Fatigue behavior and oxidation resistance of carbon/ceramic composites reinforced with continuous carbon fibers

The aim of this work was to compare fatigue behavior and oxidation resistance of pitch-derived CC (carbon) composite with CC/ceramic (carbon/ceramic) composites obtained by impregnation of CC composite with polysiloxane-based preceram and their subsequent heat treatment. Two types of CC/ceramic composites were studied; CC/SiCO composite obtained at 1000 °C, and CC/SiC composite obtained at 1700 °C. Both types of composites show much better fatigue mechanical performance in comparison to pure CC composite. CC/SiCO composite had 3 times better fatigue properties, and CC/SiC composite 4.5 times better fatigue properties than the reference CC composite. After a fatigue test composites partially retain their mechanical properties, and normalized residual modulus in the direction perpendicular to laminates exceeds 50% for CC and CC/SiCO composites. In the other directions normalized residual modulus is higher than 80% for all composites. Oxidative tests led at 600 °C in air atmosphere indicated oxidation resistance of CC/SiC composites.     

Synthesis,structure, and properties of silicon oxycarbide aerogels derived from tetraethylortosilicate /polydimethylsiloxane

Porous silicon oxycarbide (SiCO) aerogel monoliths were prepared by the sol-gel method using Tetraethylortosilicate/Polydimethylsiloxane as organic-inorganic precursors. The precursor gels were dried by supercritical ethanol fluid and pyrolyzed at 1200 °C in nitrogen atmosphere to form SiCO aerogels. The as-prepared SiCO aerogels are amorphous and present a network microstructure, surface area of 198.04 m²/g, average pore diameter of 56 nm, and pore volume of 0.648 cm³/g. The thermal conductivity of aerogel monoliths is only 0.027 W/m·K at 25 °C (Hot disk method). The atom ratios of Si, C, O elements in the SiCO aerogels are 30.77%, 14.67%, 54.56% respectively. The network microstructure of the SiCO aerogels are retained until 1100 °C, and the chemical groups and crystal phase structures are kept up until 1200 °C. There is only 1.65% of weight-loss until the same heated at 1200 °C in air, which is one of the highest thermally stable temperatures for SiCO aerogels ever reported.     

Joining of SiC ceramics via a novel liquid preceramic polymer (V-PMS)

A novel liquid preceramic polymer (V-PMS) was synthsized by modifying polymethylsilane (PMS) with 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane ([CH₃(CH₂CH)SiO]₄, D4Vi), for joining SiC ceramics under ambient pressure. The obtained V-PMS with a viscosity of 125 Pas at room temperature exhibits excellent thermal properties and bonding strength. The ceramic yield of V-PMS treated at 1200 °C under Ar atmosphere is 84.5%, which is 38.3% higher than the original PMS. The shear strengths of the SiC joints joined by V-PMS at 800 °C, 1000 °C and 1200 °C under N₂ atmosphere are 11.9 MPa, 34.5 MPa and 29.9 MPa, respectively. The excellent performances make the obtained V-PMS promising candidates for joining SiC ceramics in high-temperature applications.     

Preparation of reaction-bonded silicon carbide with well controlled structure by tape casting method

Tape casting is a reliable and cost effective method for producing thin ceramic sheets with uniform and tailored microstructures, especially for multilayered composite materials. In this paper, SiC/C tapes were prepared by tape casting method. After lamination and binder removal, porous preforms with homogeneous microstructure and narrow pore sizes distribution were developed. Then, dense reaction bonded SiC ceramics (RBSCs) were obtained by silicon infiltration into these preforms. The highest bending strength of the RBSCs can reach 410 ± 14 MPa. Moreover, impregnation of phenolic resin into the porous preforms before silicon infiltration could help to develop RBSCs with lower residual silicon content and higher flexural strength which can be as high as 598 ± 112 MPa.     

