High thermal-conductivity rGO/ZrB2-SiC ceramics consolidated from ZrB2-SiC particles decorated GO hybrid foam with enhanced thermal shock resistance

Graphene derivative materials exhibit excellent mechanical and thermal properties, which have been extensively used to toughen ceramics and improve thermal shock resistance. To overcome the thermal agglomeration of graphene oxide (GO) during heating and drying process, ZrB₂-SiC particles decorated GO hybrid foam with uniformly anchored ceramic particles was synthesized by electrostatic self-assembly and liquid nitrogen-assisted freeze-drying process. Densified rGO/ZrB₂-SiC ceramics with varying microstructure, thermal physical and mechanical properties were obtained by adjusting the content of decorated ceramic particles. Although the flexural strength of rGO/ZrB₂-SiC ceramics have an attenuation compared with that of ZrB₂-SiC ceramic, the thermal conductivity, work of fracture and thermal shock resistance are greatly improved. rGO/ZrB₂-SiC ceramics exhibit delayed fracture and increasing R-curve behavior during the crack propagation. The novel preparation technology allows for the well dispersion of rGO in ZrB₂-SiC ceramics and can be easily extended to other ceramic or metal materials systems.     

Influence of in-situ synthesized Zr-Al-C on microstructure and toughening of ZrB2-SiC composite ceramics fabricated by spark plasma sintering

Zr-Al-C was in-situ synthesized as a toughening component in ZrB₂-SiC ceramics by spark plasma sintering (SPS) ball-milled ZrB₂-based composite powders with SiC and graphite powders. The phase composition of Zr-Al-C toughened ZrB₂-SiC (ZSA) composite ceramics fabricated through the two-step process (ball milling and SPS) did not change dramatically with varying content of Zr-Al-C which shows a major phase of Zr₃Al₄C₆. With increasing Zr-Al-C content, the fracture toughness of the ZSA ceramics initially increased and then decreased when the content reached 40 vol%. The ZSA ceramic with 30 vol% Zr-Al-C exhibited a maximum fracture toughness value of 5.96 ± 0.31 MPa m^1/2, about 22% higher than that of the ZSA ceramic with 10 vol% Zr-Al-C. When the Zr-Al-C content goes beyond 30 vol%, the higher open porosity and component agglomeration led to the relatively lower fracture toughness. Crack deflection and bridging resulted from the weak interface bonding between Zr-Al-C and matrix phases and the weak internal layers of Zr-Al-C crystals, leading to longer crack paths and, hence, the toughened ZSA composite ceramics. Compared to the one-step in-situ synthesis process of Zr-Al-C and the direct incorporation process of synthesized Zr-Al-C grains, the two-step in-situ synthesis process not only led to the more uniform distribution of different components but also resulted in a much larger size of Zr-Al-C grains with a large aspect ratio causing longer crack propagation path as the result of crack deflection and bridging. The larger Zr-Al-C grains combined with the more homogeneous microstructure achieve the most substantial toughening of the ZSA composite ceramics. This work points out a promising approach to control and optimize the microstructure and improve the fracture toughness of ZrB₂-SiC composite ceramics by selecting the incorporation process of compound reinforcement components.     

Enhanced mechanical properties and thermal shock resistance of Cf/ZrB2-SiC composite via an efficient slurry injection combined with vibration-assisted vacuum infiltration

An efficient slurry injection combined with vibration-assisted vacuum infiltration process has been developed to fabricate 3D continuous carbon fiber reinforced ZrB₂-SiC ceramics. Homogenous distribution between carbon fiber and ceramic was achieved successfully, leading to an enhancement in mechanical properties. The C_f-PyC/ZrB₂-SiC composite exhibited a typical non-brittle fracture mode with a superior fracture toughness of 6.72 ± 0.21 MPa·m^1/2 and an extraordinary work of fracture of 2270 J/m², respectively, increasing by nearly 14.8 % and 36 % as compared with those of a parent composite fabricated by only slurry injection and slurry infiltration. The enhancement in fracture toughness and work of fracture were attributed to multiple toughening mechanism including crack deflection, PyC coated fiber bundles pull-out and fiber bridging. Moreover, a critical thermal shock temperature difference of 814 °C was achieved, higher than that of traditional ZrB₂-based ceramics. This work presents an efficient approach to fabricate high-performance C_f/UHTCs with uniform architecture.     

