Compatibility of CVD SiC and SiCf/SiC Composites with High Temperature Helium Simulating Very High Temperature Gas-Cooled Reactor Coolant Chemistry

The chemical compatibility aspects of CVD β-SiC and SiC_f/SiC composites with a VHTR specific helium coolant were examined. The specimens were exposed to helium gas containing 20 Pa H₂, 5 Pa CO, 2 Pa CH₄, and 0.02–0.1 Pa H₂O, which is an expected VHTR coolant chemistry. Oxidation tests were carried out at 900 and 950 °C for up to 250 h. β-SiC and SiC_f/SiC composites had an excellent compatibility with the expected VHTR helium coolant environment. The oxidation of β-SiC as a matrix material of the SiC_f/SiC composite reacted in a passive oxidation regime owing to the presence of water vapor. A condensed version of the oxide SiO₂ formed at an early stage of oxidation and the growth of this oxide layer was very limited as the oxidation time increased up to 250 h. The recession of the pyrolytic carbon interphase of SiC_f/SiC composite could not be observed in the test range.     

SiCf/Ti-60热稳定性研究

本文对采用磁控溅射先驱丝法制备的SiC_f/Ti-60复合材料进行不同温度下长时间热暴露实验,分析了热等静压态和热暴露态复合材料界面区结构稳定性及元素扩散规律。研究结果表明,界面反应层主要产物为TiC,纤维中C、Si元素和基体中Ti及其它合金元素进行互扩散;C元素扩散速率较快,在界面处和基体内形成TiC,基体中的TiC主要集中分布在α相晶界处。SiC_f/Ti-60复合材料反应层长大受扩散控制并遵循抛物线定律,界面反应层长大指数因子为2.27×10_-4 m/s_1/2,界面反应层长大激活能为118 kJ/mol。     

Influence of an O2 Type Oxidizing Environment on SiCf/SiC Composites: Properties/Microstructure Relationship

Ceramic matrix composites have been identified as a potential material of core structure for the fourth generation of fission nuclear reactors. Regarding their excellent mechanical behavior in very harsh conditions (high temperature and high irradiation flux), the CVI–SiC_f/SiC composites with pyrocarbon interlayer are of prime interest for the fuel cladding in the gas-cooled fast reactor. Although the working atmosphere is helium in these advanced reactors, the presence of oxidizing impurities could have a significant role on the mechanical behavior of materials subjected to long-term exposures. Within this framework, this study was intended to investigate the influence of oxidation on the SiC_f/SiC composites mechanical properties. Different pre-damage states were intentionally introduced by mechanical tensile tests on plate specimens before performing an oxidation treatment of 1,000 h at 1,000 °C under helium with 10 ppm of O₂. The degradation of the composite was determined from the mechanical behavior of post-exposure specimens. Results were correlated both with microstructural observations of the damage and with characterizations of the generated oxides at the surface of the composites. The most severe decline of mechanical properties occurs for the higher predamaged loadings. Indeed in this case, the silica formed during the oxidation of SiC is not in sufficient quantities to fill the cracks.     

高温循环下SiC-C/SiBCN复合材料的力学性能研究

采用化学气相沉积(CVD)结合前驱体浸渍裂解(PIP)技术制备了SiC涂层的C/Si C和C/SiBCN复合材料,研究了高温循环氧化对2种复合材料弯曲性能的影响。结果表明,与SiC-C/SiC相比,SiC-C/SiBCN复合材料的平均室温抗弯曲强度约为605 MPa,增幅达到126.6%。在1000和1200℃循环3次后,Si C-C/SiBCN的剩余抗弯曲强度分别为417和342 MPa,强度保留率分别为68.9%和56.5%,显著优于SiC-C/Si C复合材料。与PIP SiC陶瓷基体相比,Si BCN基体的孔隙率更低,高温下SiBCN氧化后形成SiO_2和B_2O_3,可以更好地降低O_2的透过率,提高材料的抗氧化性能和强度保留率。     

