Oxidation protection of C/C composites with a multilayer coating of SiC and Si + SiC + SiC nanowires

An oxidation protective Si–SiC coating with randomly oriented SiC nanowires was prepared on the SiC-coated carbon/carbon (C/C) composites by a two-step technique. First, a porous network of SiC nanowires was produced using chemical vapor deposition. This material was subjected to pack cementation to infiltrate the porous layer with a mixture of Si and SiC. The nanowires in the coating could efficiently suppress the cracking of the coating by various toughening mechanisms including nanowire pullout, nanowire bridging, microcrack deflection and good interaction between nanowire/matrix interface. The results of thermogravimetric analysis and thermal shock showed that the coating had excellent oxidation protection for C/C composites between room temperature and 1500 °C. These results were confirmed by two additional oxidation experiments conducted at temperature of 900 and 1400 °C, which demonstrated that the coating could efficiently protect C/C composites from oxidation at 900 °C for more than 313 h or at 1400 °C for more than 112 h.     

A mullite/SiC oxidation protective coating for carbon/carbon composites

To protect carbon/carbon (C/C) composites against oxidation, a mullite coating was prepared on SiC precoated C/C composites by a hydrothermal electrophoretic deposition process. The phase composition, microstructure and oxidation resistance of the prepared mullite/SiC coatings were investigated. Results show that hydrothermal electrophoretic deposition is an effective route to achieve crack-free mullite coatings. The mullite/SiC coating displays excellent oxidation resistance and can protect C/C composites from oxidation at 1773 K for 322 h with a weight loss rate of only 4.89 × 10^?4 g/cm² h. The failure of the multi-layer coatings is considered to be caused by the volatilization of silicate glass layer, the formation of microholes and microcracks on the coating surface and the formation of penetrative holes between the SiC bonding layer and the C/C matrix at 1773 K. The corresponding high temperature oxidation activation energy of the coated C/C composites at 1573–1773 K is calculated to be 111.11 kJ/mol.     

Ablation behaviour of a TaC coating on SiC coated C/C composites at different temperatures

To improve the ablation resistance of carbon/carbon (C/C) composites, a TaC coating was prepared by supersonic plasma spraying on SiC coated C/C composites. The microstructure and morphology of the coatings were characterised by Scanning Electron Microscopy and X-ray diffraction. The ablation properties were studied at different temperatures under oxyacetylene torch. At 2100 °C, the oxides were blown away and resulted in high ablation rates: 1.2×10^?2 mm/s and 3.9×10^?3 g/s. However, most oxides can remain in ablation centre and serve as a coating at low temperature (1900 and 1800 °C). Therefore, the TaC/SiC coated samples exhibited zero linear ablation rate and lower mass ablation rate.     

HfC nanowires to improve the toughness and oxidation resistance of Si-Mo-Cr/SiC coating for C/C composites

To improve the oxidation resistance of carbon/carbon (C/C) composites, a dense HfC nanowire-toughened Si-Mo-Cr/SiC multilayer coating was prepared by chemical vapor deposition (CVD) and pack cementation. The microstructure, thermal shock and isothermal oxidation resistance of the coating were investigated. HfC nanowires could improve the toughness of the coating and suppress the coating cracking. After incorporating HfC nanowires in the coating, both of the thermal shock and isothermal oxidation resistance of the coating were obviously improved. The multilayer coating with HfC nanowires could effectively protect C/C composites at 1773 K for 270 h, whose weight loss is only 0.19%. The good oxidation resistance is mainly attributed to the formation of a compound glass layer containing SiO₂ and Cr₂O₃.     

Oxidation protection of carbon fibers by coating with alumina and/or titania using atomic layer deposition

Alumina and titania coatings were deposited by atomic layer deposition onto carbon fibers at temperatures of 200 °C or below and reduced pressure. The coatings were smooth, uniform and conformed to the fiber surface. Thermogravimetric analysis (TGA) revealed that the coatings improved the oxidation resistance of the carbon fibers: the oxidation onset temperature of uncoated fibers and fibers coated with 66 nm of alumina was 630 °C. For fibers coated with 20 nm of titania it was 550 °C. Double layer coatings by 50 nm of alumina followed by 13 nm of titania yielded an oxidation onset temperature of 660 °C, while changing the order of the layers, i.e., coating fibers first with 20 nm of titania followed by 30 nm of alumina yielded an oxidation onset temperature of 750 °C. These TGA results were confirmed by a set of additional oxidation experiments conducted at a fixed temperature of 550 °C using a tube furnace in air. In this latter set of additional experiments, the times needed for a complete oxidation of the above mentioned samples were 8 h, 12 h, 10 h, 13 h, and 30 h, respectively.     

