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.     

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.     

Flash spark plasma sintering of cold-Pressed TiB2-hBN

Further improvements over the unprecedented gains in energy and time efficiency already achieved by the flash spark plasma sintering (FSPS) technique were won by eliminating the pre-sintering stage from the process. Cold-pressed discs (Ø 35 mm) of TiB₂-hBN were successfully flash sintered from powder to nearly dense material (up to 97%) in less than 110 s (∼60 s sintering time) in a SPS furnace. The issue of thermal gradients during FSPS was resolved and improvements to the homogeneity of the sample were achieved by modifying the experimental set-up to restrict the current flow through the system. In addition to ease of automation, another advantage of the proposed die-less FSPS configuration is a texturing effect typically achieved by hot forging.     

Microstructure and flexural strength of hafnium diboride via flash and conventional spark plasma sintering

Microstructure evolution in bulk hafnium diboride ceramics prepared by spark plasma sintering in flash regime was compared with conventional spark plasma sintering. The conventional and flash spark plasma sintering resulted in ceramics with a high relative density exceeding 96% of their theoretical density. A remarkably fine grain size distribution was noticed for the specimen prepared in the flash regime. This atypical microstructure evolution provides a possible insight into the mechanism of flash sintering for conductive bulks. The room temperature flexural strength of the hafnium diboride processed by flash SPS was 650 MPa which is 140 MPa higher than the sample produced by conventional SPS.     

In-situ graphene platelets formation and its suppression during reactive spark plasma sintering of boron carbide/titanium diboride composites

Boron carbide composites with 10 vol.% TiB₂ were prepared by reactive sintering of B₄C, TiO₂, and carbon black powder mixture at the temperature of 1800 °C, under a pressure of 70 MPa in a vacuum. The combined effects of electric current and in-situ reactions led to a significant overheating of the central part of the sample, while no overheating was observed for hot press and non-reactive SPS processes. A lower electrical resistivity of TiB₂ produced a significant Joule heating of boron carbide, leading to its partial decomposition to form gaseous boron and graphene platelets. Homogenous, fully dense and graphene-free samples were obtained when employing an insulating Al₂O₃ paper during reactive SPS. A short dwell time (30 s after a degassing step of 6 min) and the uniform distribution of fine TiB₂ grains were the main advantages of isolated SPS over the reactive hot press and SPS processes, respectively.     

Preparation of tungsten diboride by a combination of boro/carbothermal reduction process and spark plasma sintering

Submicron tungsten diboride (WB₂) powder was successfully synthesized with the ratio of WO₃:B₄C:C = 2:1.1:5. The effects of carbon sources (carbon black or graphite) and heat treatment temperatures (1100, 1200, 1300 ℃) on the phase composition and microstructure of the as-synthesized WB₂ powder samples were studied. The results showed that ultrafine WB₂ powders with oxygen content of 1.65 wt% and 2.04 wt% were obtained by carbon black and graphite at 1300 ℃, respectively. The relatively density of the as-sintered WB₂ samples achieve ~ 91 % and ~ 87 % without any kind of sintering additive after spark plasma sintering at 1500 °C under 30 MPa for 10 min. The formation mechanism of the WB₂ powders synthesized by boro/carbothermal reduction was proposed and verified by thermodynamic calculation according to the phases present in the powder synthesized at different temperatures.     

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.     

Microstructure and mechanical properties of spark plasma sintered TiB2 ceramics combined with a high-entropy alloy sintering aid

A high-entropy alloy (HEA), CoCrFeNiMn_0.5Ti_0.5, is used as a sintering aid for the densification of TiB₂ sintered by spark plasma sintering. The HEA content in the starting TiB₂-HEA mixture is varied from 0 to 10?wt-%. The microstructure and mechanical properties of the sintered samples are analysed and the optimum HEA content of 10% is found for the preparation of the TiB₂-HEA ceramics, allowing combining high mechanical properties (Vickers hardness of 2174.64?HV and flexural strength of 427.69?MPa) and high relative density of 99.1%.     