Effect of thermal-cooling cycle treatment on thermal expansion behavior of particulate reinforced aluminum matrix composites

Two micron SiC particles with angular and spherical shape and the sub-micron Al2O3 particles with spherical shape were introduced to reinforce 6061 aluminium by squeeze casting technology.Microstructures and effect of thermal-cooling cycle treatment(TCCT) on the thermal expansion behaviors of three composites were investigated.The results show that the composites are free of porosity and SiC/Al2O3 particles are distributed uniformly.Inflections at about 300 °C are observed in coefficient of thermal expansion(CTE) versus temperature curves of two SiCp/Al composites,and this characteristic is not affected by TCCT.The TCCT has significant effect on thermal expansion behavior of SiCp/Al composites and CTE of them after 3 cycles is lower than that of 1 or 5 cycles.However,no inflection is observed in Al2O3p/Al composite,while TCCT has effect on CTE of Al2O3p/Al composite.These results should be due to different relaxation behavior of internal stress in three composites.     

Effects of dip-coated BN interphase on mechanical properties of SiCf/SiC composites prepared by CVI process

BN interphase was successfully synthesized on SiC fiber fabrics by dip-coating process using boric acid and urea as precursors under N₂ atmosphere. The morphology of BN interphase was observed by SEM, and the structure was characterized by XRD and FT-IR spectra. The SiC_f/SiC composites with dip-coated BN interphase were fabricated by chemical vapor infiltration (CVI) process, and the effects of BN interphase on the mechanical properties of composites were investigated. The results show that the SiC fibers are fully covered by BN interphase with smooth surface and turbostratic structure (t-BN), and the thickness is about 0.4 μm. The flexural strengths of SiC_f/SiC composites with and without BN interphase are about 180 and 95 MPa, respectively. Compared with the as-received SiC_f/SiC composites, the composites with BN interphase exhibit an obvious toughened fracture behavior. From the microstructural analysis, it can be confirmed that the BN interphase plays a key part in protecting the fibers from chemical attack during matrix infiltration and weakening interfacial bonding, which can improve the mechanical properties of SiC_f/SiC composites remarkably.     

Process study, microstructure, and matrix cracking of SiC fiber reinforced MoSi2 based composites

SiC fiber reinforced SiAlON-MoSi₂ composites have been manufactured by a concurrent fiber winding and low pressure plasma spraying (LPPS) technique to produce a multilayer, circumferentially fiber reinforced composite ring. The LPPS parameters for SiAlON-MoSi₂ powder were optimized by a two-level experimental design approach followed by further optimization, which provided a smooth sprayed surface, low matrix porosity, and high deposition efficiency. The microstructure of SiAlON-MoSi₂ matrix consisted of a lamellar structure built up of individual splats and a uniform distribution of discontinuous SiAlON splats throughout the MoSi₂ matrix. The spray/wind composites exhibited 2% porosity and well-controlled fiber distribution. High temperature consolidation led to the formation of a thick reaction zone at the fiber-matrix interface by a chemical reaction between C coating and MoSi₂. Matrix cracking occurred in SiC _f (15 vol.%)/MoSi₂ after cooling from 1500 to 25 °C and was attributed to the large tensile residual stresses in the matrix developed on cooling because of coefficient of thermal expansion (CTE) mismatch between matrix and fiber. The addition of 40 vol.% SiAlON into the MoSi₂ effectively eliminated the matrix cracking by reducing the matrix-fiber CTE mismatch. Predictions of matrix cracking stress on the basis of residual stresses in the composites showed that the maximum permissible fiber volume fraction to avoid matrix cracking was 6% for SiC _f /MoSi₂ and 23% for SiC _f /SiAlON(40 vol.%)-MoSi₂.     