Dynamic oxidation and protection of the PAN pre-oxidized fiber C/C composites

Pre-oxidized fibers as reinforcement are candidates for reducing the overall cost of C/C composites with superior properties. This study investigated the dynamic oxidation and protection of the pre-oxidized fiber C/C composites (Pr-Ox-C-C). According to the Arrhenius equation, the oxidation kinetics of the Pr-Ox-C-C consisted of two different oxidation mechanism with the transition point was at about 700 °C. Scanning electron microscopy investigation showed that oxidation initiated from the fiber/matrix interface of composites, whereas the matrix carbon was easily oxidized. To improve the anti-oxidant properties of Pr-Ox-C-C, a ceramic powder-modified organic silicone resin/ZrB₂-SiC coating was prepared by the slurry method. The coated samples were subjected to isothermal oxidation for 320 h at 700 °C, 800 °C, 900 °C, 1000 °C and 1100 °C with incurred weight losses of ? 1.6%, 0.77%, ? 1.28%, 0.68% and 1.19%, respectively. After 110 cycles of thermal shock between 1100 °C and room temperature, a weight loss of 1.30% was obtained. The Arrhenius curve presented four different phases and mechanisms for coating oxidation kinetics. The excellent oxidation resistance properties of the prepared coating could be attributed to the inner layer which was able to form B₂O₃-Cr₂O₃-SiO₂ glass to cure cracks, and the ZrB₂-SiC outer layer that could provide protective oxides to reduce oxygen infiltration and to seal bubbles.     

Wear behavior of SiC nanowire-reinforced SiC coating for C/C composites at elevated temperatures

To improve the wear resistance of SiC coating on carbon/carbon (C/C) composites, SiC nanowires (SiCNWs) were introduced into the SiC wear resistant coating. The dense SiC nanowire-reinforced SiC coating (SiCNW-SiC coating) was prepared on C/C composites using a two-step method consisting of chemical vapor deposition and pack cementation. The incorporation of SiCNWs improved the fracture toughness of SiC coating, which is an advantage in wear resistance. Wear behavior of the as-prepared coatings was investigated at elevated temperatures. The results show that the wear resistance of SiCNW-SiC coating was improved significantly by introducing SiC nanowires. It is worth noting that the wear rate of SiCNW-SiC coating was an order of magnitude lower than that of the SiC coating without SiCNWs at 800 °C. The wear mechanisms of SiCNW-SiC coating at 800 °C were abrasive wear and delamination. Pullout and breakage of SiC grains resulted in failure of SiC coating without SiCNWs at 800 °C.     

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.     

Improved ablation resistance of C–C composites using zirconium diboride and boron carbide

Zirconium diboride and boron carbide particles were used to improve the ablation resistance of carbon–carbon (C–C) composites at high temperature (1500 °C). Our approach combines using a precursor to ZrB₂ and processing them with B₄C particles as filler material within the C–C composite. An oxyacetylene torch test facility was used to determine ablation rates for carbon black, B₄C, and ZrB₂–B₄C filled C–C composites from 800 to 1500 °C. Ablation rates decreased by 30% when C–C composites were filled with a combination of ZrB₂–B₄C particles over carbon black and B₄C filled C–C composites. We also investigated using a sol–gel precursor method as an alternative processing route to incorporate ZrB₂ particles within C–C composites. We successfully converted ZrB₂ particles within C–C composites at relatively low temperatures (1200 °C). Our ablation results suggest that a combination of ZrB₂–B₄C particles is effective in inhibiting the oxidation of C–C composites at temperatures greater than 1500 °C.     

MoSi2-based oxidation protective coatings for SiC-coated carbon/carbon composites prepared by supersonic plasma spraying

To protect carbon/carbon (C/C) composites against oxidation, MoSi₂-based oxidation protective coatings for SiC-coated carbon/carbon composites were prepared on them by supersonic plasma spraying. The MoSi₂-based coatings primarily consist of MoSi₂, Mo₅Si₃ and glassy SiO₂. Only a few pinholes and some microcracks are observed on the surface and no through-thickness cracks penetrate the cross-section. Weight loss of the MoSi₂-based coated specimens is only 1.14% after 400 h oxidation in air at 1773 K and the coated C/C composites remain intact after 11 thermal cycles between 1773 K and room temperature. The outstanding anti-oxidation ability is mainly attributable to the formation of SiO₂-based layer on the surface of MoSi₂-based coatings.     

