The temperature-dependent fracture strength model for ultra-high temperature ceramics

Breaking down the entire structure of a material implies severing all the bonds between its atoms either by applying work or by heat transfer. Because bond-breaking is indifferent to either means, there is a kind of equivalence between heat energy and strain energy. Based on this equivalence, we assume the existence of a constant maximum storage of energy that includes both the strain energy and the corresponding equivalent heat energy. A temperaturedependent fracture strength model is then developed for ultrahigh temperature ceramics （UHTCs）. Model predictions for UHTCs, HfB2, TiC and ZrB2, are presented and compared with the experimental results. These predictions are found to be largely consistent with experimental results.

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.

Porous Ultra-high Temperature Ceramics for Ultra-high Temperature Thermal Protection System

Ultra-high temperature ceramics(UHTCs)are a family of borides,carbides and nitrides of transition elements such as hafnium,zirconium,tantalum and niobium.They exhibit the highest known melting points,good mechanical strength,good chemical and thermal stability under certain conditions.In last decade,researchers dedicated to characterize porous UHTCs aiming to develop novel thermal insulating materials that could withstand temperatures over 2000℃.In this article,the preparation and characteristics of porous UHTCs were reviewed.Dry processing,colloidal processing and solution processing routes have been used to prepare porous UHTCs with porosities ranging from 5%to 97%and pore sizes ranging from hundreds of nanometers to hundreds of micrometers.The obtained porous UHTCs are chemically and dimensionally stable at temperatures up to 2000℃ during static state high-temperature thermal aging.

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.

Microstructure and Oxidation Behavior of ZrB_(2)-SiC Ceramics Fabricated by Tape Casting and Reactive Melt Infiltration

ZrB_(2)-based ceramics typically necessitate high temperature and pressure for sintering,whereas ZrB_(2)-SiC ceramics can be fabricated at 1500℃using the process of reactive melt infiltration with Si.In comparison to the conventional preparation method,reactive synthesis allows for the more facile production of ultra-high temperature ceramics with fine particle size and homogeneous composition.In this work,ZrSi_(2),B4C,and C were used as raw materials to prepare ZrB_(2)-SiC via combination of tape casting and reactive melt infiltration herein referred to as ZBC ceramics.Control sample of ZrB_(2)-SiC was also prepared using ZrB_(2) and SiC as raw materials through an identical process designated as ZS ceramics.Microscopic analysis of both ceramic groups revealed smaller and more uniformly distributed particles of the ZrB_(2) phase in ZBC ceramics compared to the larger particles in ZS ceramics.Both sets of ceramics underwent cyclic oxidation testing in the air at 1600℃for a cumulative duration of 5 cycles,each cycle lasting 2 h.Analysis of the oxidation behavior showed that both ZBC ceramics and ZS ceramics developed a glassy SiO_(2)-ZrO_(2) oxide layer on their surfaces during the oxidation.This layer severed as a barrier against oxygen.In ZBC ceramics,ZrO_(2) is finely distributed in SiO_(2),whereas in ZS ceramics,larger ZrO_(2) particles coexist with glassy SiO_(2).The surface oxide layer of ZBC ceramics maintains a dense structure because the well-dispersed ZrO_(2) increases the viscosity of glassy SiO_(2),preventing its crystallization during the cooling.Conversely,some SiO_(2) in the oxide layer of ZS ceramics may crystallize and form a eutectic with ZrO_(2),leading to the formation of ZrSiO_(4).This leads to cracking of the oxide layer due to differences in thermal expansion coefficients,weakening its barrier effect.An analysis of the oxidation resistance shows that ZBC ceramics exhibit less increase in oxide layer thickness and mass compared to ZS ceramics,suggesting superior oxidation resistance of ZBC ceramics.

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.

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.

Sol–gel derived porous ultra-high temperature ceramics

Ultra-high temperature ceramics(UHTCs)are considered as a family of nonmetallic and inorganic materials that have melting point over 3000℃.Chemically,nearly all UHTCs are borides,carbides,and nitrides of early transition metals(e.g.,Zr,Hf,Nb,Ta).Within the last two decades,except for the great achievements in the densification,microstructure tailoring,and mechanical property improvements of UHTCs,many methods have been established for the preparation of porous UHTCs,aiming to develop high-temperature resistant,sintering resistant,and lightweight materials that will withstand temperatures as high as 2000℃for long periods of time.Amongst the synthesis methods for porous UHTCs,sol–gel methods enable the preparation of porous UHTCs with pore sizes from 1 to 500μm and porosity within the range of 60%–95%at relatively low temperature.In this article,we review the currently available sol–gel methods for the preparation of porous UHTCs.Templating,foaming,and solvent evaporation methods are described and compared in terms of processing–microstructure relations.The properties and high temperature resistance of sol–gel derived porous UHTCs are discussed.Finally,directions to future investigations on the processing and applications of porous UHTCs are proposed.

