Influence of carbon nanotubes as secondary phase addition on the mechanical properties and amorphization of boron carbide

The mechanical properties and amorphization response of a carbon nanotube (5 wt.%) boron carbide (CNT-B₄C) composite with 1 μm grain size are investigated, and compared to those of coarse-grained (10 μm grain size) and ultrafine-grained (0.3 μm grain size) monolithic boron carbides. The quasi-static and dynamic uniaxial compressive strengths for CNT-B₄C were statistically the same as those of the ultrafine-grained ceramic and higher than the coarse-grained material, contradicting the expected grain size hierarchy (Hall-Petch-type relationship). Addition of CNTs to B₄C resulted in decreased quasi-static hardness compared to the large grain size material; however, dynamic hardness was substantially improved compared to quasi-static values. CNT pullout and crack bridging were observed to be possible toughening mechanisms. Finally, Raman spectroscopy was used to quantify amorphization, and it was concluded that addition of CNTs to boron carbide does not alter the propensity for amorphization, but does improve mechanical properties by enhanced toughening.     

High‐Strength B4C–TaB2 Eutectic Composites Obtained via In Situ by Spark Plasma Sintering

The in situ synthesis/consolidation of B₄C–TaB₂ eutectic composites by spark plasma sintering (SPS) is reported. Samples for the evaluation of bending strength were cut from specimens with diameters of 30 mm. The sample prepared for the three‐point flexural strength test had fibers of tantalum diboride with diameter of 1.3 ± 0.4 μm distributed in the B₄C matrix, thereby reducing composites brittleness and yielding an indentation fracture toughness of up to 4.5 MPa·m^1/2. Furthermore, the Vickers hardness of B₄C–TaB₂ eutectics formed by SPS was as high as 26 GPa at an indentation load of 9.8 N. The flexural strength of the B₄C–TaB₂ system has been reported for the first time. Some steps were identified in the load–displacement curve, suggesting that micro‐ and macrocracking occurred during the flexural test. Ceramic composites with a eutectic structure exhibited a room‐temperature strength of 430 ± 25 MPa. Compared with other eutectic composites of boron carbide with transition‐metal diborides, room‐temperature strength the B₄C–TaB₂ was 40% higher than that of B₄C–TiB₂ ceramics, demonstrating advantage of the in situ synthesis/consolidation of eutectic composites by SPS.     

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.     

Amorphization‐induced volume change and residual stresses in boron carbide

The residual pressure surrounding quasistatic and dynamic Vickers indentations in boron carbide was quantitatively mapped in 3 dimensions using Raman spectroscopy. These maps were compared against similar maps of amorphization intensity and optical micrographs of deformed regions to determine the roles of amorphization and damage upon indentation‐induced residual stress. Stress relaxation was observed near radial cracks, spalled regions, and graphitic inclusions. A positive correlation was found between high levels of residual stress and the number of amorphized sites detected. Finite element simulations were conducted to model the indentation‐induced residual stress fields in the absence of amorphization and cracking. The simulations underpredicted the average residual pressure observed through Raman spectroscopy, implying that amorphization contributes to increased pressure in the material. This pressure is interpreted as potential evidence of volumetric expansion of the amorphized material which is less ordered and hence exerts compressive forces on the surrounding crystalline matrix.     

Reaction‐Bonded Boron Carbide/Magnesium–Silicon Composites

Reaction‐bonded boron carbide was manufactured by infiltrating porous boron carbide preforms at 1273 K with a Mg‐Si eutectic alloy. The resulting composite material consists, in addition to the original B₄C, of SiC, Mg₂Si, and a Mg‐rich complex boride/carbide Mg_x(Al,Si)_y(B,C)_z phase. The composites display high hardness (1700 HV), Young's modulus (356 MPa) and a moderate bending strength (230 MPa). The ballistic efficiency (of about 6.7), as determined by the depth of penetration method, is much higher than that of alumina and similar to that of silicon‐infiltrated reaction‐bonded composites.     

