Mechanical behaviour and microstructure of Cf/ZrC,Cf/SiC and Cf/ZrC – SiC composites

Cf/ZrC, Cf/SiC and Cf/ZrC–SiC composites were successfully prepared by polymer infiltration and pyrolysis (PIP) using polycarbosilane and a liquid ZrC precursor. The densification process, mechanical properties and microstructures were studied in a view of comparison. After the same total 20 PIP cycles, the Cf/ZrC, Cf/SiC and Cf/ZrC–SiC composites had flexural strengths of 50.1±5.3, 285.7±22.6, 141.5±13.1?MPa respectively; elastic moduli of 7.8±0.9, 57.1±3.2 and 45.1±2.6?GPa respectively; and fracture toughness of 2.5±0.2, 10.4±0.9 and 10.9±1.1?MPa m^1/2 respectively. With the introduction of high modulus SiC phase into the ZrC matrix, the densification and modulus of the matrix were improved; as a result, the Cf/ZrC–SiC composite showed higher mechanical properties compared to Cf/ZrC.     

Densification,microstructure, and mechanical properties of ZrC–SiC ceramics

ZrC–SiC ceramics were fabricated by high-energy ball milling and reactive hot pressing of ZrH₂, carbon black, and varying amounts of SiC. The ceramics were composed of nominally pure ZrC containing 0 to 30 vol% SiC particles. The relative density increased as SiC content increased, from 96.8% for nominally pure ZrC to 99.3% for ZrC-30 vol% SiC. As SiC content increased from 0 to 30 vol%, Young's modulus increased from 404 ± 11 to 420 ± 9 GPa and Vickers hardness increased from 18.5 ± 0.7 to 23.0 ± 0.5 GPa due to a combination of the higher relative density of ceramics with higher SiC content and the higher Young's modulus and hardness of SiC compared to ZrC. Flexure strength was 308 ± 11 MPa for pure ZrC, but increased to 576 ± 49 MPa for a SiC content of 30 vol%. Fracture toughness was 2.3 ± 0.2 MPa·m^1/2 for pure ZrC and increased to about 3.0 ± 0.1 MPa·m^1/2 for compositions containing SiC additions. The combination of high-energy ball milling and reactive hot pressing was able to produce ZrC–SiC ceramics with sub-micron grain sizes and high relative densities with higher strengths than previously reported for similar materials.     

Influence of sol–gel derived ZrO2 and ZrC additions on microstructure and properties of ZrB2 composites

ZrB₂ powder was coated with 5% ZrOC sol–gel precursor and sintered by SPS. Relative densities >98% were achieved at 1800 °C with minimal grain growth and an intergranular phase of ZrC. Carbon content in the precursor determined the type of reinforcing phase and porosity of the sintered composites. XRD, SEM and EDS studies indicated that carbon deficiency resulted in ZrO₂ retention, improving ZrB₂ densification with oxide particle reinforcement. Excess carbon resulted in ZrC formation as the reinforcing phase, but could yield porosity and residual carbon at grain boundaries. These two types of ZrB₂ composites displayed different densification and microstructural evolution that explain their contrasting properties. In the extreme oxidative environment of oxyacetylene ablation, the composites with ZrC-C maintained superior leading edge geometry; whereas for mechanical strength, a bias towards the residual ZrO₂ content was beneficial. This highlighted the sensitivity of processing carbon-precursors in the initial sol–gel process and the carbon content in ZrB₂-based composite systems.     

SPS densification and microstructure of ZrB2 composites derived from sol–gel ZrC coating

A technique for densifying ultra high temperature ceramic composites while minimising grain growth is reported. As-purchased ZrB₂ powder was treated with a zirconia-carbon sol–gel coating. Carbothermal reduction at 1450 °C produced 100–200 nm crystalline ZrC particles attached on the surface of ZrB₂ powders. The densification behaviour of the sol–gel coated powder was compared with both the as-purchased ZrB₂ and a compositionally similar ZrB₂–ZrC mixture. All three samples were densified by spark plasma sintering (SPS). The ZrB₂ reference sample was slow to densify until 1800 °C and was not fully dense even at 2000 °C, while the sol–gel modified ZrB₂ powder completed densification by 1800 °C. The process was studied by ram displacement data, gas evolution, SEM, and XRD. The sol–gel coated nanoparticles on the ZrB₂ powder played a number of important roles in sintering, facilitating superior densification by carbothermal reduction, nanoparticle coalescence and solid-state diffusion, and controlling grain growth and pore removal by Zener pinning. The sol–gel surface modification is a promising technique to develop ultra-high temperature ceramic composites with high density and minimum grain growth.     