Active filler controlled polymer pyrolysis – A promising route for the fabrication of advanced ceramics

A novel polyborosiloxane (BoSiVi) containing methyl and vinyl groups with Titanium Silicide (TiSi₂) filler was employed for the preparation of silicon and titanium containing ceramic phases. Ceramic phase evolution was studied from the above mentioned preceramic system at 900, 1200, 1500, 1800 and 2000 °C respectively under argon atmosphere. Reactive nature of TiSi₂ with pyrolytic by-products of BoSiVi led to the formation of different ceramic phases at different firing temperatures. XRD analysis confirmed the evolution of carbide (TiC, TiB, SiC etc.) and oxide (TiOC, SiO₂ etc.) ceramic phases in the temperature regime of 900 °C to 1500 °C. FESEM-EDX analysis of the ceramic phases, heat treated at 1500 °C, proved the formation of Si-Ti-O-C ceramic nano-fibers by Vapor-Liquid-Solid (VLS) method. BoSiVi+TiSi₂ system heat treated at 1800 °C and 2000 °C exhibited the evolution of pure non-oxide ceramic phases along with Ti₃SiC₂ MAX phase.     

Microstructure and high-temperature strength of silicon carbide with 2000 ppm yttria

A dense silicon carbide (SiC) ceramic with a very high flexural strength at 2000 °C (981 ± 128 MPa) was obtained by conventional hot-pressing with extremely low additive content (2000 ppm Y₂O₃). Observations using high-resolution transmission electron microscopy (HRTEM) showed that (1) homophase (SiC/SiC) boundaries were clean without an intergranular glassy phase and (2) junction pockets consisted of nanocrystalline Y-containing phase embedded in an amorphous Y-Si-O-C-N phase. The excellent strength at 2000 °C was attributed to the clean SiC/SiC boundary and the strengthening effect of plastic deformation.     

Thermal conversion of carbon fibres/polysiloxane composites to carbon fibres/ceramic composites

The aim of this work is to investigate the thermal conversion of carbon fibres/polysiloxane composites to carbon fibres/ceramic composites. The conversion mechanism of four different resins to the ceramic phase in the presence of carbon fibres is investigated. The experiments were conducted in three temperature ranges, corresponding to composite manufacturing stages, namely up to 160 °C, 1000 °C and finally 1700 °C.The study reveals that the thermal conversion mechanism of pure resins in the presence of carbon fibres is similar to that without fibres up to 1000 °C. Above 1000 °C thermal decomposition occurs in both solid (composite matrix) and gas phases, and the presence of carbon fibres in resin matrix produces higher mass losses and higher porosity of the resulting composite samples in comparison to ceramic residue obtained from pure resin samples. XRD analysis shows that at temperature of 1700 °C composite matrices contain nanosized silicon carbide. SEM and EDS analyses indicate that due to the secondary decomposition of gaseous compounds released during pyrolysis a silicon carbide protective layer is created on the fibre surface and fibre–matrix interface. Moreover, nanosized silicon carbide filaments crystallize in composite pores.Owing to the presence of the protective silicon carbide layer created from the gas phase on the fibre–matrix interface, highly porous C/SiC composites show significantly high oxidation resistance.     

High temperature strength of silicon carbide sintered with 1 wt.% aluminum nitride and lutetium oxide

A heat-resistant SiC ceramic was developed from submicron β-SiC powders using a small amount (1 wt.%) of AlN–Lu₂O₃ additives at a molar ratio of 60:40. Observation of the ceramic using high-resolution transmission electron microscopy (HRTEM) showed a lack of amorphous films in both homophase (SiC–SiC) boundaries and junction areas. The junction phase consisted of Lu–Si–O elements, and the homophase boundaries contained Lu, Al, O, and N atoms as segregates. The ceramic maintained its room temperature (RT) strength up to 1600 °C. The flexural strength of the ceramic was 630 MPa and 633 MPa at RT and 1600 °C, respectively.     

Mechanical behavior of zirconium diboride–silicon carbide ceramics at elevated temperature in air

