In Situ Fabrication of B4C–NbB2 Eutectic Composites by Spark–Plasma Sintering

This contribution reports, for the first time, the sintering, microstructure and properties of in situ synthesized/consolidated eutectic composites by spark–plasma sintering (SPS). SPS involves a number of processing parameters that may be used to tailor the composition of eutectic composites. It was shown that pressure may be used as a means of controlling the eutectic formation. By changing the pressure, temperature and composition, we propose a processing route that results in the in situ formation of strengthened eutectic composites, consisting of a matrix (B₄C, and B₄C–NbB₂ composite) and also containing regularly distributed whiskers of NbB₂. The composites with the eutectic composition of 35 mol.% NbB₂ obtained by SPS exhibit a high Vickers hardness (26–27 GPa) and indentation fracture toughness (~6 MPa·m^1/2).     

Spark plasma sintering and high-temperature strength of B6O–TaB2 ceramics

Tantalum diboride – boron suboxide ceramic composites were densified by spark plasma sintering at 1900 °C. Strength and fracture toughness of these bulk composites at room temperature were 490 MPa and 4 MPa m^1/2, respectively. Flexural strength of B₆O–TaB₂ ceramics increased up to 800 °C and remained unchanged up to 1600 °C. At 1800 °C a rapid decrease in strength down to 300 MPa was observed and was accompanied by change in fracture mechanisms suggestive of decomposition of boron suboxide grains. Fracture toughness of B₆O–TaB₂ composites showed a minimum at 800 °C, suggestive a relaxation of thermal stresses generated from the mismatch in coefficients of thermal expansion.Flexural strength at elevated temperatures for bulk TaB₂ reference sample was also investigated.Results suggest that formation of composite provides additional strengthening/toughening as in all cases flexural strength and fracture toughness of the B₆O–TaB₂ ceramic composite was higher than that reported for B₆O monoliths.     

Spark plasma sintering of B4C and B4C-TiB2 composites: Deformation and failure mechanisms under quasistatic and dynamic loading

Spark plasma sintering (SPS) was employed to consolidate powder specimens consisting of B₄C and various B₄C-TiB₂ compositions. SPS allowed for consolidation of pure B₄C, B₄C-13 vol.%TiB₂, and B₄C-23 vol.%TiB₂ composites achieving ≥99 % theoretical density without sintering additives, residual phases (e.g., graphite), and excessive grain growth due to long sintering times. Electron and x-ray microscopies determined homogeneous microstructures along with excellent distribution of TiB₂ phase in both small and larger-scaled composites. An optimized B₄C-23 vol.%TiB₂ composite with a targeted low density of ～3.0 g/cm³ exhibited 30–35 % increased hardness, fracture toughness, and flexural bend strength compared to several commercial armor-grade ceramics, with the flexural strength being strain rate insensitive under quasistatic and dynamic loading. Mechanistic studies determined that the improvements are a result of a) no residual graphitic carbon in the composites, b) interfacial microcrack toughening due to thermal expansion coefficient differences placing the B₄C matrix in compression and TiB₂ phase in tension, and c) TiB₂ phase aids in crack deflection thereby increasing the amount of intergranular fracture. Collectively, the addition of TiB₂ serves as a toughening and strengthening phase, and scaling of SPS samples show promise for the manufacture of ceramic composites for body armor.     

High‐temperature strength and plastic deformation behavior of niobium diboride consolidated by spark plasma sintering

Bulk niobium diboride ceramics were consolidated by spark plasma sintering (SPS) at 1900°C. SPS resulted in dense specimens with a density of 98% of the theoretical density and a mean grain size of 6 μm. During the SPS consolidation, the hexagonal boron nitride (h‐BN) was formed from B₂O₃ on the powder particle surface and residual adsorbed nitrogen in the raw diboride powder. The room‐temperature strength of these NbB₂ bulks was 420 MPa. The flexural strength of the NbB₂ ceramics remained unchanged up to 1600°C. At 1700°C an increase in strength to 450 MPa was observed, which was accompanied by the disappearance of the secondary h‐BN phase. Finally, at 1800°C signs of plastic deformation were observed. Fractographic analysis revealed a number of etching pits and steplike surfaces suggestive of high‐temperature deformation. The temperature dependence of the flexural strength of NbB₂ bulks prepared by SPS was compared with data for monolithic TiB₂, HfB₂ and ZrB₂. Our analysis suggested that the thermal stresses accumulated during SPS consolidation may lead to additional strengthening at elevated temperatures.     