Effects of high-temperature annealing on the microstructure and properties of C/SiC–ZrC composites

C/SiC–ZrC composites were prepared by a combining slurry process with precursor infiltration and pyrolysis, and then annealed from 1200 °C to 1800 °C. With rising annealing temperature, their mass loss rate increased, and the flexural strength and modulus decreased from 227.9 MPa to 41.3 MPa and from 35.3 GPa to 22.7 GPa, respectively. High-temperature annealing, which elevated thermal stress and strengthened interface bonding, was harmful to the flexural properties. However, it improved the ablation properties by increasing the crystallization degree of SiC matrix. The mass loss rate and linear recession rate decreased with increasing annealing temperature and those of the samples annealed at 1800 °C were 0.0074 g/s and 0.0011 mm/s respectively. Taking mechanical and ablation properties into consideration simultaneously, the optimum annealing temperature was 1600 °C.     

Polymer precursor synthesis of novel ZrC–SiC ultrahigh-temperature ceramics and modulation of their molecular structure

In this study, ZrC–SiC composite ceramics were prepared with varying Zr/Si molar ratios using sol–gel method. Composites were characterized by Fourier-transform infrared spectroscopy (FT–IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman spectroscopy, and energy-dispersive X-ray spectroscopy (EDS). FT–IR analysis confirmed macromolecular network structure of composites, in which the precursor is composed of polyvinyl butyral (PVB) as main chain, silane molecules are interlinked via –OH moieties in PVB side chains, and Zr atoms are crosslinked with Si in corresponding proportion. Ceramic precursor begins to decompose at a temperature exceeding 1300 °C and is completely transformed into ZrC–SiC composite ceramics with corresponding Zr/Si molar ratio at 1600 °C. Raman spectroscopy and TEM results reveal that after annealing at 1600 °C, ZrC powder uniformly covers surface of SiC ceramics, and high-crystallinity graphite carbon covers ZrC powder.     

可溶性前驱体法制备ZrC粉末的研究进展

碳化锆具有耐烧蚀,耐腐蚀的性质,高熔点,高硬度以及良好的机械稳定性,受到了广泛的关注,在表面保护材料,耐火材料和航空航天超高温结构材料等领域有广泛的应用。液相前驱体法制备ZrC粉末节约设备费,工艺周期短,合成所需温度低,能在很短时间内获得分子水平的混合得到前驱体,且粉末粒径小,而且可用于浸渍法对表面进行覆盖,是一种很有前景的粉体制备技术。本文主要综述了ZrC粉末的液相可溶性前驱体制备技术,并详细分析了目前各制备技术的特点。     

Microstructure and properties of ablative C/ZrC–SiC composites prepared by reactive melt infiltration of zirconium and vapour silicon infiltration

C/ZrC-SiC composites with a density of 3.09 g/cm³ and a porosity of 4.8% were prepared by reactive melt infiltration and vapour silicon infiltration. The flexural strength and modulus were 235 MPa and 18.3 GPa, respectively, and the fracture toughness was 7.0 MPa m^1/2. The formation of SiC and ZrSi₂ during vapour silicon infiltration, at the residual cracks and pores in the C/ZrC, enhanced the interface strength and its mechanical properties. The high flexural strength (223 MPa, c. 95% of the original value) after oxidation at 1600 °C for 10 min indicated the excellent oxidation resistance of the composites after vapour silicon infiltration. The mass loss and linear recession rate of the composites were 0.0071 g/s and 0.0047 mm/s, respectively and a fine ablation morphology was obtained.     

Fabrication and properties of 2D C/C–ZrB2–ZrC–SiC composites by hybrid precursor infiltration and pyrolysis

Abstract

Two dimensional C/C–ZrB₂–ZrC–SiC composites were fabricated through precursor infiltration and pyrolysis process using a mixture of polycarbosilane and ZrB₂ precursor and ZrC precursor as the impregnant. The microstructures, mechanical properties and ablation properties of the composites were investigated. The results showed that the homogeneity of the composite improved on using novel precursors that can dissolve with polycarbosilane through the formation of nanocomposite matrix. The flexural strength and fracture toughness first increased and then decreased on increasing the pyrocarbon content in the composite. Compared with the C/C–SiC composite, the ablation resistance of C/C–ZrB₂–ZrC–SiC composite was greatly enhanced. The mass loss rate and linear recession rate exposed to the plasma torch were 1?7 mg/s and 1?8 μm/s, respectively. The formation of a ZrO₂–SiO₂ glassy layer on the surface significantly contributed to the excellent ablative property of the composite.     