Effect of pyrolytic carbon coating on the microstructure and fracture behavior of the Cf/ZrB2-SiC composite

The high sintering temperature and interface interaction seriously degraded the toughening effects of continuous carbon fiber in ZrB₂-SiC ceramic. The pyrolytic carbon coated carbon fiber reinforced ZrB₂-SiC composite (C_f-PyC/ZrB₂-SiC) with desirable properties was successfully achieved via brushing nano ZrB₂-SiC slurry followed by spark plasma sintering at relatively low sintering temperature. The fabricated C_f-PyC/ZrB₂-SiC composite presented a non-brittle fracture feature and a remarkable enhancement in comparison with the ZrB₂-SiC composite reinforced by the as-received carbon fiber (C_f-AS/ZrB₂-SiC). The fracture toughness and critical crack size were increased from 5.97?±?0.18–7.66?±?0.24?MPa?m^1/2 and from 91.6 to 164.5?µm, respectively. A high work of fracture of 1915?J/m² for C_f-PyC/ZrB₂-SiC composite was achieved, almost four times higher than that of the C_f-AS/ZrB₂-SiC composite (463?J/m²). Multiple toughening mechanisms contributed to such enhancement, such as crack deflection, fiber bridging, fiber pull-out and crack branching. This work provides a feasible approach to fabricate high-performance fiber reinforced ceramic composites having a high work of fracture.     

Study on toughening mechanisms of pyrolytic carbon interface layer in Cf/ZrB2-SiC composites using in-situ tensile experimental and numerical methods

The toughening mechanism in continuous fiber toughened ZrB₂-SiC ceramic matrix (C_f/ZrB₂-SiC) composites was studied upon introduction of pyrolytic carbon coating at the fiber/matrix interface. The real-time deformation behavior, surface crack initiation and evolution of C_f/ZrB₂-SiC composites under tensile load were studied using in-situ scanning electron microscopy (SEM) to determine the typical damage modes and toughening mechanisms. A refined microscopic representative volume element (RVE) inserting the cohesive zone elements was established to study the PyC interface layer damage by using finite element method. It was found that PyC interface layer damage induced by thermal residual stress (TRS) was one of critical factors affecting the mechanical performance of the C_f/ZrB₂-SiC composites. The critical thickness of the interface layer was also further determined by analyzing the effect of interface layer thickness on the distribution of TRS, which can guide the design of PyC interface layer for manufacturing the C_f/ZrB₂-SiC composites.     

Characterization and mechanical properties of Cf/ZrB2-SiC composites fabricated by a hybrid technique based on slurry impregnation,polymer infiltration and pyrolysis and low-temperature hot pressing

The continuous carbon fiber reinforced ZrB₂-SiC composite was fabricated successfully via a hybrid technique based on nano ceramic slurry impregnation, polymer infiltration and pyrolysis and low-temperature hot pressing. The C_f/ZrB₂-SiC composites exhibited non-brittle fracture modes and the chemical interaction at the fiber/matrix interfaces was effectively inhibited owing to the low sintering temperature. The S2-C_f/ZrB₂-SiC composite presented the highest mechanical properties with fracture toughness of 4.47?±?0.15?MPa?m^1/2 and the work of fracture of 877?J/m², which was attributed to the multiple length-scale toughening mechanisms including the macroscopic toughening mechanisms of crack deflection and crack branching, the micro toughening mechanisms of fiber bridging and fiber pull-out. This work presented a novel and effective method to fabricate high-performance continuous carbon fiber reinforced ceramic matrix composites.     

A novel vibration-assisted slurry impregnation to fabricate Cf/ZrB2-SiC composite with enhanced mechanical properties

The three dimensional needle-punched carbon fiber reinforced ZrB₂-SiC composite (C_f/ZrB₂-SiC) with highly uniform distribution was fabricated successfully via a novel vibration-assisted slurry impregnation and low-temperature (1450 °C) hot pressing technique using nanosized ZrB₂ powders. The carbon fiber/ceramic matrix interfaces were clear without obvious reaction products detected by the high resolution transmission electron microscopy (HR-TEM), indicating the degradation of carbon fiber was effectively inhibited. The C_f/ZrB₂-SiC composite exhibited a typical non-brittle fracture feature with a high work of fracture of 1104 J/m², which was approximately twice that of composite fabricated only by slurry impregnation and hot pressing. The enhancement in work of fracture was attributed to multiple toughening mechanisms of continuous carbon fibers such as extensive fiber bridging and pull-out accompanied by obvious crack deflection and branching. This work provides a valuable potential of preparing continuous carbon fiber reinforced ceramic composites with uniform component distribution and enhanced mechanical properties.     