Reaction mechanism and microstructure development of strain tolerant in situ SiC–BN composites

The reaction mechanism and microstructure development of strain tolerant in situ SiC–BN composites fabricated from the in situ reaction of Si₃N₄, B₄C and C were investigated. This exothermic reaction took place at about 1400°C in an argon atmosphere according to the results of X-ray diffraction analysis and differential thermal analysis. The reaction finished after hot pressing at 1700°C for 60 min, and densification occurred mainly in the temperature range of 1700°C to 2000°C. In spite of poor sinterability of BN, composites with rather high density were obtained. Chemical composition analysis of the composites obtained showed that there was no obvious change in the composition after hot pressing. The in situ formed SiC was of the β-type with a quasi-spherical shape, whereas the in situ BN was graphitic hexagonal with a flake shape, and was located at the grain boundaries of SiC. The composite obtained showed a very fine and homogeneous microstructure. The bending strength of the composite was high, while the elastic modulus decreased substantially.     

Microstructures and Properties of the C/Zr-O-Si-C Composites Fabricated by Polymer Infiltration and Pyrolysis

A way to improve the ablation properties of the C/SiC composites in an oxyacetylene torch environment was investigated by the precursor infiltration and pyrolysis route using three organic precursors (zirconium butoxide, polycarbosilane, and divinylbenzene). The ceramic matrix derived from the precursors at 1200 °C was mainly a mixture of SiC, ZrO₂, and C. After annealing at 1600 °C for 1 h, ZrO₂ partly transformed to ZrC because of the carbothermic reductions and completely transformed to ZrC at 1800 °C in 1 h. The mechanical properties of the composites decreased with increasing temperature, while the ablation resistance increased due to the increasing content of ZrC. Compared with C/SiC composites, the ablation resistance of the C/Zr-O-Si-C composites overwhelms because of the oxide films which formed on the ablation surfaces. And, the films were composed of two layers: the porous surface layer (the mixture of ZrO₂ and SiO₂) and the dense underlayer (SiO₂).     

Oxidation behavior of C/C composites with SiC/ZrSiO4–SiO2 coating

A SiC/ZrSiO₄–SiO₂ (SZS) coating was successfully fabricated on the carbon/carbon (C/C) composites by pack cementation, slurry painting and sintering to improve the anti-oxidation property and thermal shock resistance. The anti-oxidation properties under different oxygen partial pressures (OPP) and thermal shock resistance of the SZS coating were investigated. The results show that the SZS coated sample under low OPP, corresponding to the ambient air, during isothermal oxidation was 0.54% in mass gain after 111 h oxidation at 1500 °C and less than 0.03% in mass loss after 50 h oxidation in high OPP, corresponding to the air flow rate of 36 L/h. Additionally, the residual compressive strengths (RCS) of the SZS coated samples after oxidation for 50 h in high OPP and 80 h in low OPP remain about 70% and 72.5% of those of original C/C samples, respectively. Moreover, the mass loss of SZS coated samples subjected to the thermal cycle from 1500 °C in high OPP to boiling water for 30 times was merely 1.61%.     

Oxidation of ZC63 Mg alloys reinforced with SiC particles between 390 °C and 500 °C in air

The ZC63 magnesium alloys reinforced with 10 wt.% of SiC particles with an average particle size of 50 μm were cast. The fabricated SiC_p/ZC63 composite consisted of an α-Mg matrix, unreacted α-SiC particles, and an intergranularly formed CuMgZn compound. It was oxidized at 390 °C to 500 °C up to 5 h in air. The oxide scales were thin and compact below 430 °C, but became porous and loose above 450 °C. They consisted primarily of MgO and a small amount of Mg₃N₂. SiC particles were stable over the temperature range explored.     

Cfiber/SiCfiller/Si–B–C–Nmatrix composites with extremely high thermal stability

Precursor-derived Si–B–C–N ceramics are well known for their outstanding thermal stability up to 2000 °C. However, if they are integrated with long ceramic fiber fabrics, the thermal stability of the respective fiber–matrix composites decreases, and the associated thermomechanical properties worsen. A method of improving the thermal stability of a fiber-reinforced Si–B–C–N-based composite up to 1700 °C by the application of SiC filler particulates is reported. The mass loss of such composites is very low even after heating to 2100 °C. Remarkably, a pre-heat treatment of the SiC filler is essential in order to achieve the thermal stability of the ceramic matrix composites by removing surface SiO₂. The composite described here retained 96% of its room-temperature strength and possessed non-brittle fracture behavior after heating at 1700 °C for 10 h in Ar. The flexural creep deformation of the composite at 1400 °C was only 0.25% after 60 h under 100 MPa pressure.     

