Characterization of carbon fiber-reinforced ultra-high temperature ceramic matrix composites fabricated via Zr-Ti alloy melt infiltration

Carbon fiber-reinforced ultra-high temperature ceramic matrix composites (C/UHTCMCs) were fabricated via Zr-Ti alloy melt infiltration (Zr-Ti MI) using carbon-carbon composite (C/C) preforms and alloys with three different compositions. Alloys were successfully infiltrated into C/C to form solid solutions of TiC and ZrC, with melting temperatures > 2900 °C. Notably, residual alloys were not observed after MI occurred at 1750 °C. Bending strength and fracture toughness of the C/UHTCMCs at room temperature and 1500 °C in air/Ar revealed that mechanical properties of the composites were similar to those of the C/C preform. During arc wind tunnel tests at 2000 °C, a recession of C/UHTCMCs fabricated using Ti-rich alloys was observed; however, this behavior was not observed for the composites prepared using Zr-rich alloys owing to the formation of a ZrO₂ solid solution. Accordingly, Zr-Ti MI is a viable method for preparing C/UHTCMCs without degrading the mechanical properties of the C/C preform, while increasing the ablation resistance.     

A review on machining of carbon fiber reinforced ceramic matrix composites

Carbon fiber reinforced ceramic matrix ceramic/polymers composites have excellent physical-mechanical properties for their specific strength, high hardness, and strong fracture toughness relative to their matrix, and they also possess a good performance of wear resistance, heat resistance, dimensional stability, and ablation resistance. It is a choice for thermal protection and high temperature structural materials. However, this kind of composites owning characteristics of high hardness and abrasion is difficult to machine which impedes the large-scale industrial application of manufacturing. This paper mainly reviews the research on machining status of carbon fiber reinforced ceramic matrix composites including carbon fiber reinforced polymer matrix composites from the aspects of conventional machining and unconventional machining method. The machining trends, problems existing in various machining methods and corresponding solutions are generalized and analyzed.     

Carbon fiber reinforced ceramic matrix composites with an oxidation resistant boron nitride interface coating

Toughening a ceramic in a ceramic matrix composite (CMC) depends on an ability of the composite to tolerate an accumulation of matrix cracks. When the reinforcement phase is carbon fiber, these cracks leave the fiber susceptible to destructive oxidation by ingress of air during high temperature exposure. Generally, a graphitic carbon interface coating is applied to carbon fibers because it provides for a weak bond between fiber and matrix that is required to promote toughening. This investigation seeks to utilize a BN coating instead of a C coating in order to promote oxidation resistance. Like graphitic carbon, BN is soft and easily cleavable. Preliminary observations that C/BN/SiC CMC's using Toray T300 carbon fibers were highly brittle and of low strength lead to a requirement of heat treating the fibers prior to the CVD of BN for toughened composites to be fabricated. It is likely heat treating removed reactive functionalities from the fiber surface to yield a weakly adhered and compliant interface.     

Ablation behaviour of ultra-high temperature ceramic matrix composites: Role of MeSi2 addition

A new class of ZrB₂ composites reinforced with 40 vol% C short fibers and containing 5 vol% SiC in combination with 5 vol% MoSi₂, HfSi₂ or WSi₂ successfully withstood extreme conditions in a oxyacetylene torch. Different responses to the torch testing were recorded depending on which secondary phase was present; this was primarily a result of the final density which ranged between 83 and 94% of the theoretical value. The temperatures achieved on the surfaces of the samples tested also varied as a function of the residual porosity and ranged from 2080 to 2240 °C. HfSi₂ additions offered the best performance and exceeded that of the baseline material that contained only SiC. It is believed that this was due to its ability to promote the elimination of porosity during densification and to the refractory nature of its oxide, HfO₂. In contrast, MoSi₂ and WSi₂ formed highly volatile oxides on the surface, which did not offer better protection than the ZrO₂-SiO₂ scale that developed in the baseline.     