Effect of short carbon fiber content on the mechanical properties of TiB2-based composites prepared by spark plasma sintering

In this study, TiB₂-30 vol% SiC composites containing 0, 5, 10, and 15 vol% short carbon fibers (C_f) were produced by spark plasma sintering (SPS). The effect of carbon fiber content on microstructure, density, and mechanical properties (micro-hardness and flexural strength) of the fabricated composites was studied. Scanning electron microscopy (SEM) results indicated that the fibers were uniformly dispersed in the TiB₂–SiC matrix using wet ball milling before SPS process. Fully dense TiB₂–SiC–C_f composites were achieved by SPS process at 1900°C for 10 min under 30 MPa. With the addition of fibers, the relative density of the composites did not change considerably. Mechanical tests revealed that microhardness was reduced about 19% by the incorporation of carbon fibers, whereas the flexural strength improved significantly. However, the flexural strength diminished by adding carbon fibers above to critical value (5 vol%) due to residual thermal stresses, nonhomogeneous structure and graphitization of carbon fibers. It was found that the composite with 5 vol% C_f had the highest flexural strength (482 MPa), which was enhanced by 20% compared with the TiB₂–SiC composite.     

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).     

Probing the spectrally selective property of NbB2-based tandem absorber coating for concentrated solar power application

Solar selective coating with good thermal stability is the primary requirement for a concentrated solar power (CSP) plant to function with better photothermal efficiency. In recent years, ultra-high-temperature ceramic-based coatings have been explored as potential materials for solar selective coatings. In this context, NbB₂/Nb(BN)/Al₂O₃ tandem absorber coating was designed to be fabricated on a stainless-steel substrate by the radio frequency magnetron sputtering of spark plasma sintered ceramic target. In the bulk form, the NbB₂ ceramic exhibits high solar absorptance (α = 0.756) and thermal emissivity (ε = 0.43), whereas the amorphous single NbB₂ coating exhibits α/ε = 0.716/0.13. Reactive sputtering of NbB₂ in nitrogen produced a semi-transparent coating with an optical bandgap of ∼2.80 eV and was used as the secondary absorber layer. Raman and X-ray photoelectron spectroscopy analyses reveal mild oxygen incorporation in the absorber layers. The developed SS/NbB₂/Nb(BNO)/Al₂O₃ tandem absorber exhibits a good solar absorptance of 0.950 and a moderate thermal emissivity of 0.15 at room temperature. The coatings exhibited good thermal stability when heated in vacuum for 5 h up to 700°C, and the selectivity (α/ε) remains above 6. The present work shows the possibility of exploring NbB₂-based tandem absorber coatings for CSP applications.     

Effect of titanium diboride on the homogeneity of boron carbide ceramic by flash spark plasma sintering

A novel method, namely flash spark plasma sintering (FSPS), combining flash sintering and electric field assisted sintering, was utilized to densify boron carbide/titanium diboride (B₄C/TiB₂) composites. Further, sintering homogeneity of the composites with different contents of TiB₂ was systematically investigated and theoretical model was built. Results indicated that addition of 50?wt% TiB2 led to the densification of B₄C/TiB₂ composite by up to 97.7% with regional range 1.9% at 1872?°C under pressure of 4?MPa in 60?s. The preferential pathway of TiB₂ network proves to disperse the central current and distribute thermal flow throughout the specimen possibly via tunneling, electronic field emission effect at first stage and lower-resistance composite pathway latter, contributing to the increased homogeneity.     

