Preparation and characterization of ZrB2-SiC ultra-high temperature ceramics by microwave sintering

ZrB₂-SiC ultra-high temperature ceramic composites reinforced by nano-SiC whiskers and SiC particles were prepared by microwave sintering at 1850°C. XRD and SEM techniques were used to characterize the sintered samples. It was found that microwave sintering can promote the densification of the composites at lower temperatures. The addition of SiC also improved the densification of ZrB₂-SiC composites and almost fully dense ZrB₂-SiC composites were obtained when the amount of SiC increased up to 30vol.%. Flexural strength and fracture toughness of the ZrB₂-SiC composites were also enhanced; the maximum strength and toughness reached 625 MPa and 7.18 MPa·m^1/2, respectively.     

Preparation and characterization of ZrB<Subscript>2</Subscript>-SiC ultra-high temperature ceramics by microwave sintering

ZrB₂-SiC ultra-high temperature ceramic composites reinforced by nano-SiC whiskers and SiC particles were prepared by microwave sintering at 1850°C. XRD and SEM techniques were used to characterize the sintered samples. It was found that microwave sintering can promote the densification of the composites at lower temperatures. The addition of SiC also improved the densification of ZrB₂-SiC composites and almost fully dense ZrB₂-SiC composites were obtained when the amount of SiC increased up to 30vol.%. Flexural strength and fracture toughness of the ZrB₂-SiC composites were also enhanced; the maximum strength and toughness reached 625 MPa and 7.18 MPa·m^1/2, respectively.     

高性能二维碳/碳复合材料的制备与性能

为获得高性能热结构复合材料,以国产T300碳纤维为原料,通过碳布预浸料交替铺层热压及液相浸渍裂解工艺方法制备了一系列二维碳/碳复合材料,并对二维碳/碳复合材料的微观结构特征、力学性能及烧蚀性能进行了测试与分析。研究结果表明:碳布规格及制备工艺对二维碳/碳复合材料力学性能有较大影响,当碳布规格选用八枚缎纹、经过碳化预处理且高温处理温度达到2 300℃时,二维碳/碳复合材料表现出较好的综合性能,拉伸强度和层间剪切强度的最大值分别高达301 MPa和12.4 MPa,达到了国际先进水平;在模拟典型服役环境考核状态下,制备的不同规格二维碳/碳复合材料的烧蚀性能基本相当,均未出现由于层间强度偏低而发生的烧蚀揭层现象,表现出较好的烧蚀均匀性和结构可靠性。      

Toughening effect of short carbon fibers in the ZrB2–ZrSi2 ceramic composites

The toughening effect of the short carbon fibers in the ZrB₂–ZrSi₂ ceramic composites were investigated, where the ZrB₂–ZrSi₂ ceramics without carbon fibers were used as the reference. The mechanical properties were evaluated by means of flexural and SENB tests, respectively. The microstructure was characterized by SEM equipped with EDS. The results found that the short carbon fibers were uniformly incorporated in the ZrB₂–ZrSi₂ matrix and the relative density was about 97.92%. The flexural strength of short carbon fiber-reinforced ZrB₂–ZrSi₂ composites is 437 MPa; the fracture toughness and the work of fracture are 6.89 MPa m^1/2 and 259 J/m², respectively, which increased significantly in comparing with composites without fibers. The microstructure analysis revealed that the improved fracture toughness could be attributed to the fiber bridging, the fiber–matrix interface debonding and the fiber pullout, which consumed more fracture energy during the fracture process.     

A multilayer MoSi2-SiC-B coating to protect SiC-coated carbon/carbon composites against oxidation

To protect carbon/carbon (C/C) composites against oxidation, a multilayer MoSi₂-SiC-B coating was prepared on the SiC-coated C/C composites by a simple and low-cost slurry method. The phase, microstructure and element distribution of the as-received coating were analyzed using X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. The as-received coating could effectively protect C/C composites against oxidation at 850 °C in air for 100 h without mass loss, which exhibits better oxidation protective ability than the multilayer MoSi₂-SiC coating prepared by the same method. At intermediate temperature (850 °C), the excellent oxidation protective ability of the coating is mainly attributed to the formation of the molten B₂O₃ for sealing the microcracks and preventing oxygen from attacking the C/C substrate.     

