Ablative and Mechanical Properties of C/C—ZrC Composites Prepared by Precursor Infiltration and Pyrolysis Process

C/C-ZrC composites with continuous ZrC matrix were prepared by precursor infiltration and pyrolysis process using zirconium-containing polymer.Ablation properties of the composites were investigated by oxyacetylene flame with heat flux of 2380 and 4180 kW/m~2,respectively.The results showed that C/C-ZrC composites exhibited excellent ablation resistance under the heat flux of 2380 kW/m~2 for 120 s and a tree-coral-like ZrO_2protective layer formed after ablation.However,when the heat flux increased to 4180 kW/m~2,the maximum temperature of ablated surface reached 2500 ℃ and a strong degradation of ablation resistance was observed due to the weak bonding between the formed ZrO_2 layer and the composites.The flexural strength of C/C-ZrC composites was 110.7 ± 7.5 MPa.There were a large number of carbon fiber bundles pull-out,and the composites exhibited a pseudo-plastic fracture behavior.     

Design,Preparation and Properties of Carbon Fiber Reinforced Ultra-High Temperature Ceramic Composites for Aerospace Applications:A Review

Carbon fiber reinforced ultra-high temperature ceramic(UHTC) composites, consisting of carbon fibers embedded in a UHTC-matrix or a C–SiC–UHTC-matrix, are deemed as the most viable class of materials that can overcome the poor fracture toughness and thermal shock resistance of monolithic UHTC materials, and also improve the oxidation resistance and ablation resistance of C/C and C/SiC composites at ultra-high temperatures. In this review, we summarize the different processing routes of the composites based on the UHTC introducing methods, including chemical vapor infiltration/deposition(CVI/D),precursor infiltration and pyrolysis(PIP), reactive melt infiltration(RMI), slurry infiltration(SI), in-situ reaction, hot pressing(HP), etc; and the advantages and drawbacks of each method are briefly discussed. The carbon fiber reinforced UHTC composites can be highly tailorable materials in terms of fiber,interface, and matrix. From the perspective of service environmental applications for engine propulsions and hypersonic vehicles, the material designs(mainly focusing on the composition, quantity, structure of matrix, as well as the architecture of carbon fibers, UHTCs and pores), their relevant processing routes and properties(emphasizing on the mechanical and ablation properties) are discussed in this paper. In addition, we propose a material architecture to realize the multi-function through changing the distribution of carbon fibers, UHTCs and pores, which will be an important issue for future development of carbon fiber reinforced UHTC composites.     

Oxidation and Mechanical Properties of SiC/SiC-MoSi_2-ZrB_2 Coating for Carbon/Carbon Composites

To improve oxidation resistance of carbon/carbon(C/C) composites,a SiC/SiC-MoSi_2-ZrB_2 double-layer ceramic coating was prepared on C/C composites by two-step pack cementation.The phase compositions and microstructures of as-prepared multilayer coating were characterized by X-ray diffraction and scanning electron microscopy.The oxidation resistance at 1773 K and the effect of thermal shock between 1773 K and room temperature on mechanical performance of coated specimens were investigated.The results show that the SiC/SiC-MoSi_2-ZrB_2 coating exhibits dense structure and is composed of SiC,Si,MoSi_2 and ZrB_2·It can protect C/C composites from oxidation at 1773 K for more than 510 h with weight loss of 0.5%.The excellent anti-oxidation performance of the coating is due to the formation of SiO_2-ZrSiO_4 complex glassy film.The coating can also endure the thermal shocks between 1773 K and room temperature for 20 times with residual flexural strength of 86.1%.     

W-Mo-Si/SiC Oxidation Protective Coating for Carbon/Carbon Composites

A W-Mo-Si/SiC double-layer oxidation protective coating for carbon/carbon （C/C） composites was prepared by a two-step pack cementation technique. XRD （X-ray diffraction） and SEM （scanning electron microscopy）results show that the coating obtained by the first step pack cementation was a thin inner buffer layer of SiC with some cracks and pores, and a new phase of （WxMo1-x）Si2 appeared after the second step pack cementation. Oxidation test shows that, after oxidation in air at 1773 K for 175 h and thermal cycling between 1773 K and room temperature for 18 times, the weight loss of the W-Mo-Si/SiC coated C/C composites was only 2.06%. The oxidation protective failure of the W-Mo-Si/SiC coating was attributed to the formation of some penetrable cracks in the coating.     

