Mechanical properties and microstructural evolution of Cansas-III SiC fibers after thermal exposure in different atmospheres

Cansas-III SiC fibers were exposed in argon, air and wet oxygen (12%H₂O+8%O₂+80%Ar) atmospheres for 1 h at 1000–1500 °C. The pristine fiber consisted of β-SiC, free carbon and SiC_xO_y phases. After exposure in air and wet oxygen, an amorphous SiO₂ layer with embedding α-cristobalite crystals formed, while stacking faults were generated in the SiC core to release the residual stress. With the increasing oxidation temperature, lots of pores formed in the oxide layer, accompanied with the thickening, cracking and spallation of oxide layer. The average tensile strength decreased with the exposure temperature increasing and the exposure atmosphere deteriorating (argon→air→wet oxygen). After exposure at 1400 °C in argon and air, the fiber strength retention rates were 84% and 70%, respectively. However, after exposure at 1300 °C in wet oxygen, the strength retention rate was only 51%, indicating the accelerating oxidation and severe strength degradation of fibers.     

Investigations on the thermal behaviours of SiC-ZrC continuous ceramic fibres

In this study, nanoscale composite SiC-ZrC ceramic fibres, derived from polyzirconocenecarbosilane (PZCS) via melt spinning, electron beam crosslinking, pyrolysis and sintering were investigated in detail. Compared with several commercial products of second-generation SiC fibres, the produced composite fibres exhibit improved thermal stability, mechanical properties and oxidation resistance. SiC grains in the fibre grew from 9.8 nm to 33.9 nm after annealing in an inert atmosphere at 1800 °C for 1 h, as well as decomposition of the SiC_xO_y phase and the growth of SiC grains affected the mechanical properties of the fibres, and the mechanical properties of the fibres were maintained at 1.1 GPa, accompanied by an increase in the modulus. After the fibres were oxidized at 1100～1400 °C for 1 h, a dense oxide layer of SiO₂-ZrO₂ was formed on the surface of the fibres, which slowed down the rate of further fibre oxidation, thus, the fibres exhibited excellent oxidation resistance.     

High temperature properties of the monolithic CVD β-SiC materials joined with a pre-sintered MAX phase Ti3SiC2 interlayer via solid-state diffusion bonding

Monolithic high purity CVD β-SiC materials were successfully joined with a pre-sintered Ti₃SiC₂ foil via solid-state diffusion bonding. The initial bending strength of the joints (∼ 220 MPa) did not deteriorate at 1000 °C in vacuum, and the joints retained ∼ 68 % of their initial strength at 1200 °C. Damage accumulation in the interlayer and some plastic deformation of the large Ti₃SiC₂ grains were found after testing. The activation energy of the creep deformation in the temperature range of 1000 – 1200 °C in vacuum was ∼ 521 kJmol⁻¹. During the creep, the linkage of a significant number of microcracks to form a major crack was observed in the interlayer. The Ti₃SiC₂ interlayer did not decompose up to 1300 °C in vacuum. A mild and well-localized decomposition of Ti₃SiC₂ to TiC_x was found on the top surface of the interlayer after the bending test at 1400 °C in vacuum, while the inner part remained intact.     

Oxidation resistance of multi-walled carbon nanotubes coated with polycarbosilane-derived SiCxOy ceramic

Multi-walled carbon nanotubes (MWCNTs) have been successfully coated with a thin SiC_xO_y coating when polycarbosilane (PCS) was used as precursor and pyrolyzed in a coke bed. Meanwhile, effect of PCS concentration on oxidation resistance of the coated MWCNTs is studied. The results showed that the pyrolysis products of PCS were composed of amorphous SiC_xO_y as the main phase, together with β-SiC and SiO₂ as the minor phases whose amount increased a little with the increase of temperature from 1000 °C to 1500 °C. The thickness of SiC_xO_y coating on the surface of MWCNTs increased a little from 1 wt.% to 5 wt.%, but decreased dramatically with PCS concentration in the range of 10-30 wt.%. The oxidation resistance of the coated MWCNTs was greatly improved in comparison with as-received ones. The oxidation peak temperature of the coated MWCNTs reached 783.7 °C, much higher than 652.2 °C for as-received ones.     

Novel process for recrystallized silicon carbide through β-α phase transformation

A novel process was investigated to produce recrystallized silicon carbide through β-α phase transformation. The specimen was prepared from carbon and β-SiC powder mixture, first by infiltration with liquid silicon at 1500 °C to form β-SiC preform with a high density, and then by heating it further up to 2200 °C. When the β-SiC particles were transformed into α-SiC at 2200 °C, the rapid grain growth occurred of the α-SiC by consuming β-SiC particles, resulting in an interconnected network structure with huge and elongated α-SiC grains. The specimen recrystallized at 2200 °C had a measured density of 2.7 g/cm³ and strength of 134 MPa. The infiltration behavior, microstructure evolution and mechanical properties of the recrystallized silicon carbide were examined and discussed.     