Synthesis and properties of conductive B4C ceramic composites with TiB2 grain network

High electrical resistance and low fracture toughness of B₄C ceramics are 2 of the primary challenges for further machining of B₄C ceramics. This report illustrates that these 2 challenges can be overcome simultaneously using core‐shell B₄C‐TiB₂&TiC powder composites, which were prepared by molten‐salt method using B₄C (10 ± 0.6 μm) and Ti powders as raw materials without co‐ball milling. Finally, the near completely dense (98%) B₄C‐TiB₂ interlayer ceramic composites were successfully fabricated by subsequent pulsed electric current sintering (PECS). The uniform conductive coating on the surface of B₄C particles improved the mass transport by electro‐migration in PECS and thus enhanced the sinterability of the composites at a comparatively low temperature of 1700°C. The mechanical, electrical and thermal properties of the ceramic composites were investigated. The interconnected conductive TiB₂ phase at the grain boundary of B₄C significantly improved the properties of B₄C‐TiB₂ ceramic composites: in the case of B₄C‐29.8 vol% TiB₂ composite, the fracture toughness of 4.38 MPa·m^1/2, the electrical conductivity of 4.06 × 10⁵ S/m, and a high thermal conductivity of 33 W/mK were achieved.     

Spark plasma sintering and characterization of ZrC-TiB2 composites

ZrC-based composites were consolidated from ZrC and TiB₂ powders by the Spark Plasma Sintering (SPS) technique at 1685 °C and 1700 °C for 300 s under 40-50-60 MPa. Densification, crystalline phases, microstructure, mechanical properties and oxidation behavior of the composites were investigated. The sintered bodies were composed of a (Zr,Ti)C solid solution and a ZrB phase. The densification behaviors of the composites were improved by increasing the TiB₂ content and applied pressure. The highest value of hardness, 21.64 GPa, was attained with the addition of 30 vol% TiB₂. Oxidation tests were performed at 900 °C for 2 h and the formation of ZrO₂, TiO₂ and B₂O₃ phases were identified by using XRD.     

Wetting,reactivity, and phase formation at interfaces between Ni–Al melts and TiB2 ultrahigh‐temperature ceramic

The wetting, reactivity, and phase formation at the liquid Ni–Al/TiB₂ ceramic interfaces have been investigated at the temperatures close to the Ni–Al liquidus line. The wetting kinetics has been studied by the sessile drop technique utilizing liquid drop dispension and high‐speed high‐resolution video imaging. It is established that the wetting behavior changes from a nonreactive for the Al‐rich melts to a dissolution‐reactive for the Ni‐rich melts. For the Ni concentration ≥40 at.%, TiB₂ precipitates are found in the solidified Ni–Al droplets after the high‐temperature interaction of the melts with TiB₂ substrates. Besides, new (Al,Ti)Ni₃ and (Al,Ti)₂Ni₂₁B₆ phases are formed due to dissolution of TiB₂ ceramic in Ni‐rich melts and subsequent solidification.     

热压烧结制备原位复合（TiB2+TiC）/Ti3SiC2复相陶瓷

采用热压烧结法制备了原位复合(TiB2+TiC)/Ti3SiC2复相陶瓷。采用X射线衍射、扫描电镜和透射电镜对材料的物相组成和显微结构进行了表征,研究了烧结温度对材料物相组成、烧结性能、显微结构与力学性能的影响。结果表明:烧结温度在1 350～1 500℃范围内,随着烧结温度的升高,合成反应进行逐渐完全,材料的密度、抗弯强度和断裂韧性显著提高。1 500℃烧结可得到致密的原位复合(TiB2+TiC)/Ti3SiC2复相陶瓷,材料晶粒发育较完善,层片状Ti3SiC2、柱状TiB2与等轴状TiC晶粒清晰可见,增强相晶粒细小,晶界干净,材料的抗弯强度、断裂韧性和Vickers硬度分别达到741 MPa,10.12 MPa.m1/2和9.65 GPa。烧结温度达到1 550℃时Ti3SiC2开始发生分解,材料的密度和力学性能又显著下降。     

Enhanced electromagnetic shielding property of cf/mullite composites fabricated by spark plasma sintering