Oxidation of AM60B Mg Alloys Containing Dispersed SiC Particles in Air at Temperatures Between 400 and 550 °C

AM60B magnesium alloys, with and without dispersed SiC particles, were oxidized between 400 and 550 °C in air. The scales generated consisted primarily of MgO and a small amount of Mg₃N₂ formed by the outward diffusion of cations (Mg, Al, Mn) and the inward diffusion of anions (N, O). The SiC particles were stable in the AM60B alloy during oxidation and increased its oxidation resistance to a certain extent. However, given the predominance of the non-protective MgO as the main oxide, the SiC_p/AM60B composites were inevitably destroyed as oxidation progressed.     

Oxidation behavior and phase transition of ZrB2–SiCw–ZrO2f ceramic

The oxidation behavior and phase transition of ZrB₂–SiC_w–ZrO_2f ceramic had been investigated by in situ high-temperature XRD, XPS, SEM, EDS and TEM measurements. The initial oxidation temperature of most ZrB₂ was 1000 °C and no significant oxidation of SiC was found up to 1200 °C. The oxidation products formed at lower temperatures would penetrate into the pores and flaws on the surface, which was beneficial to crack healing. In order to improve the oxidation resistance of this system, it should be focused on decreasing the oxygen diffusivity and the volume expansion caused by phase transition.     

连续氮化硅纤维的氧化行为与高温影响研究

连续氮化硅陶瓷纤维是透波／承载一体化陶瓷基复合材料的关键原材料,也是制约复合材料耐高温性能与力学性能的关键因素。本文系统研究了国防科技大学研制的连续氮化硅纤维的抗氧化性能,分析了高温处理后纤维的组成结构与力学性能变化规律。结果表明：1000°C氧化1h后纤维强度高于原始纤维强度,主要是形成的玻璃相能减少和弥补纤维的表面缺陷。随着空气中处理温度提高,氧含量增加,纤维表面形成的SiO₂层逐渐变厚,纤维强度明显降低。纤维在1200°C氧化1h后强度保留率为63%,表明在此温度以下纤维有较好的服役性能。另一方面,氮化硅纤维在1450°C N₂中处理1h的强度保留率为57%,表现出良好的耐高温性能。纤维表面氧化对其在N₂下的耐高温性能具有不利影响,1000°C氧化的纤维在1450°C处理后丧失强度,1500℃处理后形成氮化硅结晶,失重明显增长,纤维内部也开始产生缺陷。     

Microstructural,thermal and mechanical characterization of TiB2–SiC composites doped with short carbon fibers

Spark plasma sintering method, at the temperature of 1800 °C under the pressure of 40 MPa for 7 min, was employed for fabrication of TiB₂–SiC-based composites. The influences of short carbon fiber (C_f) addition (2 wt%) on microstructural, mechanical and thermal properties of TiB₂–SiC ceramics were studied. Carbon fiber addition increased the relative density of sintered composite which observed to have direct effect on mechanical and thermal properties. The mechanical properties of composites were measured by nanoindentation method. Hardness and elastic modulus of TiB₂/SiC interfaces in carbon fiber doped composite were measured 27.1 GPa and 445 GPa, respectively, while these values were obtained 24.2 GPa and 422 GPa for carbon-free sample. The thermal diffusivity of samples was measured by laser flash technique (LFT). It was found that TiB₂–SiC–C_f composite has a higher thermal conductivity (55 w/m.K) compared to TiB₂–SiC ceramic with a value of 54.8 w/m.K.     