Temperature-induced fibre/matrix interactions in porous alumino silicate ceramic matrix composites

The thermal stability of alumino-silicate fibre (Nextel 720)/porous mullite matrix composites was investigated in the temperature range between 1300 and 1600°C. In the as-prepared state the fibres consist of mullite plus α-Al₂O₃, while the porous mullite matrix includes minor amounts of a SiO₂-rich glass phase. Temperature-controlled reactions between the silica-rich glass phase of the matrix and α-Al₂O₃ at the rims of the fibres to form mullite have been observed. At the end of this process, virtually all glass phase of the matrix is consumed. Simultaneously, alumina-free layers about 1 μm thick are formed at the periphery of the fibres. The mullite forming process is initiated above about 1500°C under short time heat-treatment conditions (2 h) and at much lower temperature (1300°C) under long-term annealing (1000 h). Subsequent to annealing below the thermal threshold, the composite is damage tolerant and only minor strength degradation occurs. Higher annealing temperatures, however, drastically reduce damage tolerance of the composites, caused by reaction-induced gradually increasing fibre/matrix bonding. According to this study, the thermal stability of alumino silicate (Nextel 720) fibre/mullite matrix composites ranges between 1500°C in short-term and 1300°C in long-term heat-treatment conditions.     

Microstructure and strengthening behavior in high content SiC nanowires reinforced SiC composites

In this study, the high-content SiC_nw reinforced SiC ceramic matrix composites (SiC_nw/SiC CMC) were successfully fabricated by hot pressing β-SiC and sintering additive (Al₂O₃-Y₂O₃) with boron nitride interphase modification SiC_nw. The effects of sintering additive content and mass fraction (5–25 wt%) of SiC_nw on the density, microstructure, and mechanical properties of the composites were investigated. The results showed that with the increase of sintering additives from 10 wt% to 12 wt%, the relative density of the SiC_nw/SiC CMC increased from 97.3% to 98.9%, attributed to the generated Y₃Al₅O₁₂ (YAG) liquid phase from the Al₂O₃-Y₂O₃ that promotes the rearrangement and migration of SiC grains. The comprehensive performance of the obtained composite with 15 wt% SiC_nw possessed the optimal flexural strength and fracture toughness of 524 ± 30.24 MPa and 12.39 ± 0.49 MPa·m^1/2, respectively. Besides, the fracture mode of the composites with 25 wt% SiC_nw content revealed a pseudo-plastic fracture behavior. It concludes that the 25 wt% SiC_nw/SiC CMC was toughened by the fiber pull-outs, debonding, bridging, and crack deflection that can consume plenty of fracture energy. The strategy of SiC nanowires worked as a main bearing phase for the fabrication of SiC/SiC CMC providing critical information for understanding the mechanical behavior of high toughness and high strength SiC nanoceramic matrix composites.     

Silicon oxycarbide-based composites produced from pyrolysis of polysiloxanes with active Ti filler

Phenyl (PPS) and methyl (PMS) containing polysiloxanes were pyrolyzed at elevated temperatures (900–1500 °C) under argon atmosphere to investigate the phase developments within the polymers. It was found that pyrolysis of the polymers under inert atmosphere up to 1300 °C leads to amorphous silicon oxycarbide (SiO_xC_y) ceramics. Conversions at higher temperatures results in the transformations into the crystalline β-SiC phases. Ceramic matrix composites (CMCs) were developed based on the active filler controlled pyrolysis (AFCOP) of polysiloxanes with active Ti filler additions. CMC monoliths were prepared with 60–80 wt.% of active Ti particulates blended into polymer precursors. Green bodies of the composites were made by warm pressing under 15 MPa pressure and ceramics were obtained by pyrolysis at elevated temperatures between 900 and 1500 °C under argon atmosphere. The results showed that due to the incorporation of active Ti fillers, formation of crystalline phases such as TiC, TiSi, and TiO occured within the amorphous matrix due to the reactions between the Ti and the polymer decomposition products. The microstructural and mechanical characterization results of the composites are presented within the paper.     