A review on laser deposition-additive manufacturing of ceramics and ceramic reinforced metal matrix composites

Ceramics and ceramic reinforced metal matrix composites (MMCs) are widely used in severe working conditions and have been applied in biomedical, aerospace, electronic, and other high-end engineering industries owing to their superior properties of high wear resistance, outstanding chemical inertness, and excellent properties at elevated temperatures. These superior properties, on the other hand, make it difficult to process these materials with conventional manufacturing methods, posing problems of high cost and energy consumptions. In response to this problem, direct additive manufacturing (AM), which is equipped with a high-power-density laser beam as heat source, has been developed and extensively employed for processing ceramics and ceramic reinforced MMCs. Compared with other direct AM processes, laser deposition-additive manufacturing (LD-AM) process excels in several aspects, such as lower labor intensity, higher fabrication efficiency, and capabilities of parts remanufacturing and functionally gradient composite materials fabrication. Besides these benefits, problems of poor bonding, cracking, lowered toughness, etc. still exist in LD-AM fabricated parts. This paper reviews developments on LD-AM of ceramics and ceramic reinforced MMCs in both bulk parts fabrication and cladding. Main issues to be solved, corresponding solutions, and the trend of development are summarized and discussed.     

Properties of ceramic fiber reinforced cement composites

Mechanical properties and preliminary durability of ceramic fiber reinforced Portland cement composites tested with wet-hot accelerating method were investigated. The results showed that the flexural strength of mortar could be increased obviously by adding ceramic fiber into it, but the effect of the flexural reinforcement was influenced by various factors, including fiber length, fiber content and kinds of matrices; the preliminary durability of ceramic fiber in ordinary Portland cement tested with wet-hot accelerating method was much better than that of alkali-resistant (AR) glass fiber. The mechanism of the durability of ceramic fiber in ordinary Portland cement is also discussed.     

Influence of brick pattern interface structure on mechanical properties of continuous carbon fiber reinforced lithium aluminosilicate glass-ceramics matrix composites

Continuous carbon fiber reinforced lithium aluminosilicate glass-ceramic matrix composites have been fabricated by sol-gel process and hot pressing technique. The results show that the Cf/β-eucryptite composites hot pressed at 1300 °C and Cf/β-spodumene composites hot pressed at 1400 °C form weak interface with brick pattern characteristics, leading to high mechanical performance. The maximum flexural strength and fracture toughness reach 571 ± 32 MPa and 9.8 ± 0.6 MPa m^1/2 for Cf/β-eucryptite composites and 640 ± 72 MPa and 19.9 ± 1.8 MPa m^1/2 for Cf/β-spodumene composites. On increasing the hot pressing temperature, the active chemical diffusion consumes brick pattern interface layer, which leads to the formation of strong bonding between carbon fiber and the matrix. As a result, the composites exhibit brittle fracture behavior and the mechanical properties decrease significantly.     

SiC fiber reinforced geopolymer composites,part 2: Continuous SiC fiber

In this paper, unidirectional SiC fiber (SiC_f) reinforced geopolymer composites (SiC_f/geopolymer) were prepared and effects of fiber contents on the microstructure and mechanical properties of the composites in different directions were investigated. The XRD results showed that addition of SiC_f retarded geopolymerization process of geopolymer matrix by weakening the typical amorphous hump. SiC_f in all the composites were well infiltrated by geopolymer matrix, but microcracks which were perpendicular to the fiber axial direction were noted in the interface area due to the thermal shrinkage of matrix during the curing process. With the increases in fiber contents, although Young's modulus of the composites increased continuously, flexural strength, fracture toughness and work of fracture increased at first, reached their peak values and then decreased. And when fiber content was 20 vol%, the composites showed the highest flexural strength, fracture toughness and work of fracture, which were 14.2, 15.2 and 81.6 times as high as those of pristine geopolymer, respectively, indicating significant strengthening and toughening effects from SiC_f. Meanwhile, SiC_f/geopolymer composites failed in different failure modes in the different directions, i.e., tensile failure mode in the x direction (in-plane and perpendicular to the fiber axial direction) and shear failure mode in the z direction (laminate lay-up direction).     

Elevated temperature tensile and bending strength of ultra-high temperature ceramic matrix composites obtained by different processes

This paper presents a comparison of microstructures and mechanical properties of different ZrB₂-based CMCs, which were manufactured in the frame of the Horizon 2020 European C³HARME research project through different processes: slurry infiltration and sintering (SIS), polymer infiltration and pyrolysis (PIP) and radio frequency chemical vapour infiltration (RF-CVI). Tensile testing with a novel optimized shape of the specimens was performed and compared with the results of flexural tests to assess the structural properties. For the first time, tensile tests up to 1600 °C were carried out on UHTCMCs. Despite the different microstructural features, all the ZrB₂-based CMCs demonstrated excellent structural properties even at elevated temperature. The characterization shows how the different amount of porosity and fibre properties, such as its stiffness, strength and elongation, affected the mechanical behaviour of the C³HARME’s composites. Finally, the role of the high level of residual thermal stresses is discussed.     

