Effects of mechanical boundary conditions on thermal shock resistance of ultra-high temperature ceramics

The effects of mechanical boundary conditions, often encountered in thermalstructural engineering, on the thermal shock resistance（TSR） of ultra-high temperature ceramics（UHTCs） are studied by investigating the TSR of a UHTC plate with various types of constraints under the first, second, and third type of thermal boundary conditions. The TSR of UHTCs is strongly dependent on the heat transfer modes and severity of the thermal environments. Constraining the displacement of the lower surface in the thickness direction can significantly decrease the TSR of the UHTC plate, which is subject to the thermal shock at the upper surface. In contrast, the TSR of the UHTC plate with simply supported edges or clamped edges around the lower surface is much better.

High speed laser cladding as a new approach to prepare ultra-high temperature ceramic coatings

Ultra-high temperature ceramic(UHTC)coatings are used to protect the hot-end components of hypervelocity aerocrafts from thermal ablation.This study provides a new approach to fabricate UHTC coatings with high speed laser cladding(HSLC)technology,and places more emphasis on investigating the formation mechanism,phase compositions,and mechanical properties of HSLC-UHTC coatings.Results show that a well-bonded interface between the coating and the tantalum alloy substrate can be formed.The coating is mainly composed of(Zr,Ta)C ceramic solid solution phase with a content of higher than 90% by volume and Ta(W)metal solid solution phase.At a relatively high powder feeding rate,the ZrC ceramic phase appears in the coating while a dense ZrC UHTC top layer with a thickness of up to~50μm is successfully fabricated.As for the mechanical properties of the HSLC coatings,the fracture toughness of the coating decreases with the increase of powder feeding rate.The increase of carbide solid solution phase can significantly improve the high temperature microhardness(552.7±1.8 HV0.5@1000℃).The innovative design of HSLC ZrC-based coatings on refractory alloys accomplishes continuous transitions on microstructure and properties from the substrate to the UHTC top layer,which is a very promising candidate scheme for thermal protection coating.

Fabrication and Thermal Structural Characteristics of Ultra-high Temperature Ceramic Struts in Scramjets

ZrB_2-SiC based ultra-high temperature ceramic（UHTC） struts were firstly proposed and fabricated with the potential application in the combustor of scramjets for fuel injection and flame-holding for their machinability and excellent oxidation/ablation resistance in the extreme harsh environment. The struts were machined with electrospark wire-electrode cutting techniques to form UHTC into the desired shape, and with laser drilling to drill tiny holes providing the channels for fuel injection. The integrated thermal-structural characteristic of the struts was evaluated in high-temperature combustion environment by the propane-oxygen free jet facility, subject to the heat flux of 1.5 MW/m^2 lasting for 300 seconds, and the struts maintained integrity during and after the first experiment. The experiments were repeated for verifying the reusability of the struts. Fracture occurred during the second repeated experiment with the crack propagating through the hole. Finite element analysis（FEA） was carried out to study the thermal stress distribution in the UHTC strut. The simulation results show a high thermal stress concentration occurs at the hole which is the crack initiation position. The phenomenon is in good agreement with the experimental results. The study shows that the thermal stress concentration is a practical key issue in the applications of the reusable UHTC strut for fuel injection structure in scramjets.

Advances in ultra-high temperature ceramics,composites,and coatings

Ultra-high temperature ceramics(UHTCs)are generally referred to the carbides,nitrides,and borides of the transition metals,with the Group IVB compounds(Zr&Hf)and TaC as the main focus.The UHTCs are endowed with ultra-high melting points,excellent mechanical properties,and ablation resistance at elevated temperatures.These unique combinations of properties make them promising materials for extremely environmental structural applications in rocket and hypersonic vehicles,particularly nozzles,leading edges,and engine components,etc.In addition to bulk UHTCs,UHTC coatings and fiber reinforced UHTC composites are extensively developed and applied to avoid the intrinsic brittleness and poor thermal shock resistance of bulk ceramics.Recently,high-entropy UHTCs are developed rapidly and attract a lot of attention as an emerging direction for ultra-high temperature materials.This review presents the state of the art of processing approaches,microstructure design and properties of UHTCs from bulk materials to composites and coatings,as well as the future directions.