Fabrication and microstructural evaluation of ZrB2/ZrC/Zr composites by liquid infiltration

The microstructure of ZrB₂/ZrC/Zr composites was examined using scanning electron microscopy, optical microscopy, and X-ray diffraction techniques. Dense ZrB₂/ZrC/Zr composites could be fabricated by the reaction sintering of molten zirconium with ZrB₂ preform. The composites were made by infiltration of molten zirconium into ZrB₂ preform, which contained 0–40 vol% B₄C, at 1900C for 10 min. The average grain size of ZrB₂ in the reaction-sintered composites decreased slightly with an increase in the volume fraction of the B₄C. The volume fraction of the solid increased with further increase of B₄C contents. The mechanical properties were measured in accordance with B₄C contents. The composites exhibited a four-point bending strength of up to 570 MPa and a fracture toughness of up to 11.5 MPa m^1/2.     

致密工艺对炭布增强2D-C/C复合材料力学性能的影响

研究了液相浸渍及化学气相法致密工艺对二维炭/炭(2D-C/ C)复合材料力学性能的影响,尤其是对层间剪切强度(ILSS)的影响.结果表明液相浸渍法增密周期短且致密效果好,但材料强度不高;而化学气相沉积(CVD)致密周期长,但材料层剪强度高;采用两种工艺联合致密,材料界面结合强度适中,且层剪强度高.     

CVI结合浆料浸渍法制备2D C/SiC复合材料的微观结构和力学性能

采用CVI结合浆料浸渍工艺制备2D C/SiC复合材料。研究了SiC微粉对复合材料微结构和力学性能的影响。结果表明,当碳纤维预制沉积SiC80h后,微粉主要渗入到纤维束间。复合材料的力学强度随着渗微粉前CVI时间的增加及渗入浆料浓度的降低而增加。微粉的渗入大大降低了材料的层间剪切强度,而对材料的拉伸强度影响较小。     

Effects of Cf/C density on microstructure and properties of 3-D Cf/ZrC composites prepared by liquid metal infiltration

Three-dimensional braided carbon fiber-reinforced ZrC matrix composites, 3-D C_f/ZrC, were fabricated by Liquid metal infiltration process at 1200 °C. Porous carbon/carbon (C_f/C) composites with various densities were used as preforms, and the effects of C_f/C density on microstructure and properties of the 3-D C_f/ZrC composites were investigated. The results show that the composites are composed of carbon, ZrC and residual metal. Both microstructure and properties of the 3-D C_f/ZrC composites are apparently affected by C_f/C density. With increasing density of C_f/C preform, the density of 3-D C_f/ZrC composites decreases while the open porosity increases. The composites obtained from the C_f/C preform with a density of 1.12 g/cm³ have the best mechanical properties, with flexural strength of 286.2 ± 11.4 MPa, elastic modulus of 83.5 ± 6.8 GPa and fracture toughness of 9.2 ± 0.6 MPa m^1/2. The composites exhibit excellent ablation resistance, and the mass rate and the linear ablation rate under an oxyacetylene torch are as low as 5.1 ± 0.4 mg s⁻¹ and 1.1 ± 0.3 μm s⁻¹, respectively.     

Fabrication of SiCf/SiC composites by chemical vapor infiltration and vapor silicon infiltration

Three-dimensional (3D) silicon carbide fiber reinforced silicon carbide matrix (SiC_f/SiC) composites, employing KD-1 SiC fibers (from National University of Defense Technology, China) as reinforcements, were fabricated by a combining chemical vapor infiltration (CVI) and vapor silicon infiltration (VSI) process. The microstructure and properties of the as prepared SiC_f/SiC composites were studied. The results show that the density and open porosity of the as prepared SiC_f/SiC composites are 2.1 g/cm³ and 7.7%, respectively. The SiC fibers are not severely damaged during the VSI process. And the SiC fibers adhere to the matrix with a weak interface, therefore the SiC_f/SiC composites exhibit non-catastrophic failure behavior with the flexural strength of 270 MPa, fracture toughness of 11.4 MPa·m^1/2 and shear strength of 25.7 MPa at ambient conditions. Moreover, the flexural strength decreases sharply at the temperature higher than 1200 °C. In addition, the thermal conductivity is 10.6 W/mk at room temperature.     