ZrC和HfC的价电子结构及其性能研究

根据固体与分子经验电子理论,对ＺｒＣ,ＨｆＣ相的价电子结构进行了定量分析,通过键距差（ＢＬＤ）方法,计算了ＺｒＣ,ＨｆＣ晶体中各键上的共价电子数。结果表明,ＺｒＣ,ＨｆＣ晶体都是靠键距为α／２的Ｚｒ－Ｃ,Ｈｆ－Ｃ最强键连接的,且该最强键是对称分布的,从而了解释了ＺｒＣ,ＨｆＣ相本质上具有超高硬度的原因。     

Polymeric liquid precursor of multi-component ZrC–SiC ceramic

Polymeric liquid ceramic precursors for the production of multi-component ZrC–SiC ceramics were prepared by reactive blending of polyzirconoxanesal, phenylacetylene-terminated polysilane and bisphenol-A type benzoxazine. The polymeric liquid precursors of ZrC–SiC ceramic have the processing capability of Precursor-Infiltration-and-Pyrolysis technique in ceramic composites fabrication. The thermal cure reactions included by the catalytic polymerisation of ethynyl groups, the ring opening polymerisation of benzoxazine rings, and the condensation of zirconate with phenolic hydroxyl and Si–H at 200–350°C. The monolithic ceramics were formed upon pyrolysis at 1000, 1200 and 1600°C in a yield of 65, 62 and 40%, respectively. X-ray diffraction and SEM–EDS results revealed that almost pure, elemental, uniformly distributed ZrC–SiC multi-component ceramic monolith was obtained through pyrolysis at 1600°C via carbothermal reduction of ZrO₂.     

Densification,microstructure, elastic and mechanical properties of reactive hot-pressed ZrB2–ZrC–Zr cermets

In this study, cermets composed of zirconium diboride and zirconium carbide with intergranular zirconium were sintered by reactive hot-pressing. Relative density exceeding 97% was obtained for the sintered cermets having four distinct compositions varying in concentration of excess Zr. Their densification behaviour was examined by monitoring displacement during sintering. The microstructure was characterized by scanning electron microscopy and X-ray diffraction, and the elastic and mechanical properties were evaluated at room temperature. The effects of Zr concentration on the densification and mechanical properties were assessed. The ZrB₂ and ZrC micron-grains coarsened with increasing amount of Zr starting material. In addition, the cermets exhibited high flexural strength (546–890 MPa) and fracture toughness (6.63–10.24 MPa m^1/2), which simultaneously increased with increasing Zr concentration. However, the elastic moduli and hardness (11–18 GPa) decreased with increasing Zr. The shear modulus and Young's modulus were in the range of 150–190 GPa and 360–440 GPa, respectively.     

Effect of PyC interphase thickness on mechanical and ablation properties of 3D Cf/ZrC–SiC composite

Three-dimensional (3D) C_f/ZrC–SiC composites were successfully prepared by the polymer infiltration and pyrolysis (PIP) process using polycarbosilane (PCS) and a novel ZrC precursor. The effects of PyC interphase of different thicknesses on the mechanical and ablation properties were evaluated. The results indicate that the C_f/ZrC–SiC composites without and with a thin PyC interlayer of 0.15 µm possess much poor flexural strength and fracture toughness. The flexural strength grows with the increase of PyC layer thickness from 0.3 to 1.2 µm. However, the strength starts to decrease with the further increase of the PyC coating thickness to 2.2 µm. The highest flexural strength of 272.3±29.0 MPa and fracture toughness of 10.4±0.7 MPa m^1/2 were achieved for the composites with a 1.2 µm thick PyC coating. Moreover, the use of thicker PyC layer deteriorates the ablation properties of the C_f/ZrC–SiC composites slightly and the ZrO₂ scale acts as an anti-ablation component during the testing.     