Microstructure and Mechanical Properties of C/C-ZrC-SiC Composites Fabricated by Reactive Melt Infiltration with Zr,Si Mixed Powders

To meet the increasing demand for advanced materials capable of operation over 2000℃for future thermal protection systems application,C/C—ZrC—SiC composites were fabricated by reactive melt infiltration(RMI) with Zr,Si mixed powders as raw materials.The structural evolution and formation mechanism of the C/C—ZrC -SiC composites were discussed,and the mechanical property of the as-prepared material was investigated by compression test.The results showed that after the RMI process,a special structure with ZrC-SiC multi-coating as outer layer and ZrC-SiC-PyC ceramics as inner matrix was formed.ZrC and SiC rich areas were formed in the composites and on the coating surface due to the formation of Zr-Si intermetallic compounds in the RMI process.Mechanical tests showed that the average compression strength of the C/C-ZrC-SiC composites was 133.86 MPa,and the carbon fibers in the composites were not seriously damaged after the RMI process.     

Influence of ZrB_2 Nanoparticles on the Mechanical and Thermal Behaviors of Carbon Nanotube Reinforced Resol Composite

The present study focuses on the thermal response of carbon ?ber-reinforced phenolic composites, where the matrix has been modi?ed with different reinforcements. Two types of materials, multiwalled carbon nanotubes and zirconium diboride(ZrB_2), were used in a new design of mixture to produce the heatresistant ablative composite system. The CNT/ZrB_2/carbon/phenolic nanocomposite(Z/NT-CR) system corresponding to CNT/carbon/phenolic nanocomposite(NT-CR) showed a reasonable decrease in mass loss and the ablation rate as compared to carbon/phenolic composite(CR). However, substantial drop in two factors was found for Z/NT-CR as compared to carbon/phenolic and NT-CR. Ablation mechanisms for all three composites were investigated by thermal gravimetric analysis in conjunction with microstructural studies using a ?eld emission scanning electron microscope. The microstructural studies revealed that CNTs acted as an ablation resistant phase for protection against 2000 °C, and the conversion from ZrB_2 to Zr O2 played an important role as an insulator in the performance of char layer in the ablation resistance.     

Oxidation and Mechanical Properties of SiC/SiC-MoSi2-ZrBa Coating for Carbon/Carbon Composites

To improve oxidation resistance of carbon/carbon （C/C） composites, a SiC/SiC-MoSi2-ZrB2 double-layer ceramic coating was prepared on C/C composites by two-step pack cementation. The phase compositions and microstructures of as-prepared multilayer coating were characterized by X-ray diffraction and scanning electron microscopy. The oxidation resistance at 1773 K and the effect of thermal shock between 1773 K and room temperature on mechanical performance of coated specimens were investigated. The results show that the SiC/SiC-MoSi2-ZrB2 coating exhibits dense structure and is composed of SiC, Si, MoSi2 and ZrB2. It can protect C/C composites from oxidation at 1773 K for more than 510 h with weight loss of 0.5%. The excellent anti-oxidation performance of the coating is due to the formation of SiO2-ZrSiO4 complex glassy film. The coating can also endure the thermal shocks between 1773 K and room temperature for 20 times with residual flexural strength of 86.1%.     

SiC Nanowires Toughed HfC Ablative Coating for C/C Composites

In order to improve ablation resistance of carbon/carbon(C/C) composites,SiC nanowires were prepared on C/C composites surface in prior through chemical vapor reaction before HfC coating.SiC nanowires grew randomly and had good combination with HfC coating.SiC nanowires toughed HfC coating had lower linear and mass ablation rates than original HfC coating.The surface was much flatter and exhibited smaller cracks in center region.The ablation mechanism of HfC coating has been changed by SiC nanowires.Thicker HfO2 fused layer was formed on the surface of the toughed HfC coating,which could provide efficient protection for C/C composites.Therefore,SiC nanowires toughed HfC coating behaved in better ablation resistance.     