Aiming to prepare high-performance electromagnetic interference (EMI) shielding materials, chopped carbon fibers were incorporated into mullite ceramic matrix via rapid prototyping process of spark plasma sintering (SPS). Results indicate that C_f/mullite composites with only 1 wt% of carbon fibers exhibit highest shielding effectiveness (SE_T) over 40 dB at a small thickness of 2.0 mm, showing great advantages both in terms of performance and thickness compared with many mature carbon/ceramic composites. The high EMI shielding properties mainly depend on two mechanisms of absorption and reflection in this present work. The enhanced absorption and reflection of electromagnetic wave are ascribed to the promotional electrical conductivity arising from the formation of conductive network by introduction of carbon fibers. Regarding enhanced electrical conductivity, notable intensified interfacial polarization on a large number of interfaces between mullite matrix and carbon fibers is also the key factor to the improved absorption, which makes absorption play a dominant role in the significant improvement of EMI SE_T. The C_f/mullite composites with excellent EMI shielding properties and thin thickness show great potential application as EMI materials.     

Ablation resistance of HfC(Si,O)-HfB2(Si,O) composites fabricated by one-step reactive spark plasma sintering

A dense HfC(Si, O)-HfB₂(Si, O) composite was fabricated by reactive spark plasma sintering using HfC and SiB₆ as starting reactants. The best ablation resistance was obtained with the composite fabricated with the addition of 15 vol.% SiB₆. After ablation under an oxyacetylene flame for 60 s, the mass and linear ablation rates of this composite were ?0.007 mg cm^?2 s^?1 and ?0.233 μm s^?1, respectively. The negative ablation rates are the result of a slight mass gain/thickness increase, which indicate that the oxidation process was stable and mechanical scouring was limited during ablation. This enhanced ablation resistance was attributed to a unique double-layered oxide formation, which possessed lower oxygen permeability and better mechanical strength. The solid solution nature of the composite and its appropriate phase composition were responsible for the stable oxide structure formation.     

Thermochemical model on the carbothermal reduction of oxides during spark plasma sintering of zirconium diboride

Carbon was used to reduce oxides in spark plasma sintered ZrB₂ ultra-high temperature ceramics. A thermodynamic model was used to evaluate the reducing reactions to remove B₂O₃ and ZrO₂ from the powder. Powder oxygen content was measured and carbon additions of 0.5 and 0.75 wt% were used. A C–ZrO₂ pseudo binary diagram, ZrO₂–B₂O₃–C pseudo ternaries, and Zr–C–O potential phase diagrams were generated to show how the reactions can be related to an open system experiment in the tube furnace. Scanning transmission electron microscopy identified impurity phases composed of amorphous Zr–B–O with lamellar BN and a Zr–C–O ternary model was calculated under SPS sintering conditions at 1900°C and 6 Pa to understand how oxides can be retained in the microstructure.     

Effect of LaB6 additions on densification,microstructure, and creep with oxide scale formation in ZrB2-SiC composites sintered by spark plasma sintering

A comparative study has been carried out on densification, microstructure, and creep with oxide-scale formation in ZrB₂-20 vol.% SiC-(7, 10 or 14 vol.%) LaB₆ composite containing B₄C and C as additives, and prepared by spark plasma sintering at 1800 °C under 70 MPa ram pressure. Addition of LaB₆ has promoted densification of composites by scavenging oxygen impurity, thereby increasing their hardness. Constant load compressive creep tests at 1300 °C under 47 and 78 MPa stresses have shown the lowest creep rate in the 10 vol.% LaB₆ composite. The stress exponents obtained for composites having 10 vol.% LaB₆ (～1.3 ± 0.1) and 14 vol.% LaB₆ (～2.6 ± 0.2) suggest respectively, grain boundary diffusion with intergranular glassy phase formation and dislocation glide as operating mechanisms. Intergranular cracking caused by grain boundary sliding appears as the damage mechanism. Oxide scales formed during creep exhibit greater thickness and defect concentration than those by isothermal exposure at 1300 °C within similar duration.