Investigation of the effect of impurity of precursor materials on Si-doped boron carbide properties

Boron carbide is a notable ceramic, with its high hardness and low density. However, it suffers a sudden loss in strength under high shear stress. Doping boron carbide with Si/B is widely used to increase its resistance to amorphization. High purity boron and silicon hexaboride precursor powders are used for doping boron carbide, but these materials have high costs and supply chain constraints. This research investigated the effect of substituting lower purity B or using pure Si powder instead of SiB₆ on materials’ properties such as elastic and mechanical properties, microstructure, and amorphization resistances. It was observed that using lower-purity boron or pure Si powder instead of SiB₆ did not significantly affect critical properties, such as fracture toughness, hardness, or amorphization resistance. However, Young's modulus values decreased as B purity decreased and as Si was used instead of SiB₆. These findings demonstrate that substituting precursor materials in Si/B co-doped B₄C is possible with little change in the material's properties. This facilitates the use of easier-to-access, cheaper production routes to be used for silicon-doped boron carbide products.     

Preparation and characterization of reduced graphene oxide-reinforced boron carbide ceramics by self-assembly polymerization and spark plasma sintering

A self-assembly polymerization process was used to prepare graphene oxide/boron carbide (GO/B₄C) composite powders, spark plasma sintering (SPS) was used to fabricate reduced graphene oxide/boron carbide (rGO/B₄C) composites at 1800 °C and 30 MPa with a soaking time of 5 min. The effects of rGO addition on mechanical properties of the composites, such as Vickers hardness, flexural strength and fracture toughness, were investigated. The results showed that GO/B₄C composite powders were successfully self-assembled and a network structure was formed at high GO contents. The flexural strength and fracture toughness of rGO/B₄C composites were 643.64 MPa and 5.56 MPa m^1/2, respectively, at 1 and 2.5 wt.% rGO content, corresponding to an increase of 99.11% and 71.6% when compared to B₄C ceramics. Uniformly dispersed rGO in rGO/B₄C composites played an important role in improving their strength and toughness. The toughening mechanisms of rGO/B₄C composites were explained by graphene pull-out, crack deflection and bridging.     

Microstructure and mechanical properties of fine-grained boron carbide ceramics fabricated by high-pressure hot pressing combined with high-energy ball milling

Dense and fine-grained boron carbide (B₄C) ceramics were fabricated via high-pressure hot pressing (100?MPa) using powders, which are prepared by high-energy ball milling. These powders were sintered at a low temperature (1800?°C) without any sintering aid. The dense and fine-grained B₄C ceramics demonstrate super high hardness, outstanding fracture toughness and modern flexure strength. The milled powders were characterised by disordered crystal structure and ultrafine particle size that ranges from a few nanometres to a few hundred nanometres. The combined contributions of high pressure and the characteristic of the milled powders guaranteed that the dense fine-grained microstructure was achieved at only 1800?°C. The grain size distribution of the ceramics was inhomogeneous and ranged from 70?nm to 1.6?µm. However, the average grain size was fine at only 430?nm, which partially contributed to the super high hardness of the B₄C ceramics. The locally concentrated areas of the small grains changed the fracture mode of the B₄C ceramics from the complete transgranular fracture to a mixture of transgranular and intergranular fractures, thereby enhancing the toughness of the B₄C ceramics. The relative density, Vickers hardness, flexure strength and fracture toughness of the obtained B₄C ceramics reached up to 99.5%, 41.3?GPa, 564?MPa and 4.41?MPa?m^1/2, respectively.     

Production of B4C coatings by CVD method in a dual impinging‐jet reactor: Chemical yield,morphology, and hardness analysis

β‐rhombohedral boron carbide (B₄C) was deposited on a tungsten substrate from a BCl₃? H₂? CH₄ gas mixture in a dual impinging‐jet chemical vapor deposition reactor. On‐line FTIR analysis of the product stream proved the formation of BHCl₂ and HCl as by products, in a competing parallel reaction. A maximum of 13% chemical yield of boron carbide was observed, and the yield was found to have increasing trend with an increase in temperature. XRD analysis proved the existence of rhombohedral B₄C phase at 1300°C without any other B₄C phases or impurities. At this temperature, the formation of 5‐fold icosahedral boron carbide crystals up to 30 micron sizes was observed. Such highly symmetric crystalline regions were observed to have a very high hardness value of 4750 kg/mm² as revealed from the microhardness analysis. The change in product morphology at low substrate temperatures resulted in a decrease in the hardness values. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Reaction‐Bonded B4C with High Hardness

Reaction‐bonded B₄C (RBBC) was fabricated through molten Si infiltrating porous B₄C preforms. A preform with a 75% relative green density was obtained by mixing two different sized B₄C powders. Carbon black added to the preform slightly reduces average pore size, but increases porosity. RBBC ceramics showed a dense and homogeneous microstructure. Vickers hardness was about 15 GPa for RBBC fabricated from a single type of B₄C powder and could reach 22–23 GPa for the carbon‐added samples after infiltration. Morphological evolution and the influence of the microstructure on the Vickers hardness were investigated and discussed.     