Effects of oxygen on the thermal stability of silicon nitride fibers

Two types of Si₃N₄ fibers with different oxygen contents were annealed in a nitrogen atmosphere at 1500 °C for 1 h. After annealing, the fiber (SN-L) containing 0.5 wt% oxygen crystallized to α-Si₃N₄ but lost its strength, whereas the fiber (SN-H) containing 4.2 wt% oxygen was amorphous and retained 63.6% of its strength. The phase transition in these fibers was mainly influenced by the oxygen level. The lower oxygen content in the SN-L favored the precipitation of an almost stoichiometric composition of α-Si₃N₄ initially at ~1450 °C with an activation energy (Ea) of 663.357 kJ/mol. Nanopores existing naturally in the fiber promoted crystallization via heterogeneous nucleation. SN-H precipitated as an amorphous SiN_xO_y metaphase preferentially at ~1400 °C with an Ea of 440.434 kJ/mol, owing to the higher oxygen content approaching that of Si₂N₂O. SiN_xO_y inhibited the crystallization of α-Si₃N₄, making SN-H more thermally stable than SN-L at temperatures above 1500 °C.     

Microstructure and mechanical properties of hot-pressed SiC nanofiber reinforced SiC composites

This study reports on the preparation and mechanical properties of a novel SiC_nf/SiC composite. The single crystal SiC nanofiber(SiC_nf) reinforced SiC ceramic matrix composites (CMC) were successfully fabricated by hot pressing the mixture of β-SiC powders, SiC_nf and Al–B–C powder. The effects of SiC_nf mass fraction as well as the hot-pressing temperature on the microstructure and mechanical properties of SiC_nf/SiC CMC were systematically investigated. The results demonstrated that the 15 wt% SiC_nf/SiC CMC obtained by hot pressing (HP) at 1850 °C with 30 MPa for 60 min possessed the maximum flexural strength and fracture toughness of 678.2 MPa and 8.33 MPa m^1/2, respectively. The nanofibers pull out, nanofibers bridging and cracks deflection were found by scanning electron microscopy, which are believed can strengthen and toughen the SiC_nf/SiC CMC via consuming plenty of the fracture energy. Besides, although the relative density of the prepared SiC_nf/SiC CMC further increased with the sintering temperature rose to 1900 °C, the further coarsend composites grains results in the deterioration of the mechanical properties for the obtained composites compared to 1850 °C.     

Facile synthesis of SiOx spheres or dumbbell-shaped β-SiC whiskers on expanded graphite by silicon vapor deposition

A facile method was developed to synthesize SiO_x spheres or dumbbell-shaped β-SiC whiskers on expanded graphite (SiO_x/EG or β-SiC/EG) by silicon vapor deposition without catalyst. With the carbon black atmosphere, the above hybrids were synthesized above 1100 °C in a graphite crucible where silicon powder was placed under the expanded graphite (EG). The growth of SiO_x spheres is controlled by vapor-solid mechanism at 1100 °C and 1200 °C. Namely, the active carbon atoms absorbed SiO (g) and Si (g) to form SiC nuclei. Then, the SiO₂, residual SiO (g) and Si (g) deposited on SiC nuclei to form SiO_x spheres. At 1300 °C and 1400 °C, the same SiO_x spheres formed on EG as well as many dumbbell-shaped β-SiC whiskers. The growth of dumbbell-shaped β-SiC whiskers is controlled by vapor-vapor and vapor-solid mechanism successively. In a word, firstly, the β-SiC whiskers with defects formed via the reaction between Si (g) and CO (g). After that, the SiO₂, residual SiO (g) and residual Si (g) preferentially deposited on defects, then deposited on other parts of β-SiC whiskers to form dumbbell-shaped SiC whiskers.     

Mechanical Properties and Microstructural Characterization of Amorphous SiCxNy Thin Films After Annealing Beyond 1100°C