TaB2–SiC–Si multiphase oxidation protective coating for SiC-coated carbon/carbon composites

To improve the oxidation resistance of the carbon/carbon (C/C) composites, a TaB₂–SiC–Si multiphase oxidation protective ceramic coating was prepared on the surface of SiC coated C/C composites by pack cementation. Results showed that the outer multiphase coating was mainly composed of TaB₂, SiC and Si. The multilayer coating is about 200 μm in thickness, which has no penetration crack or big hole. The coating could protect C/C from oxidation for 300 h with only 0.26 × 10^?2 g²/cm² mass loss at 1773 K in air. The formed silicate glass layer containing SiO₂ and tantalum oxides can not only seal the defects in the coating, but also reduce oxygen diffusion rates, thus improving the oxidation resistance.     

Influence of the carbonization temperature on the mechanical properties of thermoplastic polymer derived C/C-SiC composites

Carbon/Carbon (C/C) composites derived from the thermoplastic polymer polyetherimide (PEI) were pyrolized up to 1000 °C, subsequently carbonized in inert atmosphere up to 2200 °C and afterwards infiltrated with liquid silicon. The investigation of fibers and matrix with Raman microspectroscopy revealed, that an increased carbonization temperature leads to an increased carbon order as well as an incipient stress-induced graphitization of the carbon matrix close to the fiber surfaces at 2200 °C. The derived C/C-SiC samples show a maximum flexural strength of 180 MPa with C/C composites treated at 2000 °C and monotonically increasing Young’s moduli ranging from 49 GPa with C/C preforms treated at 1600 °C up to 59 GPa after carbonization at 2200 °C. The carbon fiber strength was evaluated with a single fiber tensile test, which showed a monotonically increased Young’s modulus and a decrease of the strength after carbonization at 2200 °C.     

A double layer nanostructure SiC coating for anti-oxidation protection of carbon/carbon composites prepared by chemical vapor reaction and chemical vapor deposition

A double layer nanostructure SiC coating was prepared by chemical vapor reaction and chemical vapor deposition to protect carbon/carbon composites from oxidation. The obtained dense coating reveals a typical crystalline structure and combines well with the substrate. The outer layer of the coating consists of SiC nanocrystals and nanowires, whereas the inner layer is mainly composed of SiC microcrystals, nanocrystals and nanowires. The oxidation and cyclic thermal shock test performed at 1400 °C in air demonstrates that the prepared dense nanostructure coating has excellent anti-oxidation behavior and thermal shock resistance at high temperature. After 400 h oxidation and 34 cycles of thermal shock from 1400 °C to room temperature, the weight loss of the coated sample is only 1.67%. In the oxidation process, the amorphous silica formed at the beginning of the oxidation crystallizes to cristobalite as oxidation time increased. The formation of cristobalite resulted in micro-cracks formed along grain boundaries in the cyclic thermal shock test. As only cracks are formed on the coating surface, it can be concluded that the formation of the penetration cracks may be the reason for the weight loss of the SiC coated composite.     

Design of an inlaid interface structure to improve the oxidation protective ability of SiC–MoSi2–ZrB2 coating for C/C composites

To improve the oxidation protective ability of SiC–MoSi₂–ZrB₂ coating for carbon/carbon (C/C) composites, pre-oxidation treatment and pack cementation were applied to construct a buffer interface layer between C/C substrate and SiC–MoSi₂–ZrB₂ coating. The tensile strength increased from 2.29 to 3.35 MPa after pre-oxidation treatment, and the mass loss was only 1.91% after oxidation at 1500 °C for 30 h. Compared with the coated C/C composites without pre-oxidation treatment, after 18 thermal cycles from 1500 °C and room temperature, the mass loss was decreased by 30.6%. The improvements of oxidation resistance and mechanical property are primarily attributed to the formation of inlaid interface between the C/C substrate and SiC–MoSi₂–ZrB₂ coating.     

Oxidation behavior and microstructure evolution of SiC-ZrB2-ZrC coating for C/C composites at 1673 K

To protect carbon/carbon (C/C) composites against oxidation, a SiC-ZrB₂-ZrC coating was prepared by the in-situ reaction between ZrC, B₄C and Si. The thermogravimetric and isothermal oxidation results indicated the as-synthesized coating to show superior oxidation resistance at elevated temperatures, so it could effectively protect C/C composites for more than 221 h at 1673 K in air. The crystalline structure and morphology evolution of the multiphase SiC-ZrB₂-ZrC coating were investigated. With the increase of oxidation time, the SiO₂ oxide layer transformed from amorphous to crystalline. Flower-like and flake-like SiO₂ structures were generated on the glass film during the oxidation process of SiC-ZrB₂-ZrC coating, which might be ascribed to the varying concentration of SiO. The oxide scale presented a two-layered structure ~130 µm thick after oxidation, consisting of a SiO₂-rich glass layer containing ZrO₂/ZrSiO₄ particles and a Si-O-Zr layer. The multiphase SiC-ZrB₂-ZrC ceramic coating exhibited much better oxidation resistance than monophase SiC, ZrB₂ or ZrC ceramic due to the synergistic effect among the different components.     