Elucidating the role of preferential oxidation during ablation:Insights on the design and optimization of multicomponent ultra-high temperature ceramics

Multicomponent ultra-high temperature ceramics(UHTCs)are promising candidates for thermal protection materials(TPMs)used in aerospace field.However,finding out desirable compositions from an enormous number of possible compositions remains challenging.Here,through elucidating the role of preferential oxidation in ablation behavior of multicomponent UHTCs via the thermodynamic analysis and experimental verification,the correlation between the composition and ablation performance of multicomponent UHTCs was revealed from the aspect of thermodynamics.We found that the metal components in UHTCs can be thermodynamically divided into preferentially oxidized component(denoted as MP),which builds up a skeleton in oxide layer,and laggingly oxidized component(denoted as ML),which fills the oxide skeleton.Meanwhile,a thermodynamically driven gradient in the concentration of MP and ML forms in the oxide layer.Based on these findings,a strategy for pre-evaluating the ablation performance of multicomponent UHTCs was developed,which provides a preliminary basis for the composition design of multicomponent UHTCs.

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 ma- terials, 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 compos- ites 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-sito reaction, hot pressing （HP）, etc; and the advantages and drawbacks of each method are briefly dis- cussed. 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 propul- sions anti 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 distri- bution of carbon fibers, UHTCs and pores, which will be an important issue for future development of carbon fiber reinforced UHTC composites.

Design and preparation of an ultra-high temperature ceramic by in-situ introduction of Zr_(2)[Al(Si)]_(4)C_(5) into ZrB_(2)-SiC:Investigation on the mechanical properties and oxidation behavior

Novel ZrB_(2)-matrix composites were designed and prepared by in-situ introducing SiC and Zr_(2)[Al(Si)]_(4)C_(5) simultaneously for the first time.The obtained composites were dense and showed good mechanical properties,especially the strength and toughness,706 MPa and 7.33 MPa·m^(1/2),respectively,coupled with high hardness of 21.3 GPa,and stiffness of 452 GPa.SiC and Zr_(2)[Al(Si)]_(4)C_(5) constituted a reinforcing system with synergistic effects including grain refinement,grain pull-out as well as crack branching,bridging,and deflection.Besides,the oxidation results of the composites showed that the oxidation kinetics followed the parabolic law at 1600℃,and the oxidation rate constants increased with the increase of Zr_(2)[Al(Si)]_(4)C_(5) content.The formation and evolution model of the oxidation structure was also investigated,and the oxide scale of the composite exhibited a three-layer structure.

Using PyC modified 3D carbon fiber to reinforce UHTC under low temperature sintering without pressure

Finding the optimum balance between strength and toughness,as well as acquiring reliable thermal shock resistance and oxidation resistance,has always been the most concerned topic in the discussion of ultra-high temperature ceramic composites.Herein,PyC modified 3D carbon fiber is used to reinforce ultra-high temperature ceramic(UHTC).The macroscopic block composite with large size is successfully fabricated through low temperature sintering at 1300℃without pressure.The prepared PyC modified 3D C_(f)/ZrC-SiC composites simultaneously possess excellent physical and chemical stability under the synergistic effect of PyC interface layer and low temperature 1/2 sintering without pressure.The fracture toughness is increased in magnitude to 13.05±1.72 MPa·m^(1/2)accompanied by reliable flexural strength of 251±27 MPa.After rapid thermal shock spanning from room temperature(RT)to 1200℃,there are no visible surface penetrating cracks,spalling,or structural fragmentation.The maximum critical temperature difference reaches 875℃,which is nearly three times higher than that of traditional monolithic ceramics.The haunting puzzle of intrinsic brittleness and low damage tolerance are resolved fundamentally.Under the protection of PyC interface layer,the carbon fibers around oxide layer and matrix remain structure intact after static oxidation at 1500℃for 30 min.The oxide layer has reliable physical and chemical stability and resists the erosion from fierce oxidizing atmosphere,ensuring the excellent oxidation resistance of the composites.In a sense,the present work provides promising universality in designability and achievement of 3D carbon fiber reinforced ceramic composites.