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.     

Effect of graphite content on properties of B4C‐W2B5 ceramic composites by in situ reaction of B‐Gr‐WC

Strip‐shaped W₂B₅ reinforced B₄C ceramic composites were prepared via in situ reaction of boron(B)‐graphite(Gr)‐WC system by powder metallurgy (P/M). In order to study the effect of the graphite content on the properties of the as‐fabricated ceramic composites, the powder mixture of B‐Gr‐WC with various amounts of Gr powder were blended and consolidated by spark plasma sintering (SPS). The sintering parameters were shown as following: sintering pressure was set as 30 MPa; The three‐step sintering temperature was 1100‐1550‐1700°C and the duration time was set as 5‐5‐6 minutes, respectively. In situ formed strip‐shaped W₂B₅ particles were dispersed homogeneously in B₄C matrix, which resulted in a remarkable improvement on the fracture toughness and mechanical properties. Appropriate 5vol% residual Gr in the composite shows positive effect on the mechanical properties which achieved an optimal counter‐balance of fracture toughness and hardness, the relative density was 99.8%, the Vickers hardness can reach 30.2 GPa, and the fracture toughness was 11.9 MPa·m^1/2 when the sintering temperature was set at 1700°C.     

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).     

Spark Plasma Sintering of Superhard B4C–ZrB2 Ceramics by Carbide Boronizing

A carbide boronizing method was first developed to produce dense boron carbide‐ zirconium diboride (“B₄C”–ZrB₂) composites from zirconium carbide (ZrC) and amorphous boron powders (B) by Spark Plasma Sintering at 1800°C–2000°C. The stoichiometry of “B₄C” could be tailored by changing initial boron content, which also has an influence on the processing. The self‐propagating high‐temperature synthesis could be ignited by 1 mol ZrC and 6 mol B at around 1240°C, whereas it was suppressed at a level of 10 mol B. B₈C–ZrB₂ ceramics sintered at 1800°C with 1 mole ZrC and 10 mole B exhibited super high hardness (40.36 GPa at 2.94 N and 33.4 GPa at 9.8 N). The primary reason for the unusual high hardness of B₈C–ZrB₂ ceramics was considered to be the formation of nano‐sized ZrB₂ grains.     

Effect of Alumina on the Structure and Mechanical Properties of Spark Plasma Sintered Boron Carbide

Uniform densification of relatively thick (~7 mm) consolidated boron carbide plates at relatively low temperatures (e.g. 1800°C) and low facture toughness are two of the primary challenges for further development of boron carbide applications. This work reports that these two challenges can be overcome simultaneously by adding 5 wt% alumina as a sintering aid. Nearly fully dense (97%), fine grained boron carbide (B₄C) samples were produced using spark plasma sintering at 1700°C and above in the B₄C‐5 wt% Al₂O₃ system. The alumina and boron carbide matrix reacted to form an Al₅O₆BO₃ (a mullite‐like phase) during sintering. The Al₅O₆BO₃ phase facilitated uniform densification via liquid phase sintering. This secondary phase is dispersed throughout the intergranular pores, providing obstacles for crack propagation and resulting in tougher boron carbide ceramics.     

Synthesis,densification, and microstructure of TaC‐TaB2‐SiC ceramics

The usual way to prepare TaC‐TaB₂ ceramics by adding B₄C to TaC leads to formation of residual C, which degrades samples’ mechanical properties. To eliminate the residual C, we suggest incorporating Si together with B₄C into TaC ceramics, resulting in new ultrahigh‐temperature ceramics (TaC‐TaB₂‐SiC). Dense ceramics (>99%) with SiC volume fraction ranging from 15.86% to 41.04% were fabricated by reactive spark plasma sintering at 1900°C for 5 minutes. The formation of SiO₂‐based transient liquid phase was evidenced by the “film” in intermediate products, which can promote densification. The fine‐grained microstructure in final products was found to be associated with the in situ formed SiC, which impeded TaC and TaB₂ grains from coarsening by the pinning effect. Besides, ultrafine TaB₂ grains (~100 nm) produced during the reaction and then rearranged in liquid also contributed to grain refinement. Compared to TaC‐TaB₂(‐C) ceramics prepared from TaC and B₄C, the acquired composites exhibit better mechanical properties, due to their fine‐grained microstructures and the elimination of residual C.     