Ablation Mechanism of Carbon/Carbon Composites Modified by HfC–SiC in Two Conditions Under Oxyacetylene Torch

C/C–HfC–SiC composites prepared by precursor infiltration and pyrolysis process were ablated by oxyacetylene torch under two different flame conditions.The ablation performance of the composites was investigated in the heat flux of 2.38 MW/m~2(HF-L) and 4.18 MW/m~2(HF-H) for 60 s.The mechanical denudation in 4.18 MW/m~2(HF-H) was higher than that in 2.38 MW/m~2(HF-L),while the results indicated that the composites had a similar and good ablation property under two different flame conditions.C/C–HfC–SiC composites can adapt the heat flux from 2.38 MW/m~2 to 4.18 MW/m~2.The HfO_2 was not melted completely in the heat flux of 2.38 MW/m~2(HF-L).So,both HfO_2 and SiO_2 layers acted as an effective barrier to the transfer of heat and oxidative gases into the underlying carbon substrate.SiO_2 was severely consumed in 4.18 MW/m~2(HF-H),where the HfO_2 molten layer played a more important role in protecting the inner composite.     

Mullite Oxidation Resistant Coating for SiC-coated Carbon/Carbon Composites by Supersonic Plasma Spraying

To improve the oxidation resistance of carbon/carbon (C/C) composites, mullite coating was prepared on the surface of SiC-coated C/C composites by supersonic plasma spraying. Phases and microstructures of mullite coating were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The coating primarily consists of a single phase of mullite (3Al2O3-2SiO2). The SEM results show that mullite coating was continuous and well bonded with the SiC inner layer without penetrating crack. Mullite coating exhibited good oxidation resistance. After 98.5 h oxidation at 1773 K and 9 thermal shock cycles between 1773 K and room temperature, the weight loss of the coated C/C composites was only 2.57%.     

Microstructure and tensile behavior of 2D-C_f/AZ91D composites fabricated by liquid–solid extrusion and vacuum pressure infiltration

2D carbon fiber reinforced AZ91 D matrix composites(2D-C_f/AZ91 D composites) were fabricated by liquid–solid extrusion and vacuum pressure infiltration technique(LSEVI). In order to modify the interface between fibers and matrix and protect the fiber, pyrolytic carbon(Py C) coating was deposited on the surface of T700 carbon fiber by chemical vapor deposition(CVD). Microstructure observation of the composites revealed that the composites were well fabricated by LSEVI. The segregation of aluminum at fiber surface led to the formation of Mg_(17)Al_(12) precipitates at the interface. The aluminum improved the infiltration of the alloy and Py C coating protected the fibers effectively. The ultimate tensile strength of 2D-C_f/AZ91 D composites was about 400 MPa. The fracture process of 2D-C_f/AZ91 D composites was transverse fiber interface cracking–matrix transferring load–longitudinal fibers bearing load–longitudinal fibers breaking.     

SiC-Si-ZrSiO_4 Multiphase Oxidation Protective Coating for Carbon/Carbon Composites

In order to improve the anti-oxidation property of carbon/carbon （C/C） composites, a novel SiC-Si-ZrSiO4 multiphase oxidation protective coating was produced on the surface of C/SiC coated carbon/carbon compo ites by a pack cementation technique. The phase composition and microstructure of the as-prepared coatings were characterized by XRD （X-ray diffraction）, SEM （scanning electron microscopy） and EDS （energy dispersive spectroscopy）. Oxidation behavior of the multiphase coated C/C composites was also investigated. It showed that the as-prepared coating characterized by excellent oxidation resistance and thermal shock re- sistance could effectively protect C/C composites from oxidation at 1773 K for 57 h in air and endure the thermal cycle between 1773 K and room temperature for 12 times, whereas the corresponding weight loss is only 1.47%. The excellent oxidation protective ability of the SiC-Si-ZrSiO4 coating could be attributed to the C/SiC gradient inner layer and the multiphase microstructure of the coating.     