Microstructure,mechanical properties and toughening mechanisms of graphene reinforced Al2O3-WC-TiC composite ceramic tool material

The low fracture toughness of Al₂O₃-based ceramics limited their practical application in cutting tools. In this work, graphene was chosen to reinforce Al₂O₃-WC-TiC composite ceramic tool materials by hot pressing. Microstructure, mechanical properties and toughening mechanisms of the composite ceramic tool materials were investigated. The results indicated that the more refined and denser composite microstructures were obtained with the introduction of graphene. The optimal flexural strength, Vickers hardness, indentation fracture toughness were 646.31?±?20.78?MPa, 24.64?±?0.42?GPa, 9.42?±?0.40?MPa?m^1/2, respectively, at 0.5?vol% of graphene content, which were significantly improved compared to ceramic tool material without graphene. The main toughening mechanisms originated from weak interfaces induced by graphene, and rugged fractured surface, grain refinement, graphene pull-out, crack deflection, crack bridging, micro-crack and surface peeling were responsible for the increase of fracture toughness values.     

Fabrication method and mechanical properties of biomimetic Cf/ZrB2-SiC ceramic composites with bouligand structures

Herein, biomimetic C_f/ZrB₂-SiC ceramic composites with bouligand structures are fabricated by combining precursor impregnation, coating, helical assembly and hot-pressing sintering. First, C_f/ZrB₂-SiC ceramic films are achieved through a precursor impregnation method using polycarbosilane (PCS). Second, the PCS-C_f/ZrB₂-SiC ceramic films are coated with ZrB₂ and SiC ceramic layers. Finally, hot-pressing sintering is employed to densify helical assembly C_f/ceramic films with a fixed angle of 30°. The microstructures and carbon fiber content on the mechanical properties of biomimetic C_f/ZrB₂-SiC ceramic composites are analyzed in detail. The results show that the coated ceramic layer on PCS-C_f/ZrB₂-SiC films can heal the cracks formed by pyrolysis of PCS, and the mechanical properties are obviously improved. Meanwhile, the mechanical properties could be tuned by the contents of the carbon fiber. The toughening mechanisms of C_f/ZrB₂-SiC ceramic composites with bouligand structures are mainly zigzag cracks, crack deflection, multiple cracks, carbon fiber pulling out and bridging.     

Fabrication and characterisation of high-performance joints made of ZrB2-SiC ultra-high temperature ceramics

Joining is crucial for ultra-high temperature ceramics (UHTCs) to be used in demanding environments due to the difficulty in manufacturing large and complex ceramic components. In this study, ZrB₂-SiC composite UHTCs parts were joined via Ni foil as filler, and the mechanical properties and oxidation behaviour of the fabricated ZrB₂-SiC/Ni/ZrB₂-SiC (ZS/Ni/ZS) joint were investigated. Firstly, dense ZrB₂-SiC composites were prepared from nano-sized powders by spark plasma sintering (SPS). The ZrB₂-SiC parts were then joined using SPS. Furthermore, the elastic modulus, hardness, shear strength and high temperature oxidation behaviour of the ZS/Ni/ZS joint were examined to evaluate its properties and performance. The experimental results showed that the ZrB₂-SiC parts were effectively joined via Ni foil using SPS and the resultant microstructures were free from any marked defects or residual metallic layers in the joint. Although the elastic modulus and hardness in the joining zone were lower than those in the base ZrB₂-SiC ceramics, the shear strength of the joint reached ∼161 MPa, demonstrating satisfactory mechanical properties. Oxidation tests revealed that the ZS/Ni/ZS joint possesses good oxidation resistance for a wide range of elevated temperatures (800–1600 ^oC), paving the way for its employment in extreme environments.     

Effect of ZrB2 powders on densification,microstructure, mechanical properties and thermal conductivity of ZrB2-SiC ceramics

With the view to improve the densification behaviour and mechanical properties of ZrB₂-SiC ceramics, three synthesis routes were investigated for the production of ZrB₂, prior to the fabrication of ZrB₂-20 vol. % SiC via spark plasma sintering (SPS). Two borothermal reduction routes, modified with a water-washing stage (BRW) and partial solid solution of Ti (BRS), were utilised, alongside a boro/carbothermal mechanism (BRCR) were utilised to synthesise ZrB₂, as a precursor material for the production of ZrB₂-SiC. It was determined that reduction in the primary ZrB₂ particle size, alongside a diminished oxygen content, was capable of improving densification. ZrB₂-SiC ceramics, with ZrB₂ derived from BRW synthesis, exhibited a favorable combination of high relative density (98.6%), promoting a marked increase in Vickers hardness (21.4 ± 1.7 GPa) and improved thermal conductivity (68.7 W·m^-1K^-1).     