Influence of equiatomic Zr/(Ti,Nb)substitution on microstructure and ultra-high strength of(Ti,Zr,Nb)C medium-entropy ceramics at 1900℃

High-temperature mechanical properties of medium-entropy carbide ceramics have attracted significant attention.Tailoring the microstructure is an effective way to improve these high-temperature mechanical properties,which can be affected by the evolution of the enthalpy and entropy,as well as by lattice distortion and sluggish diffusion.In this study,the effects of equiatomic Zr/(Ti,Nb)substitution(Zr content of 10-40 at%)on the microstructure and high-temperature strength of(Ti,Zr,Nb)C medium-entropy ceramics were investigated.The grain size of the(Ti,Zr,Nb)C medium-entropy ceramics was refined from 9.4±3.7 to 1.1±0.4μm with an increase in the Zr content from 10.0 to 33.3 at%.A further increase in the Zr content to 40 at%resulted in a slight increase in the grain size.At 1900℃,the(Ti,Zr,Nb)C medium-entropy ceramics with the Zr contents of 33.3 and 40 at%exhibited ultra-high flexural strengths of 875±43 and 843±71 MPa,respectively,which were higher than those of the transition metal carbides previously reported under similar conditions.Furthermore,relatively smooth grain boundaries,which were detected at a test temperature of 1000℃,transformed into curved and serrated boundaries as the temperature increased to 1900℃,which may be considered the primary reason for the improved high-temperature flexural strength.The associated mechanism was analyzed and discussed in detail.

C/SiC喷管及其超高温抗氧化涂层烧蚀行为模拟研究

目的提高C/SiC材料发动机喷管的高温抗烧蚀性能。方法基于质量、能量守恒和物性方程建立发动机喷管内燃气湍流模型,应用数值模拟方法计算喷管基体和各涂层的线烧蚀速率,并验证模型的准确性。通过比较不同种类涂层的抗烧蚀性能及涂层间匹配性,建立多元复合涂层体系,分析体系烧蚀行为及烧蚀机理,对HfO2-ZrC-SiC-C/SiC四元体系在不同温度下的线烧蚀速率进行计算。结果 Hf系、Zr系涂层抗氧化烧蚀性能优异,最大线烧蚀速率皆处于0.3~1.2μm/s之间。HfO2具有良好的抗烧蚀性能和自身稳定性。相较其他体系,HfO2-ZrC-SiC-C/SiC体系喷管的喉部及扩散段线烧蚀率更低。体系在7 MPa下,分别在1700、2100、2500、2900K计算了线烧蚀速率,最大线烧蚀速率区域产生了迁移现象,各温度梯度线烧蚀速率分别提高了174%、20.22%、18.04%。结论 HfO2能够有效地降低喷管收敛段的烧蚀速率,且适合作为复合涂层体系最外层。温度升高明显加剧了化学反应烧蚀和机械剥蚀,高温度下机械剥蚀是烧蚀的主要因素。

Fabrication and microstructure of ZrB_2–ZrC–SiC coatings on C/C composites by reactive melt infiltration using ZrSi_2 alloy