The mechanical properties of zirconium diboride–silicon carbide (ZrB₂–SiC) ceramics were characterized from room temperature up to 1600 °C in air. ZrB₂ containing nominally 30 vol% SiC was hot pressed to full density at 1950 °C using B₄C as a sintering aid. After hot pressing, the composition was determined to be 68.5 vol% ZrB₂, 29.5 vol% SiC, and 2.0 vol% B₄C using image analysis. The average ZrB₂ grain size was 1.9 μm. The average SiC particles size was 1.2 μm, but the SiC particles formed larger clusters. The room temperature flexural strength was 680 MPa and strength increased to 750 MPa at 800 °C. Strength decreased to ～360 MPa at 1500 °C and 1600 °C. The elastic modulus at room temperature was 510 GPa. Modulus decreased nearly linearly with temperature to 210 GPa at 1500 °C, with a more rapid decrease to 110 GPa at 1600 °C. The fracture toughness was 3.6 MPa·m^½ at room temperature, increased to 4.8 MPa·m^½ at 800 °C, and then decreased linearly to 3.3 MPa·m^½ at 1600 °C. The strength was controlled by the SiC cluster size up to 1000 °C, and oxidation damage above 1200 °C.     

Synthesis and characterization of carbon-enriched silicon oxycarbides

Polyhydridomethylsiloxane (PHMS) is a very practical and versatile source for a broad range of silicon oxycarbide (SiOC) and other silicon containing ceramic materials. PHMS modifications and crosslinking is conveniently achieved by dehydrocoupling and hydrosilylation reactions. The molecularly level mixed carbon content of the derived SiOC can be incrementally increased by reacting PHMS with 0–40 mol% of divinylbenzene (DVB) using 5 ppm of Pt catalyst relative to PHMS. With ceramic yields exceeding 80 wt.% and a dense microstructure, the derived carbon-enriched SiOCs exhibit significantly higher chemical stability compared with other high-carbon content polymer derived ceramics. Phase separation and nanocrystallinity are inhibited to at least 1200 °C for all the evaluated samples and the materials are completely amorphous. Very fine nanocomposite microstructures are obtained at 1450 °C, consisting of 5–10 nm graphite regions and amorphous SiOC domains with no significant porosity. Synthesis and microstructure characterization of the new carbon-enriched SiOC are discussed in comparison to the sole PHMS pyrolyzed product.     

Effect of grain growth on the thermal conductivity of liquid-phase sintered silicon carbide ceramics

The effect of grain growth on the thermal conductivity of SiC ceramics sintered with 3 vol% equimolar Gd₂O₃-Y₂O₃ was investigated. During prolonged sintering at 2000 °C in an argon or nitrogen atmosphere, the β → α phase transformation, grain growth, and reduction in lattice oxygen content occurs in the ceramics. The effects of these parameters on the thermal conductivity of liquid-phase sintered SiC ceramics were investigated. The results suggest that (1) grain growth achieved by prolonged sintering at 2000 °C accompanies the decrease of lattice oxygen content and the occurrence of the β → α phase transformation; (2) the reduction of lattice oxygen content plays the most important role in enhancing the thermal conductivity; and (3) the thermal conductivity of the SiC ceramic was insensitive to the occurrence of the β → α phase transformation. The highest thermal conductivity obtained was 225 W(m K)⁻¹ after 12 h sintering at 2000 °C under an applied pressure of 40 MPa in argon.     

Process-tolerant pressureless-sintered silicon carbide ceramics with alumina-yttria-calcia-strontia

Process-tolerant SiC ceramics were prepared by pressureless sintering at 1850–1950 °C for 2 h in an argon atmosphere with a new quaternary additive (Al₂O₃-Y₂O₃-CaO-SrO). The SiC ceramics can be sintered to a > 94% theoretical density at 1800–1950 °C by pressureless sintering. Toughened microstructures consisting of relatively large platelet grains and small equiaxed grains were obtained when SiC ceramics were sintered at 1850–1950 °C. The presently fabricated SiC ceramics showed little variability of the microstructure and mechanical properties with sintering within the temperature range of 1850–1950 °C, demonstrating process-tolerant behavior. The thermal conductivity of the SiC ceramics increased with increasing sintering temperature from 1800 °C to 1900 °C due to decreases of the lattice oxygen content of the SiC grains and residual porosity. The flexural strength, fracture toughness, and thermal conductivity of the SiC ceramics sintered at 1850–1950 °C were in the ranges of 444–457 MPa, 4.9–5.0 MPa m^1/2, and 76–82 Wm^?1 K^?1, respectively.     