Mechanical behaviour of carbon fibre reinforced TaC/SiC and ZrC/SiC composites up to 2100°C

The microstructure and elevated temperature mechanical properties of continuous carbon fibre reinforced ZrC and TaC composites were investigated. Silicon carbide was added to both compositions to aid sintering during hot pressing. Fibres were homogeneously distributed and no fibre degradation was observed at the interface with the ceramic matrix even after testing at 2100 °C. The flexural strength increased from 260 to 300 MPa at room temperature to ∼450 MPa at 1500 °C, which was attributed to stress relaxation. At 1800 °C, the strength decreased to ∼410 MPa for both samples. At 2100 °C plastic deformation resulted in lower strength at the proportional limit (210–320 MPa), but relatively high ultimate strength (370–440 MPa). The sample containing ZrC had a lower ultimate strength, but higher failure strain at 2100 °C due to the weak fibre/matrix interface that resulted in fibre-dominated composite behaviour.     

自蔓延高温技术制备ZrC粉体(英文)

采用自蔓延高温合成(self-propagating high-temperature synthesis,SHS)技术,以 Zr+C 为反应体系合成了 ZrC 粉末。研究了实验参数对 SHS过程中点火电流、燃烧温度的影响。采用了 3 种碳源,研究了其对最终产物形貌及化学组成的影响。通过添加不同含量的 NaCl 作为 SHS 稀释剂,控制产物粒径及形貌。结果表明:炭黑是高温自蔓延法制备 ZrC 粉体的最佳碳源。由该体系制备的 ZrC 粉末粒径在 0.5～1 μm之间,氧含量为 0.38%。随稀释剂 NaCl 含量增加,体系燃烧温度降低,产物粒径减小。当 NaCl 含量为 30% (质量分数)时,体系燃烧温度下降至 1 810 K,产物 ZrC 粉末的粒径减小至 50 nm。     

ZrC改性C/C复合材料的抗氧化涂层研究

为了提高C/C复合材料的高温抗氧化性能，采用含锆有机溶剂实现了对C/C复合材料的ZrC改性，通过粉末包埋法在其表面制备了SiC过渡层，通过溶胶凝胶法制备了外部的复合陶瓷氧阻挡层。设计三因素三水平的正交试验，研究了ZrC改性增重、过渡层厚度和氧阻挡层厚度三个主要因素对C/C复合材料高温抗氧化性能的影响。9个样品在1600℃马弗炉中进行了30 min的静态氧化测试，结果表明，ZrC改性增重5%、过渡层厚度为60μm和氧阻挡层厚度为80μm的样品抗氧化性能最好，质量损失率仅约5.51%。     

High shear strength and ductile ZrC–SiC/austenitic stainless steel joints bonded with Ti/Ni foam interlayer

A transient-liquid-phase (TLP) diffusion bonding method was employed to join ZrC–SiC ceramic and austenitic stainless steel by using Ti foil and various density Ni foam as interlayer. The Ti–Ni TLP contributed to a firm bonding between ceramic and foam interlayer while avoiding liquid infiltration in foam structure. The influence of holding time on the microstructure of the TLP reaction layer was investigated. The shear tests showed the joints with foam interlayer exhibited ductile failure mode and improved fracture work in comparison with the one with dense Ni interlayer. A maximum shear strength of 117.2 MPa was reached when the relative density of Ni foam was 0.57. The fracture behaviors of the joints during shear test were in-situ observed.     

ZrC–SiC复相陶瓷先驱体的制备与性能

以聚锆氧烷(PNZ)为锆源树脂、炔基聚硅烷(PEPSI)为硅源树脂、双酚A型苯并噁嗪(BOZ)为碳源树脂,制备一种低成本高效率Zr C-Si C复相陶瓷先驱体。Zr C-Si C复相陶瓷先驱体适合陶瓷基复合材料的循环浸渍-裂解工艺,通过炔基的催化聚合、苯并噁嗪的开环聚合和锆氧烷与酚羟基、硅氢键的缩合聚合,在200~350℃热固化。N2气氛,优化配方中PNZ、PEPSI、BOZ的质量比为1.00:0.30:0.30)。在1 000、1 200、1 400和1 600℃高温裂解陶瓷的产率分别为64%、62%、62%和37%。通过1 600℃碳热还原反应,得到高度结晶和分布均匀的Zr C-Si C复相陶瓷。Zr C-Si C先驱体是理想的低成本超高温陶瓷基体树脂。