Interfacial Structure and Formation Mechanism of Ultrasonic-assisted Brazed Joint of SiC Ceramics with Al—12Si Filler Metals in Air

Ultrasonic-assisted brazing of SiC ceramics was performed by filling with an Al—12Si alloy at a low temperature of 620 °C in air. The interfacial characteristics and formation mechanism were investigated. The joint shear strength reached 84–94 MPa using the ultrasonic time of 2–16 s. The fracture morphology showed that the fracture path initiated and propagated in the joint alloy. The thin film of amorphous SiO 2 that formed on the SiC surface was non-uniformly decomposed and diffused into the liquid Al—12Si alloy under the cavitation erosion effect of ultrasound. Abnormal isolated blocks of Al_2 SiO_5 compounds formed at the interface between Al—12Si and a thicker SiO_2 layer formed during the thermal oxidation treatment of the Si C ceramic. The SiO_2 layer on the Si C ceramic did not hinder or impair the wetting and bonding process, and a stronger bond could form between Al—12Si and SiO_2 or Si C in ultrasonicassisted brazing.     

Effect of SiC Location on the Ablation of C/C-SiC Composites in Two Heat Fluxes

How layer-segregated distribution of SiC affects the ablation of C/C-SiC composites was studied in the present work.A certain amount of SiC particles was deposited at the non-woven(C/C—SiC-1) and web(C/C-SiC-2) layer of 2D needle-punched carbon fibre fabric reinforced pyrocarbon composites,respectively.Ablation under oxyacetylene torch demonstrated that the two composites have similar ablation rates in heat flux of 2.38 MW/m~2 whereas ablation rates of C/C-SiC-2 were much higher than those of C/C—SiC-1 when heat flux was 4.18 MW/m~2.SiO_2 covered partially the defective surface of both composites in the lower heat flux.The different SiC locations induced distinct defects and then led to the two composites' dissimilar ablation rates in the higher heat flux.     

Fabrication of barium-strontium aluminosilicate coatings on C/SiC composites via laser cladding

Barium-strontium aluminosilicate(BSAS) and Si/BSAS coatings were fabricated on the surface of C/SiC composites via a two-step laser cladding process. The microstructure, mechanical properties, and the water vapor corrosion behavior of the samples were investigated. The BSAS coating was found to be tightly bonded to the substrate and only a few pores and microcracks were observed. The introduction of a silicon middle layer was revealed to reduce thermal stress and promote the healing of defects formed during the laser cladding process. To evaluate the corrosion resistance, the BSAS and Si/BSAS-coated C/SiC composites were exposed to an atmosphere of 50% H_2O and 50% O_2 at 1250 °C. The resulting weight change and flexural strength were measured as a function of the corrosion time. The addition of the silicon middle layer below the BSAS top layer resulted in a better resistance to water vapor corrosion. Furthermore, the Si/BSAS-coated samples showed a lower weight loss and a smaller reduction in flexural strength than the BSAS-coated and the uncoated samples during water vapor corrosion. Thus, laser cladding is demonstrated to be an effective and feasible method to fabricate high-quality ceramic coatings on C/SiC composites. The introduction of a silicon middle layer can inhibit defect formation during the laser cladding process and protect the composite from water vapor corrosion.     

Preparation and Microstructure of a Si-Mo Fused Slurry Coating on Carbon/Carbon Composites for Oxidation Protection

A coating of composition Si-40Mo (wt pct) was prepared by fused slurry coating method on the two-dimensional carbon/carbon (2D-C/C) composite to improve oxidation resistance. In the procedure of the fabrication, pure St slurry inner layer in the pre-coating was necessary to apply because of infiltration of liquid Si into the substrate during the sintering. The coating consists of Si continuous phase and MoSi2 particles. In addition, the infiltration of Si into the substrate and the SiC reaction layer between the coating and the C/C composite were observed. Oxidation resistance and the thermal shock resistance of the Si-Mo fused sluury coating were quite excellent at 1730℃     

Microstructure and Tribological Behavior of a TiO_2/hBN Composite Ceramic Coating Formed via Micro-arc Oxidation of Ti–6Al–4V Alloy