Polymer-derived mullite–SiC-based nanocomposites

Ceramic mullite–SiC nanocomposites were successfully produced at temperatures below 1500 °C by the polymer pyrolysis technique. An alumina-filled poly(methylsilsesquioxane) compound was prepared by mechanically mixing and cross-linking via a catalyst prior to pyrolysis. Heat treatment of warm pressed alumina/polymer bulk samples under the exclusion of oxygen (inert argon atmosphere) up to 1500 °C initiated crystallization of mullite even at pyrolysis temperatures as low as 1300 °C. The influence of the filler and of the pyrolysis temperature on the crystallization behavior of the materials has been investigated. Based on thermal analysis in combination with elemental analysis and X-ray powder diffraction studies four polymer mixtures differing in type and content of nano-alumina powders were examined. Nano-sized γ-Al₂O₃ powders functionalized at the surface by octylsilane groups proved to be more reactive towards the preceramic polymer leading to the formation of a larger weight fraction of mullite crystals at lower processing temperatures (1300 °C) as compared to native nano-γ-Al₂O₃ filler. Moreover, the functionalized nano-alumina particles offer an enhanced homogeneity of the distribution of alumina nano-particles in the starting polysiloxane system. In consequence, the received ceramic samples exhibited a nano-microstructure consisting of crystals of mullite with an average dimension in the range of 60–160 nm and silicon carbide crystals in the range of 1–8 nm.     

Fabrication and properties of ultra highly porous silicon carbide by the gelation–freezing method

Silicon carbide (SiC) with ultra high porosity and unidirectionally oriented micrometer-sized cylindrical pores was prepared using a novel gelation–freezing (GF) method. Gelatin, water and silicon carbide powder were mixed and cooled at 7 °C. The obtained gels were frozen from ?10 to ?70 °C, dried using a vacuum freeze drier, degreased at 600 °C and then sintered at 1800 °C for 2 h. The gels could be easily formed into various shapes, such as cylinders, large pipes and honeycombs using molds. Scanning electron microscopy (SEM) observations of the sintered bodies showed a microstructure composed of ordered micrometer-sized cylindrical cells with unidirectional orientation. The cell size ranging from 34 to 147 μm could be modulated by changing the freezing temperatures. The numbers of cells for the samples frozen at ?10 and ?70 °C were 47 and 900 cells/mm², respectively, as determined from cross-sections of the sintered bodies. The resulting porous SiC with a total porosity of 86%, exhibited air permeability from 2.3 × 10^?11 to 1.0 × 10^?10 m², which was the same as the calculated ideal permeability, and high compressive strength of 16.6 MPa. The porosity, number of cells, air permeability and strength of the present porous SiC were significantly higher than that reported for other porous SiC ceramics.     

Influence of silicon carbide particle size on the microstructure and mechanical properties of zirconium diboride–silicon carbide ceramics

The influence of silicon carbide (SiC) particle size on the microstructure and mechanical properties of zirconium diboride–silicon carbide (ZrB₂–SiC) ceramics was investigated. ZrB₂-based ceramics containing 30 vol.% SiC particles were prepared from four different α-SiC precursor powders with average particle sizes ranging from 0.45 to 10 μm. Examination of the dense ceramics showed that smaller starting SiC particle sizes led to improved densification, finer grain sizes, and higher strength. For example, ceramics prepared from SiC with the particle size of 10 μm had a strength of 389 MPa, but the strength increased to 909 MPa for ceramics prepared from SiC with a starting particle size of 0.45 μm. Analysis indicates that SiC particle size controls the strength of ZrB₂–SiC.     

Microstructural evolution of multi-walled carbon nanotubes in the presence of mixture of silicon and silica powders at high temperatures

Microstructural evolution of multi-walled carbon nanotubes (MWCNTs) in the presence of mixture of silicon and silica powders in a coke bed is studied in the temperature range of 1000–1500 °C by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and thermogravimetry–differential scanning calorimetry (TG–DSC). The results showed that a thin amorphous SiO₂ coating was formed on the surface of MWCNTs at the temperature below 1300 °C. With the increase of the treated temperature, the coating became thicker, 3–7 nm in thickness at 1400 °C and a maximum of 10 nm at 1500 °C. Meanwhile, SiC nanowires and SiC nanocrystals around Ni catalyst at the tip of MWCNTs were formed at 1400 °C and 1500 °C, which were related to the vapor–vapor (V–V) and vapor–liquid–solid (V–L–S) reactions between SiO (g) and CO (g) or C (s), respectively. The oxidation resistance of all the treated MWCNTs was better than that of as-received ones. The oxidation peak temperature reached 804.2 °C for the treated MWCNTs, much higher than 652.2 °C for as-received ones.     