The effect of thermal annealing on structure and mechanical properties of amorphous SiC_xN_y (y ≥ 0) thin films was investigated up to 1500°C in air and Ar. The SiC_xN_y films (2.2–3.4 μm) were deposited by reactive DC magnetron sputtering on Si, Al₂O₃ and α‐SiC substrates without intentional heating and at 600°C. The SiC target with small excess of carbon was sputtered at various N₂/Ar gas flow ratios (0–0.48). The nitrogen content in the films changes in the range 0–43 at.%. Hardness and elastic modulus (nanoindentation), change in film thickness, film composition, and structure (Raman spectroscopy, XRD) were investigated in dependence on annealing temperature and nitrogen content. All SiC_xN_y films preserve their amorphous structure up to 1500°C. The hardness of all as‐deposited and both air‐ and Ar‐annealed SiC_xN_y films decreases with growth of nitrogen content. The annealing in Ar at temperatures of 1100°C–1300°C results in noticeable hardness growth despite the ordering of graphite‐like structure in carbon clusters in nitrogen free films. Unlike the SiC, this graphitization leads to hardness saturation of SiCN films starting above 900°C, especially for films with higher nitrogen content (deposited at higher N₂/Ar). This indicates the practical hardness limit achievable by thermal treatment for SiC_xN_y films deposited on unheated substrates. The ordering in carbon phase is facilitated by the presence of nitrogen in the films and its extent is controlled by the N/C atomic ratio. The suppression of graphitization was observed for N/C ranging between 0.5–0.7. Films deposited at 600°C show higher hardness and oxidation resistance after annealing in comparison with those deposited on unheated substrates. Hardness reaches 40 GPa for SiC and ~28 GPa for SiC_xN_y (35 at.% of nitrogen). Such a high hardness of SiC film stems from its partial crystallization. Annealing of SiC_xN_y film (35 at.% of N) in Ar at 1400°C is accompanied by formation of numerous hillocks (indicating heterogeneous structure of amorphous films) and redistribution of film material.     

Microstructure and mechanical strength of transient liquid phase bonded Ti3SiC2 joints using Al interlayer

Based on the structure characteristic of Ti₃SiC₂ and the easy formation of Ti₃Si_1−xAl_xC₂ solid solution, a transient liquid phase (TLP) bonding method was used for bonding layered ternary Ti₃SiC₂ ceramic via Al interlayer. Joining was performed at 1100–1500 °C for 120 min under a 5 MPa load in Ar atmosphere. SEM and XRD analyses revealed that Ti₃Si(Al)C₂ solid solution rather than intermetallic compounds formed at the interface. The mechanism of bonding is attributed to aluminum diffusing into the Ti₃SiC₂. The strength of joints was evaluated by three point bending test. The maximum flexural strength reaches a value of 263 ± 16 MPa, which is about 65% of that of Ti₃SiC₂; for the sample prepared under the joining condition of 1500 °C for 120 min under 5 MPa. This flexural strength of the joint is sustained up to 1000 °C.     

Formation of porous SiC ceramics via recrystallization

In this study, porous SiC ceramics with interconnected huge plate-like grains were fabricated from oxidized β-SiC powder with 1 wt% B₄C. When the β–α SiC phase transformation occurred at 2100 °C, rapid grain growth of α-SiC consumed the unstable β-SiC matrix resulting in an interconnected network structure with huge plate-like grains. The oxidation of β-SiC powder and the addition of B₄C are necessary conditions for rapid grain growth. The observed results are discussed based on thermodynamic considerations. The measured porosity of the specimens sintered at 2100 °C for 30 min was 47% and the mean pore size was 6–7 μm. The strength of the sintered specimen was 45 ± 5 MPa.     

Effect of interface types on the heat-resistance of Cansas-II SiCf /SiC composites

The heat-resistance of the Cansas-II SiC/CVI-SiC mini-composites with a PyC and BN interface was studied in detail. The interfacial shear strength of the SiC/PyC/SiC mini-composites decreased from 15 MPa to 3 MPa after the heat treatment at 1500 °C for 50 h, while that of the SiC/BN/SiC mini-composites decreased from 248 MPa to 1 MPa, which could be mainly attributed to the improvement of the crystallization degree of the interface and the decomposition of the matrix. Aside from the above reasons, the larger declined fraction of the interfacial shear strength of the SiC/BN/SiC mini-composites might also be related to the gaps in the BN interface induced by the volatilization of B₂O₃·SiO₂ phase, leading to a significant larger declined fraction of the tensile strength of the SiC/BN/SiC mini-composites due to the obvious expansion of the critical flaws on the fiber surface. Therefore, compared with the CVI BN interface, the CVI PyC interface has better heat-resistance at high temperatures up to 1500 °C due to the fewer impurities in PyC.     

Influence of Y2O3 addition on the mechanical and oxidation behaviour of carbon fibre reinforced ZrB2/SiC composites

The influence of Y₂O₃ addition on the microstructure, thermo-mechanical properties and oxidation resistance of carbon fibre reinforced ZrB₂/SiC composites was investigated. Y₂O₃ reacted with oxide impurities present on the surface of ZrB₂ and SiC grains and formed a liquid phase, effectively lowering the sintering temperature and allowing to reach full density at 1900 °C. The presence of a carbon source (fibres) led to additional reactions which resulted in the formation of new secondary phases such as yttrium boro-carbides. Mechanical properties were significantly enhanced compared to the un-doped composite. Further tests at high temperatures resulted in strength increase up to 700 MPa at 1500 °C which was attributed to stress relaxation. Oxidation tests carried out at 1500 °C and 1650 °C in air showed that the presence of the Y-based secondary phases enhanced the growth of ZrO₂ grains, but offered limited protection to oxygen due to the lower availability of surficial SiO₂ formed from SiC.     