Effect of graphite flake on the mechanical properties of hot pressed ZrB2-SiC ceramics

A ZrB₂ ceramic containing 20 vol.% SiC and 10 vol.% graphite flake (ZrB₂-SiC-G) was fabricated by hot pressing. It was shown that the fracture toughness was improved due to the introduction of graphite flake, whereas the flexure strength and hardness decreased slightly. The fracture toughness of ZrB₂-SiC-G composite was 6.1 ± 0.3 MPa·m^1/2, which was much higher than that of monolithic ZrB₂, ZrB₂-SiC composite and similar ZrB₂-SiC-C composite. The toughening mechanisms are crack deflection and branching as well as stress relaxation near the crack tip. The results here pointed to a potential method for improving fracture toughness of ZrB₂-based ceramics.     

Preparation of B4C-ZrB2-SiC eutectic ceramics by arc melting method

The B₄C-ZrB₂-SiC ternary composites with super hard and high toughness were obtained by arc melting in argon atmosphere. Microstructures were observed by SEM, and phase compositions were analyzed by XRD. The hardness and fracture toughness of ternary composites are 28 GPa and 4.5 MPa·m^1/2. The eutectic mole composition is 0.39B₄C-0.25ZrB₂-0.36SiC, and the eutectic lamellar microstructure is composed of B₄C matrix with the lamellar ZrB₂ and SiC grains.     

ZrB2-ceramic toughened by refractory metal Nb prepared by hot-pressing

ZrB₂–Nb (ZN) composites were prepared through hot-pressing at a temperature of 1800 °C. A contribution of Nb was believed a significant influence on the sinterability, microstructure and mechanical properties of ZN composites. The values of flexural strength of ZN composites rang from 395 to 773 MPa, who are dependent on Nb contents. The highest strength obtained for the ZN composite containing 25 vol.% Nb (773 MPa). A fracture toughness of 7.1 MPa m^1/2 of ZN was revealed, which was much higher than that of monolithic ZrB₂. The improvement in fracture toughness strongly depended on an introduction of Nb–ZrB₂ matrix. Crack deflection and branching were believed to be the toughening mechanism of ZN.     

Pressureless sintering ZrB2-SiC ceramics at low temperatures

ZrB₂-SiC ceramics are prepared by pressureless sintering using ZrB₂ powders and liquid polycarbosilane (LPCS) precursors. The LPCS can effectively reduce the sintering temperature. The phases of the sintered ceramics are characterized by X-ray diffraction, and their morphologies are observed by scanning electron microscopy. From these results, it is learned that LPCS can provide free carbon and silicon at high temperatures. Therefore, the oxides on the ZrB₂ surface can be removed by free carbon, and the densification process can be promoted by silicon. These coupled effects make it possible to pressureless sinter the ZB₂-SiC ceramics at low temperatures.     

ZrB2 coating for the oxidation protection of carbon fiber reinforced silicon carbide matrix composites

In order to improve the anti-oxidation performance of carbon fiber reinforced silicon carbide matrix (C/SiC) composites, ZrB₂ coating was prepared on the surface of C/SiC composites by a two-step technique of pack cementation method. The anti-oxidation properties of coated composites were investigated. The results showed that ZrB₂ coating was obtained by the method, which was homogenous and dense. The weight loss percentage of the coated composites was only 1.52 after oxidation in air at 1500 °C for 30 min, which exhibited excellent oxidation resistance.     