ZrB_2–ZrC–SiC ternary coatings on C/C composites are investigated by reactive melt infiltration of ZrSi_2 alloy into pre-coatings. Two different pre-coating structures, including porous B_4C–C and dense C/B, are designed by slurry dip and chemical vapor deposition(CVD) process respectively. The coating prepared by reactive melt infiltration(RMI) into B_4C–C presents a flat and smooth surface with a three-layer cross-sectional structure, namely interior SiC transition layer, gradient ZrB_2–ZrC–SiC layer, and ZrB_2–ZrC exterior layer. In comparison, the coating prepared by RMI into C/B shows a more granular surface with a different three-layer cross-sectional structure, interior unreacted B–C pre-coating layer, middle SiC layer, and exterior ZrB_2–ZrC–ZrSi_2 layer. The forming mechanisms of the specific microstructures in two coatings are also investigated and discussed in detail.

Thermal shock behavior of ZrB2-SiC ceramics with different quenching media

The thermal shock behavior of ZrB2-SiC ceramics was studied with water, air and methyl silicone oil as quenching media, respectively. The temperature of all coolants was room temperature （25℃） and the residual strength of the ceramics after quenching was tested. The strength of the ceramics after water quenching had an obvious drop when the temperature difference, AT, was about 275℃, while the residual strength of the specimens quenched by air and silicone oil only varied a little and even increased slightly when the temperature difference was higher than 800℃. The different thermal conductive coefficient of the coolants and surface heat transfer coefficient resulted in the differences in the thermal shock behavior. The formation of oxidation layer was beneficial for improving the residual strength of the ceramics after quenching.

Oxidation behavior of non-stoichiometric(Zr,Hf,Ti)C_(x) carbide solid solution powders in air

Multi-component solid solutions with non-stoichiometric compositions are characteristics of ultra-high temperature carbides as promising materials for hypersonic vehicles.However,for group IV transition-metal carbides,the oxidation behavior of multi-component non-stoichiometric(Zr,Hf,Ti)C_(x)carbide solid solution has not been clarified yet.The present work fabricated four kinds of(Zr,Hf,Ti)C_(x)carbide solid solution powders by free-pressureless spark plasma sintering to investigate the oxidation behavior of(Zr,Hf,Ti)C_(x)in air.The effects of metallic atom composition on oxidation resistance were examined.The results indicate that the oxidation kinetics of(Zr,Hf,Ti)C_(x)are composition dependent.A high Hf content in(Zr,Hf,Ti)C_(x)was beneficial to form an amorphous Zr-Hf-Ti-C-0 oxycarbide layer as an oxygen barrier to enhance the initial oxidation resistance.Meanwhile,an equiatomic ratio of metallic atoms reduced the growth rate of(Zr,Hf,Ti)O_(2)oxide,increasing its phase stability at high temperatures,which improved the oxidation activation energy of(Zr,Hf,Ti)C_(x).

Fabrication and microstructure evolution of C_(sf)/ZrB_(2)-SiC composites via direct ink writing and reactive melt infiltration

Fiber damage and uniform interphase preparation are the main challenges in conventional short fiber reinforced ceramic matrix composites.In this work,we develop a novel processing route in fabrication of short carbon fiber reinforced ZrB_(2)-SiC composites(C_(sf)/ZrB_(2)-SiC)overcoming the above two issues.At first,C_(sf) preforms with oriented designation and uniform PyC/SiC interphase are fabricated via direct ink writing(DIW)of short carbon fiber paste followed by chemical vapor infiltration.After that,ZrB_(2) and SiC are introduced into the preforms by slurry impregnation and reactive melt infiltration,respectively.Microstructure evolution and optimization of the composites during fabrication are investigated in detail.The as-fabricated C_(sf)/ZrB_(2)-SiC composites have a bulk density of 2.47 g/cm^(3),with uniform weak interphase and without serious fiber damage.Consequently,non-brittle fracture occurs in the C_(sf)/ZrB_(2)-SiC composites with widespread toughening mechanisms such as crack deflection and bridging,interphase debonding,and fiber pull-out.This work provides a new opportunity to the material design and selection of short fiber reinforced composites.