Fracture and property relationships in the double diboride ceramic composites by spark plasma sintering of TiB2 and NbB2

Bulk titanium diboride–niobium diboride ceramic composites were consolidated by spark plasma sintering (SPS) at 1950°C. SPS resulted in dense specimens with a density exceeding 98% of the theoretical density and a multimodal grain size ranging from 1 to 10 μm. During the SPS consolidation, the pressure was applied and released at 1950 and 1250°C, respectively. This allowed obtaining a two-phase composite consisting of TiB₂ and NbB₂. For these ceramics composites, we evaluated the flexural strength and fracture toughness and room and elevated temperatures. Room-temperature strength of thus produced bulks was between 300 and 330 MPa, at 1200°C or 1600°C an increase in strength up to 400 MPa was observed. Microstructure after flexure at elevated temperatures revealed the appearance of the needle-shape subgrains of NbB₂, an evidence for ongoing plastic deformation. TiB₂–NbB₂ composites had elastic loading stress curves at 1600°C, and at 1800°C fractured in the plastic manner, and strength was ranged from 300 to 450 MPa. These data were compared with a specimen where a (Ti,Nb)B₂ solid solution was formed during SPS to explain the behavior of TiB₂–NbB₂ ceramic composites at elevated temperatures.     

Synthesis and Properties of MoSi2–MoB–SiC Ceramics

MoB and SiC particulate reinforced MoSi₂ matrix composites were synthesized in situ from Mo, Si, and B₄C powder mixtures by self‐propagating high‐temperature synthesis (SHS). The SHS MoSi₂–MoB–SiC products were vacuum hot‐pressed (HPed) at 1400°C for 90 min to fabricate high‐density (> 97.5% relative density) bulk composites. Microstructure refinement and improvements in the Vickers hardness and fracture toughness of the HPed composites were observed with increasing B₄C content in the reaction mixture. The HPed composite of composition MoSi₂–0.4MoB–0.1SiC exhibited grain size of 1–5 μm, Vickers hardness of 12.5 GPa, bending strength of 537 MPa, and fracture toughness of 3.8 MPa.m^1/2. These excellent mechanical properties indicate that MoB and SiC particulate reinforced MoSi₂ composites could be promising candidates for structural applications.     

High-temperature strength behavior of tantalum diboride to 2000°C

This study investigated the high-temperature strength of spark plasma sintered tantalum diboride (TaB₂) for the first time. TaB₂ exhibited a unique elastic fracture behavior below 1900°C, unlike other transition metal diborides. The consolidation process involved spark plasma sintering at 2000–2200°C yielding dense TaB₂ samples. The flexural strength was measured at elevated temperatures up to 2000°C, showing a quite high flexural strength of 400 ± 20 MPa at 1900°C. These findings provide valuable insights into the high-temperature behavior of TaB₂, highlighting its potential for advanced applications.     

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.     

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.     

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.     

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.     

Microstructure evolution and phase transformation of TiB2/SiC/B4C composites synthesized from Ti‐SiC‐B4C ternary system

Bulk TiB₂/SiC/B₄C composites have been synthesized from Ti‐SiC‐B₄C ternary system with different Ti weight percentages via reactive hot pressing at 1800°C under an applied pressure of 30 MPa for 1.5 h. By Ti amount increasing, the flexural strength curve exhibited an “M‐like” tendency reaching the maximum value of 512.36 MPa for 30 wt.% Ti. Microstructural evolution of the composites from conterminously large matrix grains to finely clear‐edged particles was observed by scanning electron microscopy. The phase transformation and element diffusion were analyzed by XRD and Energy Disperse Spectroscopy. A hybrid reinforcing mechanism of fracture and crack deflection is proposed to illustrate the change in flexural strength.     

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

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

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.     

Growth and Microstructure‐Dependent Hardness of Directionally Solidified WC–W2C Eutectoid Ceramics

Directionally solidified WC–W₂C ceramics containing 40 at% carbon, corresponding to the WC–W₂C eutectoid composition, were produced by laser surface melt processing. The resulting microstructures showed a lamellar‐type eutectic/eutectoid microstructure with the WC minor phase embedded in the W₂C matrix phase. The interlamellar spacing (λ) in the eutectoid regions followed the relationship Vλ^3.8 = constant, with the smallest spacing of 331 ± 36 nm achieved in the 3.24 mm/s processed sample. The indentation hardness increased with decreasing interlamellar spacing, and a Vickers indentation hardness of 28.5 GPa was achieved in the sample with the smallest interlamellar spacing. The directionally solidified WC–W₂C materials show enhanced indentation mechanical properties in comparison to previously reported WC–Co composites and WC‐based materials.     

