CNT addition on densification,microstructure and mechanical properties of B4C ceramics

Monolithic B₄C ceramics and B₄C–CNT composites were prepared by spark plasma sintering (SPS). The influence of particle size, heating rate, and CNT addition on sintering behavior, microstructure and mechanical properties were studied. Two different B₄C powders were used to examine the effect of particle size. The effect of heating rate on monolithic B₄C was investigated by applying three different heating rates (75, 150 and 225 °C/min). Moreover, in order to evaluate the effect of CNT addition, B₄C–CNT (0.5–3 mass%) composites were also produced. Fully dense monolithic B₄C ceramics were obtained by using heating rate of 75 °C/min. Vickers hardness value increased with increasing CNT content, and B₄C–CNT composite with 3 mass% CNTs had the highest hardness value of 32.8 GPa. Addition of CNTs and increase in heating rate had a positive effect on the fracture toughness and the highest fracture toughness value, 5.9 MPa m^1/2, was achieved in composite with 3 mass% CNTs.     

Microstructure and mechanical properties of B4C matrix composites prepared via hot-pressing sintering with Pr6O11 as additive

High-performance B₄C-PrB₆ composites were prepared via hot-pressing sintering with matrix phase B₄C and with 2–5 wt% Pr₆O₁₁ as additive. The effects of different sintering processes and Pr₆O₁₁ content on the microstructure and mechanical properties of the composites were studied in detail. It is found that increasing sintering temperature and pressure will contribute to the densification of B₄C-PrB₆ composites. Coarse grains are formed in B₄C without additives at high temperature conditions, resulting in the decrease of the densification. Pr₆O₁₁ can effectively hinder the formation of coarse grains and finally promote the densification of the composites. The main toughening mechanisms of composites was crack deflection. The composites with 4 wt% Pr₆O₁₁ prepared at 2050 °C and 25 MPa had the best comprehensive mechanical properties. The relative density, hardness, flexural strength and fracture toughness reached to 98.9%, 37.6 GPa, 339 MPa and 4.4 MP am^1/2, respectively.     

Structure and mechanical properties of hot-pressed B4C-NdB6 composites

High-performance B₄C-NdB₆ composites were fabricated by hot-pressing sintering at the temperature of 2050 °C for 20 min holding time and 20 MPa pressure with Nd₂O₃ (1～4 wt%) as the aiditive. The effects of Nd₂O₃ on the sintering process of the B₄C were studied. The reaction mechanisms of B₄C and Nd₂O₃ at different temperature were investigated. Based on the results of TG-DSC and thermodynamic calculation,. NdB₆ was formed via Nd₂O₃ react with B₄C in the sintering process, which greatly enhanced the densification of B₄C and promoted the sintering process. The flexural strength, fracture toughness and hardness of the B₄C-NdB₆ composites rose to 366.42 MPa, 5.27 MPa m^1/2 and 38 GPa by adding 3 wt% Nd₂O₃, respectively. The coexistence of transgranular and intergranular fracture is the major fracture mode. The phenomenon of pull-out contributed to improvement of the fracture toughness.     

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.