Preparation of SiCf/Si–O–C composites by impregnation pyrolysis of polysiloxane and its electromagnetic wave absorption properties

High-temperature structural electromagnetic wave (EMW) absorption materials are increasing in demand because they can simultaneously possess the functions of mechanical load-bearing, heatproof, and EMW absorption. Herein, SiC_f/Si–O–C composites were prepared by precursor impregnation pyrolysis using continuous SiC fibers needled felt as reinforcement and polysiloxane as a precursor, respectively. The phase composition, microstructure, complex permittivity, and EMW absorption properties of SiC_f/Si–O–C composites after annealing at various temperatures were investigated. The annealing at 1400–1500°C affects positively the EMW absorption performance of the composites, because the β-SiC microcrystals and SiC nanowires were generated by the activation of carbothermal reduction reaction in the composites, and the aspect ratio of SiC nanowires increased with the rise of temperature. The composites exhibit optimal EMW absorption performance, with the effective absorption bandwidth covering the entire X-band and the minimum reflection loss (RL_min) of −32.8 dB at 4.0 mm when the annealing temperature is raised to 1500°C. This is because that the impedance matching is improved as the rising of ε′ and decreasing of ε″ due to the conversion of free carbon in the composite into SiC nanowires.     

Effects of oxidation cross-linking and sintering additives (TiN,B) on the formation and heat-resistant performance of polymer-derived SiC(Ti,B) films

Effects of oxidation cross-linking and sintering additives (TiN, B) on the microstructure formation and heat-resistant performance of freestanding SiC(Ti, B) films synthesized from Ti, B-containing polycarbosilane (TiB-PCS) precursor were investigated. TiB-PCS green films were first cross-linked for 1 h, 2 h, 3 h and 4 h, respectively, and then pre-sintered at 950 °C. Finally, they were sintered at 1800 °C to complete the conversion from organic films to inorganic SiC(Ti, B) films. The results reveal that curing time has a great impact on the uniformity and density of SiC(Ti, B) films. TiB-PCS films cured for 3 h yield the best quality SiC(Ti, B) films, which are composed of β-SiC crystals, C clusters, α-SiC nano-crystals, a small amount of TiB₂ and B₄C. TiB₂ and B₄C are both steady phases which can inhibit abnormal growth of β-SiC, effectively reduce sintering temperature and help consume excess C from decomposition of amorphous SiOxCy. After high temperature annealing at 1500 °C, 1600 °C and 1700 °C in argon, SiC(Ti, B) films still keep excellent mechanical properties, which makes them attractive candidate materials for microelectromechanical systems (MEMS) used at ultra-high temperatures (exceeding 1500 °C).     

Single crystalline mullite fibres obtained by the internal crystallisation method: Microstructure and creep resistance

Single crystalline mullite fibres, which are expected to be an excellent reinforcement for high temperature composite materials, can be produced by using the internal crystallisation method. The present paper sheds light to mechanisms of crystallisation of mullite fibres under conditions of the internal crystallisation method, which is actually crystallisation of a melt in the continuous channels of a molybdenum carcass. Mullite occurs to appear close to 2:1 composition independent of the composition of the melt. Inclusions of a silica-based glassy phase are also present on the periphery of a fibre. The glassy phase yields a decrease in the creep resistance of mullite fibres at temperatures above 1500 °C. Still, the fibres obtained from the raw material with the Al₂O₃/SiO₂ molar ratio of 2.05 have excellent creep resistance at a temperature of 1400 °C and fairly high creep resistance at 1500 °C.     

Phase Evolution of Ti3SiC2 Annealing in Vacuum at Elevated Temperatures

The thermal decomposition of Ti₃SiC₂ in vacuum furnace up to 1500°C has been investigated. The results show that the mild decomposition of Ti₃SiC₂ commences at 1300°C and the higher the holding temperature, the larger the volatilization of Si atoms. The Ti₃SiC₂ decomposition occurs simultaneously on the surface and in the bulk. Four phases coexist at 1400°C and 1450°C and the Ti₅Si₃C_x phase appears in the bulk and/or surface. Diffusion distance, rate, and volatilization of Si contribute to the porous structure and the presence of Ti₅Si₃C_x. The evolution of furnace pressure reflects the decomposition kinetics of Ti₃SiC₂.