High-performance B4C–TiB2–SiC composites with tuneable properties fabricated by reactive hot pressing

In this work, we systematically studied the effects of powder characteristics (B₄C, TiC and Si powders) on the existential form of toughening phases (SiC and TiB₂) as well as the overall microstructure and properties of B₄C–TiB₂–SiC composites fabricated by reactive hot pressing. The particle size of the TiC powder plays a largely determining role in the development of novel toughening phases, the TiB₂–SiC composite structure, that are formed in the B₄C matrix, while the Si particle size affects the agglomerate level of the SiC phase. The TiB₂–SiC composite structure and SiC agglomerates enhance the fracture toughness, but decrease the flexural strength. Both the microstructure and mechanical properties of B₄C–TiB₂–SiC composites can be effectively tuned by regulating the combinations of the particle sizes of the starting powders. The B₄C–TiB₂–SiC composites demonstrate flexural strength, fracture toughness and Vickers hardness in the respective range of 567–632 MPa, 5.11–6.38 MPa m^1/2, and 34.8–35.6 GPa.     

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.     

Ultra-high elevated temperature strength of TiB2-based ceramics consolidated by spark plasma sintering

Spark plasma sintering of TiB₂–boron ceramics using commercially available raw powders is reported. The B₄C phase developed during reaction-driven consolidation at 1900 °C. The newly formed grains were located at the grain junctions and the triple point of TiB₂ grains, forming a covalent and stiff skeleton of B₄C. The flexural strength of the TiB₂–10 wt.% boron ceramic composites reached 910 MPa at room temperature and 1105 MPa at 1600 °С. Which is the highest strength reported for non-oxide ceramics at 1600 °C. This was followed by a rapid decrease at 1800 °C to 480–620 MPa, which was confirmed by increased number of cavitated titanium diboride grains observed after flexural strength tests.     

ZrB2–SiC–G Composite Prepared by Spark Plasma Sintering of In‐Situ Synthesized ZrB2–SiC–C Composite Powders

To avoid introduction of milling media during ball‐milling process and ensure uniform distribution of SiC and graphite in ZrB₂ matrix, ultrafine ZrB₂–SiC–C composite powders were in‐situ synthesized using inorganic–organic hybrid precursors of Zr(OPr)₄, Si(OC₂H₅)₄, H₃BO₃, and excessive C₆H₁₄O₆ as source of zirconium, silicon, boron, and carbon, respectively. To inhabit grain growth, the ZrB₂–SiC–C composite powders were densified by spark plasma sintering (SPS) at 1950°C for 10 min with the heating rate of 100°C/min. The precursor powders were investigated by thermogravimetric analysis–differential scanning calorimetry and Fourier transform infrared spectroscopy. The ceramic powders were analyzed by X‐ray diffraction, X‐ray photoelectron spectroscopy, and scanning electron microscopy. The lamellar substance was found and determined as graphite nanosheet by scanning electron microscopy, Raman spectrum, and X‐ray diffraction. The SiC grains and graphite nanosheets distributed in ZrB₂ matrix uniformly and the grain sizes of ZrB₂ and SiC were about 5 μm and 2 μm, respectively. The carbon converted into graphite nanosheets under high temperature during the process of SPS. The presence of graphite nanosheets alters the load‐displacement curves in the fracture process of ZrB₂–SiC–G composite. A novel way was explored to prepare ZrB₂–SiC–G composite by SPS of in‐situ synthesized ZrB₂–SiC–C composite powders.     

A new route to fabricate SiB4 modified C/SiC composites

In order to improve the oxidation and thermal shock resistance of 2D C/SiC composites, dense SiB₄–SiC matrix was in situ formed in 2D C/SiC composites by a joint process of slurry infiltration and liquid silicon infiltration. The synthesis mechanism of SiB₄ was investigated by analyzing the reaction products of B₄C–Si system. Compared with the porous C/SiC composites, the density of C/SiC–SiB₄ composites increased from 1.63 to 2.23 g/cm³ and the flexural strength increased from 135 to 330 MPa. The thermal shock behaviors of C/SiC and C/SiC–SiB₄ composites protected with SiC coating were studied using the method of air quenching. C/SiC–SiB₄ composites displayed good resistance to thermal shock, and retained 95% of the original strength after being quenched in air from 1300 °C to room temperature for 60 cycles, which showed less weight loss than C/SiC composite.