Thermal properties and performance of carbon fiber-based ultra-high temperature ceramic matrix composites (Cf-UHTCMCs)

The thermophysical properties of carbon fiber-based ultra-high temperature ceramic matrix composites have been determined to aid designers who need these properties when considering using the composites in ultra-high temperature aerospace applications. The coefficient of thermal expansion (CTE) and thermal diffusivity of the composites were measured parallel and perpendicular to the ply direction; the thermal conductivity was measured using the laser-flash method and the heat capacity calculated from the relationship between the thermal diffusivity, density, and thermal conductivity. Both the CTE and thermal conductivity showed higher values across the ply and increased with increasing temperature as expected, whilst the thermal diffusivity showed higher values parallel to the ply and increased smoothly with temperature. In addition, two different but related oxyfuel torch tests, based on oxyacetylene and oxypropane, were used to evaluate the thermo-ablation behavior of the composites. The tests showed how good the composites were at withstanding the ultra-high temperatures, high heat fluxes, and gas velocities involved.     

Synthesis of Hf6Ta2O17 superstructure via spark plasma sintering for improved oxidation resistance of multi-component ultra-high temperature ceramics

Ultra-high temperature ceramics (UHTCs) have shown aspiration to overcome challenges in the thermal protection system (TPS) by designing new materials referred to as multi-component UHTCs (MC-UHTCs) in the compositional space. MC-UHTCs have shown remarkable improvement in oxidation resistance due to the formation of the Hf₆Ta₂O₁₇ superstructure during plasma exposure. Herein, the Hf₆Ta₂O₁₇ superstructure is synthesized via a solid-state reaction between HfO₂ and Ta₂O₅ powder mixtures during spark plasma sintering (SPS). The compositions chosen are 50 vol% of HfO₂ -50 vol% of Ta₂O₅ (50HO-50TO) and 70 vol% of HfO₂ -30 vol% of Ta₂O₅ (70HO-30TO). The phase quantification via Rietveld analysis showed Hf₆Ta₂O₁₇ as a principal phase with some residual Ta₂O₅ phase in both the samples. The high-temperature thermal stability of the samples was evaluated using high-velocity plasma jet exposure for up to 3 min. 50HO-50TO was able to withstand the intense plasma condition, which is attributed to the higher content of the Hf₆Ta₂O₁₇ phase (～84%) and lower strain in the Ta₂O₅ phase. The augmentation in the Hf₆Ta₂O₁₇ phase to 94.7% (in 50HO-50TO) post plasma exposure has been attributed to the invariant transformation from a liquid state to Hf₆Ta₂O₁₇ at temperatures >2500 °C during testing. The mechanical integrity is elucidated from the insignificant change in the hardness ～13.3 GPa before and 11.2 GPa after plasma exposure of the 50HO-50TO sample. As a result, the Hf₆Ta₂O₁₇ superstructure's thermo-mechanical stability suggests developing novel oxidation-resistant MC-UHTCs in compositional space for reusable space vehicle applications.     

Fabrication and characterization of carbon fiber reinforced SiC ceramic matrix composites based on 3D printing technology

A novel method has been developed to fabricate carbon fiber reinforced SiC (C_f/SiC) composites by combining 3D printing and liquid silicon infiltration process. Green parts are firstly fabricated through 3D printing from a starting phenolic resin coated carbon fiber composite powder; then the green parts are subjected to vacuum resin infiltration and pyrolysis successively to generate carbon fiber/carbon (C_f/C) preforms; finally, the C_f/C preforms are infiltrated with liquid silicon to obtain C_f/SiC composites. The 3D printing processing parameters show significant effects on the physical properties of the green parts and also the resultant C_f/C preforms, consequently greatly affecting the microstructures and mechanical performances of the final C_f/SiC composites. The overall linear shrinkage of the C_f/SiC composites is less than 3%, and the maximum density, flexural strength and fracture toughness are 2.83?±?0.03?g/cm³, 249?±?17.0?MPa and 3.48?±?0.24?MPa m^1/2, respectively. It demonstrates the capability of making near net-shape C_f/SiC composite parts with complex structures.     