Effects of porous C/C density on the densification behavior and ablation property of C/C–ZrC–SiC composites

C/C–ZrC–SiC composites were prepared by precursor infiltration and pyrolysis process using a mixture solution of organic zirconium-containing polymer and polycarbosilane as precursors. Porous carbon/carbon (C/C) composites with density of 0.92, 1.21 and 1.40 g/cm³ were used as preforms, and the effects of porous C/C density on the densification behavior and ablation resistance of C/C–ZrC–SiC composites were investigated. The results show that the C/C preforms with a lower density have a faster weight gain, and the obtained C/C–ZrC–SiC composites own higher bulk density and open porosity. The composites fabricated from the C/C preforms with a density of 1.21 g/cm³ exhibit better ablation resistance with a surface temperature of over 2400 °C during ablation. After ablation for 120 s, the linear and mass ablation rates of the composites are as low as 1.02 × 10⁻³ mm/s and −4.01 × 10⁻⁴ g/s, respectively, and the formation of a dense and continuous coating of molten ZrO₂ solid solution is the reason for their great ablation resistance.     

Effect of PyC interphase thickness on mechanical behaviors of SiBC matrix modified C/SiC composites fabricated by reactive melt infiltration

A dense carbon fiber reinforced silicon carbide matrix composites modified by SiBC matrix (C/SiC-SiBC) was prepared by a joint process of chemical vapor infiltration, slurry infiltration and liquid silicon infiltration. The effects of pyrolytic carbon (PyC) interphase thickness on mechanical properties and oxidation behaviors of C/SiC-SiBC composites were evaluated. The results showed that C/SiC-SiBC composites with an optimal PyC interphase thickness of 450 nm exhibited flexural strength of 412 MPa and fracture toughness of 24 MPa m^1/2, which obtained 235% and 300% improvement compared with the one with 50 nm-thick PyC interphase. The enhanced mechanical properties of C/SiC-SiBC composites with the increase of interphase thickness was due to the weakened interfacial bonding strength and the decrease of matrix micro-crack amount associated with the reduction of thermal residual stress. With the decrease in matrix porosity and micro-crack density, C/SiC-SiBC composites with 450 nm-thick interphase exhibited excellent oxidation resistance. The residual flexural strength after oxidized at 800, 1000 and 1200 °C in air for 10 h was 490, 500 and 480 MPa, which increased by 206%, 130% and 108% compared with those of C/SiC composites.     

Microstructure and oxidation resistance of C-AlPO4–mullite coating prepared by hydrothermal electrophoretic deposition for SiC-C/C composites

Oxidation resistant C-AlPO₄–mullite coating for SiC pre-coated carbon/carbon composites (SiC-C/C) was prepared by a novel hydrothermal electrophoretic deposition process. The phase composition, surface and cross-section microstructure of the as-prepared multi-layer coatings were characterized by X-ray Diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The influence of deposition voltage on phase composition, microstructure and oxidation resistance of the as-prepared coatings was particularly investigated. Results show that the outer layer coating mainly composed of C-AlPO₄ and mullite phase can be achieved after the hydrothermal electrophoretic deposition. The thickness, density and anti-oxidation property of the C-AlPO₄–mullite coating was improved with the increase of deposition voltage from 160 V to 200 V. The multi-layer coating prepared at a voltage of 200 V exhibit excellent anti-oxidation property, which can effectively protect C/C composites from oxidation in air at 1773 K for 324 h with a weight loss of 1.01%. The failure of the multi-layer coatings is due to the generation of cross-holes in the coating, which cannot be self-cured by the metaphosphate and silicate glass layer after long time oxidation at 1773 K.     

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.     

Dynamic oxidation resistance and residual mechanical strength of ZrB2-CrSi2-SiC-Si/SiC coated C/C composites

To improve oxidation resistance of carbon/carbon (C/C) composites, a multiphase double-layer ZrB₂-CrSi₂-SiC-Si/SiC coating was prepared on the surface of C/C composites by pack cementation. Thermogravimetry analysis showed that the as-prepared coating could provide effective oxidative protection for C/C composites from room temperature to 1490 °C. After thermal cycling between 1500 °C and room temperature, the fracture behaviors of the as-prepared specimens changed and their residual flexural strengths decreased as thermal cycles increased. The specimen after 20 thermal cycles presented pseudo-plastic fracture characteristics and relatively high residual flexural strength (83.1%), while the specimen after 30 thermal cycles failed catastrophically without fiber pullout due to the severe oxidation damage of C/C substrate especially the brittleness of the reinforcement fibers.