Microstructure and mechanical properties of ZrB2-SiC composites

A ZrB₂-based composite containing 20 vol.% nanosized SiC particles (ZSN) was fabricated at 1900 °C for 30 min under a uniaxed load of 30 MPa by hot-pressing. The microstructure and mechanical properties of the composite were investigated. It was shown that the grain growth of ZrB₂ matrix was effectively suppressed by submicrosized SiC particles located along the grain boundaries. In addition, the mechanical properties of ZSN composite were strongly improved by incorporating the nanosized SiC particles into a ZrB₂ matrix, especially for flexural strength (925 ± 28 MPa) and fracture toughness (6.4 ± 0.3 MPa•m^1/2), which was much higher than that of monolithic ZrB₂ and ZrB₂-based composite with microsized SiC particles, respectively. The formation of intragranular nanostructures plays an important role in the strengthening and toughening of ZrB₂ ceramic.     

C/C复合材料ZrB2基超高温陶瓷涂层的研究进展

ZrB₂基超高温陶瓷因其优异的高温抗氧化和烧蚀等性能,成为C/C复合材料理想的热防护涂层材料。本文从以下几个方面对C/C复合材料表面用ZrB₂基超高温陶瓷涂层的研究现状进行了综述:介绍了ZrB₂基超高温陶瓷涂层体系的主要制备技术,并对比了其制备的涂层抗氧化性和抗烧蚀性,总结了各制备方法的优点与不足;从单元、双元、三元材料掺杂改性的角度,详述了ZrB₂基复合涂层常见的材料体系,总结了其改性思路;介绍了ZrB₂基涂层在多层结构设计与开发方面的研究现状。最后简要展望了ZrB₂基超高温陶瓷涂层未来的研究方向。     

Thermodynamic study on co-deposition of ZrB2-SiC from ZrCl4-BCl3-CH3SiCl3-H2-Ar system

Thermodynamics phase diagram of ZrB₂-SiC co-deposited from precursors of ZrCl₄-BCl₃-CH₃SiCl₃ (methyltrichlorosilane, MTS)-H₂-Ar has been investigated in detail by using the FactSage code and its embedded database (130 species being involved). The yields of condensed phases in the co-deposition process have been examined as the functions of the inject reactant ratios of BCl₃ / (BCl₃ + MTS) and H₂ / (ZrCl₄ + BCl₃ + MTS), and the temperature at a fixed pressure of 5 kPa. The results show that their yields strongly depend on the molar ratios of the inject reactants and the temperature. Consequently, the pure ZrB₂-SiC composite without free C, B₄C, ZrC and ZrSi can be co-deposited under the ideal condition by adjusting the reactant ratios and the temperature. The gas-phase equilibrium concentration distribution shows that the high input amount of H₂ is favorable for the co-deposition of ZrB₂ and SiC at a fixed ratio of ZrCl₄:BCl₃:MTS:Ar. In the end, the theoretical results can lay down guidelines for increasing the experimental yields of ZrB₂ and SiC.     

Tensile properties of polyacrylonitrile- and pitch-based hybrid carbon fiber/polyimide composites with some nanoparticles in the matrix

The tensile properties and fracture behavior of polyacrylonitrile (PAN)- and pitch-based hybrid carbon fiber/polyimide composites with several types of nanoparticles (25 nm C, 20–30 nm β-SiC, 130 nm β-SiC, 80 nm SiO₂, and 300 nm SiO₂) added to the matrix were investigated. The tensile stress–strain curves of PAN- and pitch-based hybrid carbon fiber/polyimide composites with 25 nm C, 20–30 nm β-SiC, and 80 nm SiO₂ nanoparticles have complex shapes (jagged trace), whereas the tensile response of hybrid carbon fiber/polyimide composites with 130 nm β-SiC and 300 nm SiO₂ nanoparticles indicates an instantaneous failure. The stress after the initial failure in hybrid carbon fiber/polyimide composites improves by adding 25 nm C, 20–30 nm β-SiC, and 80 nm SiO₂ nanoparticles to the matrix and correlates with the fracture toughness of the polyimide matrix.