Effects of carbon additives on the properties of ZrB2–based composites: A review

This review presents the recent achievements on carbon additives incorporated in ZrB₂ ceramics, improved properties, and their advancements. Monolithic ZrB₂ ceramics have broad potential applications, but their critical drawbacks such as poor damage tolerance, and weak oxidation and ablation resistance confines their applicability. It is an important issue to resolve these shortages in physiochemical properties by engineering the composite ingredients and process design of the ceramic counterparts for an extensive production and applications, which are especially essential in high–tech industries and products. Carbon additives have exceptional characteristics including low density, low cost, and excellent thermo–mechanical stability. These materials have been incorporated in ZrB₂ ceramics to enhance their efficiency and form practical composite ceramics. Although addition of the secondary carbonaceous phases is generally supposed to improve the mechanical properties of ZrB₂ composites, it may also result in a decrease in other aspects of performance, comparing with monolithic ZrB₂ ceramics. In this work, we reviewed the methods and strategies for the preparation of carbon modulated ZrB₂ ceramic composites. Moreover, the advantages, disadvantages, and the productivity of the introduced composite ceramics have been explored and featured.     

Processing and properties of ZrB2-SiC composites obtained by aqueous tape casting and hot pressing

ZrB₂-SiC composites with different SiC content were prepared through aqueous tape casting and hot pressing. The influences of dispersant, SiC content and binder content on the rheological properties of slurries were investigated and the conditions for preparing stable ZrB₂-SiC suspensions were optimized. After tape casting and drying, the green ZrB₂-SiC tapes showed good flexibility, lubricious surface and homogeneous microstructure. The ZrB₂ ceramics could be densified to 97.2% after hot-pressing, while the ZrB₂ containing 20 and 30 vol% SiC ceramics were nearly fully densified (>99%). The sintered ZrB₂-20 vol% SiC ceramic had improved mechanical properties compared with ZrB₂ ceramic. Further increase in SiC content resulted in lower flexural strength and fracture toughness. SEM and TEM showed a fine microstructure with a clear grain boundary. The fracture mode changed from intragranular type for ZrB₂ to both intragranular and intergranular type for ZrB₂-SiC composites.     

Comparative evaluation of two different methods for thermal shock resistance of laminated ZrB2-SiCw/BN ceramics

The thermal shock resistance (TSR) of laminated ZrB₂–SiC_w/BN ceramic was evaluated through indentation-quench and quenching-strengthening methods. It was correspondingly compared to monolithic ZrB₂–SiC_w ceramic. In the indentation-quench method with consideration to crack propagation on the surface layer, the critical thermal shock temperature of laminated ZrB₂–SiC_w/BN ceramic with surface residual tensile stress was 550?°C, which was lower than monolithic ZrB₂–SiC_w ceramic (600?°C). Unlike the microscopic method of crack growth measurement through indentation-quench testing, the quenching-strengthening method, which was based on the macroscopic properties of the material, mainly characterizing the residual strength subsequently to thermal shock, the critical thermal shock temperatures of the laminates and monolithic were 609?°C and 452?°C, respectively. Compared to the brittle fracture of ZrB₂–SiC_w ceramics, the deflection, bifurcation and delamination of the cracks as the main TSR mechanisms of the laminated ceramics, were revealed through quenching-strengthening method, which was more suitable for the TSR characterization of laminated ceramics.     

Reactive hot pressing route for dense ZrB2-SiC and ZrB2-SiC-CNT ultra-high temperature ceramics

The in-situ exothermic reactions between ZrC_0.8, B₄C and Si have assisted densification and allowed to obtain fully dense ZrB₂-31 wt.%SiC ultra-high temperature ceramics within 6 min at 1750 °C. The use of zirconium carbide instead of metallic zirconium in the green body obviated the possibility of in-situ SHS process and allowed to apply the pressure at low temperatures. The latter provided a first densification stage just above 1050 °C. A slight carbon excess was created in the green body to preserve the carbon nanotubes. The developed reactive hot pressing route (1830 °C, 3 min, 30 MPa) has been successfully used to obtain ZrB₂-SiC ceramics containing 8 vol.% of multi-wall carbon nanotubes (MW-CNT). The carbon nanotubes survived the thermal cycle and could be clearly observed in the sintered ceramics. The CNT addition improved the fracture toughness of the composite from 4.3 MPa m^1/2 for ZrB₂-31 wt.%SiC to 6.8 MPa m^1/2 for ZrB₂-29 wt.%SiC-CNT.     