A composite coating containing hexagonal boron nitride(hBN) particles and titanium oxide(TiO_2) was formed on the surface of Ti–6Al–4V alloy via micro-arc oxidation(MAO). The effect of quantity of the hBN-particles added into electrolyte on microstructure, composition, and wear behavior of the resulting composite coatings was investigated. Microstructure, phase composition, and tribological behavior of the resulting MAO coatings were evaluated via scanning electron microscopy, X-ray diffraction, and ball-on-disc abrasive tests. The results reveal that the TiO_2/hBN composite coating consisting of rutile TiO_2, anatase TiO_2, and an hBN phase was less porous than particle-free coating. Furthermore, the presence of hBN particles in the MAO coating produced an improved anti-friction property. The composite coating produced in the electrolyte containing 2 g/L of hBN particles exhibited the best wear resistance.The outer loose layer of the MAO coatings was removed by a mechanical polishing process, which led to a significant improvement in the wear resistance and anti-friction properties of the MAO coatings and highlighted an essential lubricating role of hBN particles in the composite coatings. However, wear mechanism of the MAO coatings was not relevant to the presence of hBN particles, where fatigue wear dominated the anti-fraction properties of the MAO coatings with and without hBN particles.     

Carbon–Iron Microfibrous Material Produced by Thermal Treatment of Self-rolled Poly(4-vinyl pyridine) Films Loaded by Fe_2O_3 Particles

Ensembles of freeze-dried self-rolled polymer micro-scrolls are explored as template media for producing carbon–iron based composites with fibrous morphology. Polymer fibres impregnated with furfuryl alcohol and loaded with Fe2O3 particles, were thermally treated under inert atmosphere at 700 °C and subsequently analysed by scanning and transmission electron microscopy, X-ray diffraction,thermogravimetric analysis, and nitrogen adsorption. The resulting material has a micro-fibrous morphology and is basically composed of metallic Fe0 and FeO particles, i.e., more than 98 wt% of the carbon/iron-based composite mass. These particles are held together by amorphous porous carbon foam obtained by in-situ carbonization of the polymer/Fe2O3 composite with evacuation of carbon from the system via COx gases released by carbo-reduction of Fe2O3. The material has significant activity in the reaction of catalytic decomposition of hydrogen peroxide in water solutions.     

Active metal brazing of SiO_2–BN ceramic and Ti plate with Ag–Cu–Ti+BN composite filler

SiO_2–BN ceramic and Ti plate were joined by active brazing in vacuum with Ag–Cu–Ti+BN composite filler.The effect of BN content,brazing temperature and time on the microstructure and mechanical properties of the brazed joints was investigated.The results showed that a continuous Ti N–Ti B_2reaction layer formed adjacent to the SiO_2–BN ceramic,whose thickness played a key role in the bonding properties.Four Ti–Cu compound layers,Ti_2Cu,Ti_3Cu_4,Ti Cu_2and Ti Cu_4,were observed to border Ti substrate due to the strong affinity of Ti and Cu compared with Ag.The central part of the joint was composed of Ag matrix,over which some fine-grains distributed.The added BN particles reacted with Ti in the liquid filler to form fine Ti B whiskers and Ti N particles with low coefficients of thermal expansion(CTE),leading to the reduction of detrimental residual stress in the joint,and thus improving the joint strength.The maximum shear strength of 31 MPa was obtained when 3 wt%BN was added in the composite filler,which was 158%higher than that brazed with single Ag–Cu–Ti filler metal.The morphology and thickness of the reaction layer adjacent to the parent materials changed correspondingly with the increase of BN content,brazing temperature and holding time.Based on the correlation between the microstructural evolution and brazing parameters,the bonding mechanism of SiO_2–BN and Ti was discussed.     

Fabrication and oxidation resistance of silicon nitride fiber reinforced silica matrix wave-transparent composites

Wave-transparent ceramic matrix composites for the high temperature use should possess excellent oxidation resistance. In this work, Si_3N_(4f)/SiO_2 composites with different fiber content were fabricated by filament winding and sol gel method. The oxidation resistance was investigated by tracking the response of flexural strength to the testing temperature. The results show that the flexural strength and toughness of the composites with fiber content of over 37% can reach high levels at around 175.0 MPa and 6.2 MPa m1/2, respectively. After 1 h oxidation at 1100?C, the flexural strength drops a lot but can still reach 114.4 MPa, which is high enough to ensure the safety of structures. However, when the oxidation temperature rises to 1200–1400?C, the flexural strengths continue to fall to a relatively low level at 50.0–66.4 MPa. The degradation at high temperatures is caused by the combination of over strong interfacial bonding, the damage of fiber and the crystallization of silica matrix.