Characterization of hot-pressed Ti3SiC2–SiC composites

The high-density Ti₃SiC₂-SiC composites with different SiC volume contents were fabricated by hot pressing technique under 35 MPa in a vacuum atmosphere at 1550 °C for 30 min. Microstructural observation showed that the distribution of SiC particulates in the Ti₃SiC₂ matrix was uniform which improved the hardness of Ti₃SiC₂–20 vol% SiC sample (13.9 GPa), compared to monolithic Ti₃SiC₂ (7.1 GPa). The sample containing 15 vol% SiC showed the highest flexural strength value, compared to the other Ti₃SiC₂-SiC samples and the monolithic Ti₃SiC₂. The fracture toughness of the Ti₃SiC₂-SiC samples was also lower than that of the monolithic Ti₃SiC₂ MAX phase.     

Interfacial reaction studies of B4C-coated and C-coated SiC fiber reinforced Ti–43Al–9V composites

The interfacial reactions of B₄C-coated and C-coated SiC fiber reinforced Ti–43Al–9V composites were investigated by scanning electron microscope and transmission electron microscope. The detailed microstructures as well as the chemical composition throughout the reaction zone were identified. For SiC_f/B₄C/TiAl composite, the reaction zone from B₄C coating to TiAl matrix is composed of 4 layers, namely, a carbon-rich layer, a mixed layer of TiB₂ + amorphous carbon, a TiC layer and a mixed layer of TiB + Ti₂AlC. For SiC_f/C/TiAl composite, the reaction zone from C coating to TiAl matrix is composed of 3 layers, namely, a fine-grained TiC layer, a coarse-grained TiC layer and a thick Ti₂AlC layer. For both kinds of composites, the reaction mechanisms of the interfacial reactions were analyzed, and the corresponding reaction kinetics were calculated. The activation energies of interfacial reaction in SiC_f/B₄C/TiAl composite and SiC_f/B₄C/TiAl composite are 308.1 kJ/mol and 230.7 kJ/mol, respectively.     

Near-net shaped Al/SiCP composites via vacuum-pressure infiltration combined with gelcasting

To solve the problem of difficult machining, the near-net shaped Al/SiC_P composites with high volume fraction of SiC particles were fabricated by vacuum-pressure infiltration. The SiC_P preform with a complex shape was prepared by gelcasting. Pure Al, Al4Mg, and Al4Mg2Si were used as the matrices, respectively. The results indicate that the optimal parameters of SiC_P suspension in gelcasting process are pH value of 10, TMAH content of 0.5 wt.%, and solid loading of 52 vol.%. The Al matrix alloyed with Mg contributes to improving the interfacial wettability of the matrix and SiC particles, which increases the relative density of the composite. The Al matrix alloyed with Si is beneficial to inhibiting the formation of the detrimental Al₄C₃ phases. The Al4Mg2Si/SiC_P composite exhibits high relative density of 99.2%, good thermal conductivity of 150 W·m⁻¹·K⁻¹, low coefficient of thermal expansion of 10.1×10⁻⁶ K⁻¹, and excellent bending strength of 489 MPa.     

Joining of Cf/SiC Composite and TC4 Using Ag-Al-Ti Active Brazing Alloy

Carbon fiber reinforced SiC (C_f/SiC) composite was successfully joined to TC4 with Ag-Al-Ti alloy powder by brazing. Microstructures of the brazed joints were investigated by scanning electron microscope, energy dispersive spectrometer, and x-ray diffraction. The mechanical properties of the brazed joints were measured by mechanical testing machine. The results showed that the brazed joint mainly consists of TiC, Ti₃SiC₂, Ti₅Si₃, Ag, TiAl, and Ti₃Al reaction products. TiC + Ti₃SiC₂/Ti₅Si₃ + TiAl reaction layers are formed near C_f/SiC composite while TiAl/Ti₃Al/Ti + Ti₃Al reaction layers are formed near TC4. The thickness of reaction layers of the brazed joint increases with the increased brazing temperature or holding time. The maximum room temperature and 500 °C shear strengths of the joints brazed at brazing temperature 930 °C for holding time 20 min are 84 and 40 MPa, respectively.