Additive manufacturing of carbon fiber reinforced ceramic matrix composites based on fused filament fabrication

For the first time, carbon fiber reinforced ceramic matrix composites (CMC) were successfully fabricated by additive manufacturing (AM) using the fused filament fabrication (FFF) technology, filaments (“CF-PEEK”) with thermoplastic polyetheretherketone (PEEK) as the matrix and C-precursor, and carbon short-fibers (< 250 μm) as reinforcements. In order to prevent a re-melting of the as-printed CFRPs (C-fiber reinforced plastics) during pyrolysis at 1000 °C in N₂ensuring the freedom of design and complex parts, a prior crosslinking step at 325 °C with a dwell time of 48 h in air was introduced to stabilize and crosslink the CFRP. Due to the stabilization and the printing of degassing channels for the pyrolysis, near net shape and complex CMC parts with different C-fiber orientations (0°; ±45°; 90°) were obtained by the liquid siliconization infiltration process (LSI). The manufactured C/C-SiC parts were characterized regarding their microstructure and mechanical properties. The reinforcing C-fibers were successfully protected during the LSI-process and flexural strengths of almost 60 MPa were obtained.     

A comparative study on the effect of carbon-based and ceramic additives on the properties of fiber reinforced polymer matrix composites for high temperature applications

Ablative composites have been in use for thermal protection of space vehicles for decades. Carbon-phenolic composites have proven to perform exceptionally well in these applications. However with development in aerospace industry their performance needs improvement. In this field, different carbon-based and ceramic additives have been introduced into ablative composite systems. This review article gives a comparative analysis of researches done in this field in the recent past. Density, ablative, thermal and mechanical properties of ablative composites with different ultra-high temperature ceramic particles i.e. ZrSi₂, Cenosphere, nano-SiO₂, BN etc. and carbon-based nanoparticles i.e. CNTs, nano-Diamonds, Graphene oxide etc. used as additives, have been compared and discussed. Emphasis is put on carbon-phenolic composite systems although some epoxy matrix systems have also been discussed for comparison.     

Ultra-high temperature ceramics: Aspiration to overcome challenges in thermal protection systems

Ultra-high temperature ceramics (UHTCs) have played a significant role in fulfilling demands for the thermal protection system (TPS) in the aerospace sector, however, a promising candidate has not emerged yet. This critical review provides typical inconsistencies and new perspectives related to UHTCs in terms of: (i) material and processing: i.e., sinterability, reinforcements, microstructural evolution, (ii) properties and performance correlation with the processing conditions and resulting microstructure, and (iii) outlook on the most promising ZrB₂-HfB₂-SiC-based composites as potential candidates for hypersonic leading edge and re-entry structures. An optimal selection of the content, size and reinforcing phase (such as silicides, refractory carbides, and carbon-based, etc.) is mandated in upgrading the thermo-mechanical performance of UHTCs to sustain elevated temperature (1700 °C), exhibiting flexural/fracture strength of >300 MPa, high thermal conductivity >14.5 Wm^?1K^?1, and high oxidation resistance (<80 gm^?2 over 2 h at 1400 °C). From emphasis on the powder purity, and sintering additives on affecting the densification, mechanical properties and high temperature oxidation, improvements in the functional performance of UHTCs are carried forward with emphasis mainly on borides and carbides. Emergence of SiC as most promising sintering additive with optimal content of ～20 vol%, and with supplemented HfB₂ addition in ZrB₂-HfB₂-SiC based UHTCs have exhibited higher oxidation resistance and may serve as conceivable entrants for hypersonic vehicles. Further, the review leads the reader to developing new materials (including silicides, MAX phases, and high entropy UHTCs), incorporating novel strategies like designing layered structures or functionally graded materials (FGM), and effective joining to allow the integration of smaller components into scaled up structures. On one hand, where plasma arc-jet exposure mimics high heat-flux exposures, the utilization of multi-length-scale computational modeling (such as finite element methods, density functional theory, ab initio etc.) allows assessing the material performance under dynamic changes (of variable partial pressure, temperatures, gradation, etc.) towards perceiving new insights into the structural stability and thermo-mechanical properties of UHTCs. This review critically underlines the present state of the art and guides the reader towards the futuristic development of new class of high-temperature materials for TPSs.     