Effect of SiC whiskers and graphene nanosheets on the mechanical properties of ZrB2-SiCw-Graphene ceramic composites

Ultrahigh temperature ZrB₂-SiC_w-Graphene ceramic composites are fabricated by hot pressing ZrB₂-SiC_w-Graphene oxide powders at 1950 °C and 30 MPa for 1 h. The microstructures of the composites are characterized by Scanning electron microscopy, Raman spectroscopy and X-ray diffraction. The results show that multilayer graphene nanosheets are achieved by thermal reduction of graphene oxide during sintering process. Compared with monolithic ZrB₂ materials, flexural strength and fracture toughness are both improved due to the synergistic effect of SiC whisker and graphene nanosheets. The toughening mechanisms mainly are the combination of SiC whisker and graphene nanosheets crack bridging, pulling out.     

High temperature oxidation behavior of ZrB2-SiC added MoSi2 ceramics

In this paper, MoSi₂, MoSi₂-20?vol% (ZrB₂-20?vol% SiC) and MoSi₂-40?vol% (ZrB₂-20?vol% SiC) ceramics were prepared using pressureless sintering. The oxidation behaviors of these MoSi₂-(ZrB₂-SiC) ceramics were investigated at 1600?°C for different soaking time of 60, 180 and 300?min, respectively. The oxidation behaviors of the MoSi₂-(ZrB₂-SiC) ceramics were studied through weight change test, oxide layer thickness measurement, and microstructure analysis. Further investigation of the oxidation behaviors of the MoSi₂-(ZrB₂-SiC) ceramics was conducted at a higher temperature of 1800?°C for 10?min. The microstructure evolution of the ceramics was also analyzed. It was finally found that the oxidation resistance of MoSi₂ was improved by adding ZrB₂-SiC additives, and the MoSi₂-20?vol% (ZrB₂-20?vol% SiC) ceramic exhibited the optimal oxidation resistance behavior at elevated temperatures. From this study, it is believe that it can give some fundamental understanding and promote the engineering application of MoSi₂-based ceramics at high temperatures.     

Mechanical properties of biomimetic ceramic with Bouligand architecture

Biomimetic Bouligand architecture is constructed in the ceramic to improve its toughness. Firstly, unidirectional carbon fiber-reinforced ZrB₂-SiC ceramic films are achieved through a vacuum-assisted filtration method using graphene oxide. Then, ceramic films are helically assembled at a fixed angle of 30° in the graphite die based on the fiber orientation. Finally, the spark plasma sintering method was utilized to densify helical assembly carbon fiber/ceramic films. By constructing Bouligand structure, high fracture toughness (7.4 MPa·m^0.5) and work of fracture (∼1055 J/m²) are achieved in ZrB₂-based ceramic. The toughening mechanisms mainly are crack deflection, twisting and branching, carbon fiber pulling out, and bridging.     

Toughening of laminated ZrB2-SiC ceramics with residual surface compression

Laminated ZrB₂-SiC ceramics with residual surface compression were prepared by stacking layers with different SiC contents. The maximum apparent fracture toughness of these laminated ZrB₂-SiC ceramics was 10.4 MPam^1/2, which was much higher than that of monolithic ZrB₂-SiC ceramics. The theoretical predictions showed that the apparent fracture toughness was strongly dependent on the position of the notch tip, which was confirmed by the SENB tests. Moreover, laminated ceramics showed a higher fracture load when the notch tip located in the compressive layer, whereas showed a lower fracture load as the notch tip within the tensile layer. The toughening effect of residual compressive stresses was verified by the appearance of crack deflection and pop-in event. The influence of geometrical parameters on the apparent fracture toughness and residual stresses was analyzed. The results of theoretical calculation indicated that the highest residual compressive stress did not correspond to the highest apparent fracture toughness.     

Ablation behavior of laminated Graphite/ZrB2-SiC ceramics in two different directions

Laminated Graphite/ZrB₂-SiC ceramics were fabricated by tape casting and hot pressing. The ablation properties of the ceramics in the parallel and the perpendicular directions were studied using an oxyacetylene torch. The mass ablation rates were 8.1?±?0.4?mg/s in the parallel direction and 0.2?±?0.1?mg/s in the perpendicular direction. The linear ablation rates were 3.1?±?0.2?µm/s in the parallel direction and 1.2?±?0.1?µm/s in the perpendicular direction. Thus, the ablation resistance of the laminated Graphite/ZrB₂-SiC ceramics in the perpendicular direction was higher than that in the parallel direction. This anisotropy was mainly attributed to the lower surface temperature in the perpendicular direction resulted from higher thermal conductivity, as well as the orientation of the weak graphite interface layer perpendicular to the ablation surface.