Synthesis of Boron Carbide by Reactive‐Pulsed Electric Current Sintering in the Presence of Tungsten Boride

The method of pulsed electric current sintering (PECS) has been used to obtain dense boron carbide (B₄C) and B₄C‐based composite materials containing tungsten boride (W₂B₅). To elucidate the role of the sintering additives and the mechanism of reactive densification, three types of materials have been obtained by PECS at 1850°C and 1900°C: “pure” B₄C, B₄C doped with 10 wt% W₂B₅, and B₄C doped with 10 wt% tungsten carbide (WC). X‐ray diffraction and X‐ray photoelectron spectroscopy have been used to determine crystallite size, phase changes, and the peculiarities of the chemical bonds of the densified materials. Structural and mechanical properties of the materials have been investigated using scanning electron microscopy, optical microscopy, ultrasound velocity measurements, and hardness tests. The electrochemical impedance spectra have been used to investigate the electrical properties of the PECS‐ed materials.     

Production of titanium-containing metal-ceramic composites based on boron carbide in the nanocrystalline state

ABSTRACT

The results of the study of the production technology, phase composition, structure and physico-mechanical properties of metal-ceramic materials based on boron carbide and their components are presented. Boron carbide was obtained by direct synthesis from chemical elements using amorphous boron and carbon black. By mechanical dispersion, solid reagents were converted into an ultrafine state. Using a chemical method, nanoscale (70–80?nm) boron carbide was synthesised from suspension solutions of amorphous boron and liquid hydrocarbons. Boron carbide-based metal-ceramic composite powder B₄C–(Co–Ni–Ti) was obtained by mechanical dispersion of the constituent components. Based on results of studying of the temperature-dependence of wetting angle of boron carbide with Co–Ni–Ti metallic alloy, the compacting modes of metal-ceramic composite powders by plasma-spark sintering and hot pressing have been developed. The influence of the component content of the binder metal (alloy) on some physico-mechanical properties (linear expansion coefficient, hardness, and bending strength) of hardmetal-ceramic materials based on boron carbide was studied. It was found that the optimum content of the metal component in the composite is ～ 25?wt-%. In the temperature range 300–600°C, the materials obtained are characterised by stable dimensional factors, since in this temperature range the thermal conductivity coefficient does not depend much on temperature. At room temperature, their bending strength is about 1?GPa. A new method of chemical synthesis of nanocrystalline ceramic compositions of boron carbide and titanium diboride using suspension solutions for the preparation of powders and their spark plasma sintering was also developed to obtain a compacted material of composition B₄C+30?wt-%TiB₂, which has a high hardness of 95 HRA (with maximum microhardness 45.6?GPa) and sufficient strength (with a bending strength of 834?MPa).     

Gel-cast hierarchical porous B4C/C preform and its role in fabricating reaction bonded boron carbide composites

The resorcinol-formaldehyde (RF) gel-casting system is employed for the first time to fabricate a hierarchical porous B₄C/C preform, which was subsequently used for the fabrication of reaction bonded boron carbide (RBBC) composites via a liquid silicon infiltration process. The effect of the carbon content and carbon structures of this perform on the microstructures and mechanical properties of B₄C/C preform and the resultant RBBC composites is reported. The B₄C/C preform (16 wt% carbon) exhibit a strength of 34±1 MPa. The obtained RBBC composites shown uniform microstructure is consisted of SiC particles bonded boron carbide scaffold and an interpenetrating residual silicon phase. The Vickers hardness, flexural strength and fracture toughness of the RBBC composites (16 wt% carbon) are 24 GPa, 452 MPa and 4.32 MPa m^1/2, respectively.     

High‐Temperature Strength of Boron Suboxide Ceramic Consolidated by Spark Plasma Sintering

The spark plasma sintering (SPS) of B₆O ceramics using a highly crystalline boron suboxide powder with a low oxygen deficiency level is reported. The monolithic boron suboxide ceramic exhibited a room‐temperature strength of 300 ± 20 MPa, which is comparable to the strength of monolithic boron carbide. With increasing flexural test temperature, the strength of the boron suboxide ceramics increased to 450 MPa at 1400°C. The increase in strength with the temperature is associated with the unique microstructure of boron suboxide grains, which allows intergranular “brittle” fracture along subgrains even at 1400°C. This suggests that even higher strengths can be achieved.