Wood-derived ultra-high temperature carbides and their composites: A review

Wood gains much attention owing to its unique characters such as cellular pore structures, low density etc. Wood-derived carbides have great potential applications as the high-temperature filters for gas or liquid, catalyst carrier, fluid/gas reservoir devices, biocatalyst supports, etc. In this paper, we review recent progress in comprehensively understanding the processing techniques, properties and applications of wood-derived carbides. The key techniques for producing wood-derived carbides involves the infiltration techniques which are categorized into six parts (slurry infiltration, polymer precursor infiltration, melting infiltration, molten salt infiltration, sol-gel infiltration, and chemical or physical vapor infiltration). The advantages and disadvantages of these techniques are discussed in details, and the according solutions for solving the problems of each technique are further proposed. The infiltration kinetics of processing carbides are also discussed in details. The investigated properties of wood-derived carbides are summarized, which includes the mechanical properties and thermal properties. The potential applications of wood-derived carbides are explored, along with an overview of the existing challenges and practical limitations. In the end, we provide future perspectives to highlight the future directions of research in this growing area.     

Multicomponent synergistically affected mechanical properties,microstructure, and oxidation resistance of Zr–Al(Si)–C based composites

Herein, in-situ Zr₃[Al(Si)]₄C₆-based composites with 10–40 vol% ZrB₂–SiC (2-to-1 molar ratio) were prepared by hot-pressing sintering at 1850 °C. The simultaneously incorporated ZrB₂–SiC constitute multicomponent reinforcements and has a synergistic effect on the matrix, which improves the sinterability, mechanical properties, and oxidation resistance of materials. It is found that both of the toughness and strength increase first and then decrease with the increasing content of ZrB₂–SiC, while the hardness increases near linearly. Zr₃[Al(Si)]₄C₆–ZrB₂–SiC shows high strength (623 MPa), toughness (7.59 MPa m^1/2), and hardness (18.6 GPa), which can be ascribed to the synergistic mechanisms of the binary ZrB₂–SiC including fine-grained strengthening, particle reinforcement, intragranular microstructure, grain's pull-out and crack bridging, etc. In addition, the oxidation kinetics of as-prepared materials follow the parabolic law, and the composite shows a low oxidation rate of 0.87 × 10⁻⁵ kg² m⁻⁴ s⁻¹ when oxidized at 1400 °C.     

Zirconium-diboride silicon-carbide composites: A review

Zirconium diboride (ZrB₂) and silicon carbide (SiC) composites have long been of interest since it was observed that ZrB₂ improved the thermal shock resistance of SiC. However, processing of these materials can be difficult due to high and different sintering temperatures and differences in the thermodynamic stability of each material. ZrB₂–SiC composites have been processed in a variety of ways including hot-pressing, spark-plasma sintering, reactive melt infiltration, pack cementation, chemical vapor deposition, chemical vapor infiltration, stereolithography, direct ink writing, selective laser sintering, electron beam melting, and binder jet additive manufacturing. Each manufacturing method has its own pros and cons. This review serves to summarize more than 60 years of research and provide a coherent resource for the variety of methods and advancements in development of ZrB₂–SiC composites.     

Synthesis and thermal performance of polymer precursor for ZrC ceramic

A novel ZrC preceramic precursor (PZC) was compounded via liquid phase chemical reaction without any organic solvent choosing ZrOCl₂·8H₂O and polyvinyl alcohol as Zr source and C source, respectively. The composition and structure of ZrC precursor were analysed through XRD, FT-IR, XPS and SEM. The results showed both Zr-O-C bonds and Zr-O bonds existed in the precursor. The results observed by SEM showed that many irregular particles were generated, whose particle sizes were mainly in the range of 0.2–3 μm. In addition, particle aggregation can be easily observed. Besides, the thermal property and pyrolysis process of PZC were studied. In accordance with XRD, the initial temperature of the earliest detection of ZrC in pyrolysis products of PZC was 1300 °C. Monoclinic ZrO₂ and tetragonal ZrO₂ can be observed at this temperature as well. Ulteriorly, when the pyrolysis temperature was risen up to 1500 °C, only ZrC ceramic can be found.     

Development of a slurry injection technique for continuous fibre ultra-high temperature ceramic matrix composites

A simple and effective slurry injection method for producing dense and uniform ultra-high ceramic matrix composites from preforms of high fibre density was developed. As this method is based on slurry injection the homogeneity is not constrained to small preform sizes; dense components of high fibre volume can be produced in theoretically any size and shape. Samples produced by this method demonstrated high and consistent densities, with the injection method obtaining densities an average 27% higher and 87% lower in variability when compared to conventional vacuum impregnation. Tomography demonstrated no bias in the ceramic powder distribution for samples produced by injection, whereas samples produced by vacuum impregnation alone displayed poor powder penetration to the centre of large samples. The new approach yielded composites that were as strong and/or more consistent in strength compared to vacuum impregnation. Thermo-ablative testing demonstrated significant improvements in protective capability for materials produced by this route.