Preparation and characterization of mesoporous silicon oxycarbide ceramics without free carbon from polysiloxane

Mesoporous silicon oxycarbide ceramics without free carbon were prepared by pyrolysis of cross-linked polysiloxane at different temperatures (1300–1450 °C) followed by post treatments. The post treatments comprised two steps (HF etching and oxidation at 650 °C in air). The sample pyrolyzed at 1300 °C after post treatments exhibits the largest specific surface area (SSA) reaching up to 204 m²/g and the biggest total pore volume (0.58 cm³/g) with an average pore size of 11.4 nm. Increasing pyrolysis temperature will lead a quick decline of SSA and total pore volume. The thermal stability of pore structure of the sample pyrolyzed at 1300 °C with post treatments was investigated in air. The SSA and total pore volume almost keeps the same up to 750 °C, and subsequently decreases with a high speed. The most possible reason is the pores are severely closed by viscous flow of SiO₂ produced from SiC nanocrystallites.     

Fabrication of porous silicon carbide ceramics with high porosity and high strength

Unique porous SiC ceramics with a honeycomb structure were fabricated by a sintering-decarburization process. In this new process, first a SiC ceramic bonded carbon (SiC/CBC) is sintered in vacuum by spark plasma sintering, and then carbon particles in SiC/CBC are volatized by heating in air at 1000 °C without shrinkage. The honeycomb structure has at least two different sizes of pores; ∼20 μm in size resulting from carbon removal; and smaller open pores of 2.1 μm remaining in the sintered SiC shell. The total porosity is around 70% and the bulk density is 0.93 mg/m³. The bending and compressive strengths are 26 MPa, and 105 MPa, respectively.     

Preparation of high-temperature organic adhesives and their performance for joining SiC ceramic

Two kinds of high-temperature organic adhesives were prepared and successfully applied to join SiC ceramic. One adhesive was composed of preceramic polymer (V-PMS) and B₄C powder (HTA-1), and the other was composed of V-PMS, B₄C powder and low melting point glass powder (HTA-2). The properties of the obtained adhesives were investigated by TGA, XRD, bonding test and SEM analysis. The results show that the obtained adhesives exhibit outstanding heat-resistant property and excellent bonding strength. The bonding strength of HTA-1 treated at 200 °C, 400 °C, 600 °C were 26.8 MPa, 18.9 MPa, 7.3 MPa, respectively. When the temperature increased to 800 °C or even higher, the shear strengths of the joints were enhanced to over 50 MPa. Moreover, by adding glass powder as the second filler, it was found that the minimum shear strength of HTA-2 was enhanced to 16.4 MPa. The excellent performances of the obtained adhesives make them as promising candidates for joining SiC ceramics for high-temperature applications.     

Effect of pyrolysis temperature on the pore structure evolution of polysiloxane-derived ceramics

Homogeneous silicon oxycarbide (SiOC) ceramic powders were prepared by pyrolysis of cross-linked polysiloxane at different temperatures (1250–1500 °C) under vacuum. The effect of pyrolysis temperature on the pore structure evolution was investigated by means of N₂ adsorption, SEM, XRD, IR and element analysis (EA). Studies showed that predominate mesoporous ceramics with the average pore size in the range of 2–13 nm were obtained after pyrolysis in this temperature range. The pore structure transformation is strongly correlated with the thermolytic decomposition process of the used precursor, such as phase separation and carbothermal reduction. At relatively lower temperature (1250–1350 °C), the ceramics had a relative small specific surface areas (35 m²/g) owing to the low degree of carbothermal reduction. However, as the carbothermal degree had an obvious augment at relative higher temperature (1400–1450 °C), the specific surface areas and total pore volume increased and reached to the maximum of 66 m²/g and 0.214 cm³/g, respectively, and subsequently decreased rapidly after 1500 °C for the reason of partial sintering of the nano-sized SiC derived from polysiloxane.