An experimental study of ultra-high temperature ceramics under tension subject to an environment with elevated temperature,mechanical stress and oxygen

Ultra-high temperature ceramic(UHTC) composites are widely used in high-temperature environments in aerospace applications. They experience extremely complex environmental conditions during service, including thermal, mechanical and chemical loading. Therefore, it is critical to evaluate the mechanical properties of UHTCs subject to an environment with elevated temperature, mechanical stress and oxygen. In this paper, an experimental investigation of the uniaxial tensile properties of a ZrB_2-SiC-graphite subject to an environment with a simultaneously elevated temperature, mechanical stress and oxygen is conducted based on a high-temperature mechanical testing system. To improve efficiency, an orthogonal experimental design is used. It is suggested that the temperature has the most important effect on the properties, and the oxidation time and stress have an almost equal effect. Finally, the fracture morphology is characterized using scanning electron microscopy(SEM), and the mechanism is investigated. It was concluded that the main fracture mode involved graphite flakes pulling out of the matrix and crystalline fracture, which indicates the presence of a weak interface in the composites.

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.

Low thermal conductivity and high porosity ZrC and HfC ceramics prepared by in-situ reduction reaction/partial sintering method for ultrahigh temperature applications

Porous ultra-high temperature ceramics(UHTCs) are potential candidates as high-temperature thermal insulation materials. However, high thermal conductivity is the main obstacle to the application of porous UHTCs. In order to address this problem, herein, a new method combining in-situ reaction and partial sintering has been developed for preparing porous Zr C and Hf C with low conductivity. In this process, porous Zr C and Hf C are directly obtained from ZrO2/C and HfO2/C green bodies without adding any pore-forming agents. The release of reaction gas can not only increase the porosity but also block the shrinkage. The asprepared porous Zr C and Hf C exhibit homogeneous porous microstructure with grain sizes in the range of 300–600 nm and 200–500 nm, high porosity of 68.74% and 77.82%, low room temperature thermal conductivity of 1.12 and 1.01 W·m-1 K-1, and compressive strength of 8.28 and 5.51 MPa, respectively.These features render porous Zr C and Hf C promising as light-weight thermal insulation materials for ultrahigh temperature applications. Furthermore, the feasibility of this method has been demonstrated and porous Nb C, Ta C as well as Ti C have been prepared by this method.

Rapid heating thermal shock study of ultra high temperature ceramics using an in situ testing method

In this paper,the rapid cooling thermal shock behaviors of ZrB_(2)-SiC ceramics were measured using traditional water quenching method,and the rapid heating thermal shock behaviors of ZrB_(2)-SiC ceramics were investigated using a novel in situ testing method.The measured critical thermal shock temperature difference for rapid cooling thermal shock was 373.6℃;however,the critical thermal shock temperature difference for rapid heating thermal shock of ZrB_(2)-SiC ceramics was measured to be as high as 1497.2℃.The thermal stress distribution states after rapid cooling thermal shock and rapid heating thermal shock testing were analyzed using finite element analysis(FEA)method.The FEA results showed that there is a tensile stress existed on the surface for rapid cooling thermal shock,whereas there is a compressive stress existed on the surface for rapid heating thermal shock.The difference of thermal stress distribution resulted in the difference of the critical temperature difference for rapid cooling thermal shock and rapid heating thermal shock.

High strength and high porosity YB2C2 ceramics prepared by a new high temperature reaction/partial sintering process

Porous ultrahigh temperature ceramics(UHTCs) are potential candidates as reusable thermal protection materials of transpiration cooling system in scramjet engine. However, low strength and low porosity are the main limitations of porous UHTCs. To overcome these problems, herein, a new and simple in-situ reaction/partial sintering process has been developed for preparing high strength and high porosity porous YB2C2. In this process, a simple gas-releasing in-situ reaction has been designed, and the formation and escape of gases can block the shrinkage during sintering process, which is favorable to increase the porosity of porous YB2C2. In order to demonstrate the advantages of the new method, porous YB2C2 ceramics have been fabricated from Y2O3, BN and graphite powders for the first time. The as-prepared porous YB2C2 ceramics possess high porosity of 57.17%–75.26% and high compressive strength of 9.32–34.78 MPa.The porosity, sintered density, radical shrinkage and compressive strength of porous YB2C2 ceramics can be controlled simply by changing the green density. Due to utilization of graphite as the carbon source, the porous YB2C2 ceramics show anisotropy in microstructure and mechanical behavior. These features render the porous YB2C2 ceramics promising as a thermal-insulating light-weight component for transpiration cooling system.

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.

振荡热压烧结ZrB_(2)-SiC陶瓷的力学性能

采用振荡热压烧结(HOP)和热压烧结(HP)工艺制备了ZrB_(2)-SiC陶瓷,研究了振荡压力对ZrB_(2)-SiC陶瓷致密化及力学性能的影响。结果表明,与采用HP工艺制备ZrB_(2)-SiC陶瓷相比,HOP工艺的致密化速率有显著提升;ZrB_(2)与SiC两相界面结合良好;HOP工艺制备的ZS30样品的硬度和断裂韧性分别达到了21.1 GPa和7.3 MPa·m^(1/2),较采用HP工艺在相同烧结参数下制备的试样有大幅提升。HOP在制备高性能ZrB_(2)-SiC陶瓷方面展现出良好发展前景。

Insight into the effect of Ti substitutions on the static oxidation behavior of (Hf,Ti)C at 2500℃

Hf-based carbides are highly desirable candidate materials for oxidizing environments above 2000℃.However,the static oxidation behavior at their potential service temperatures remains unclear.To fill this gap,the static oxidation behavior of(Hf,Ti)C and the effect of Ti substitutions were investigated in air at 2500℃ under an oxygen partial pressure of 4.2 kPa.After oxidation for 2000 s,the thickness of the oxide layer on the surface of(Hf,Ti)C bulk ceramic is reduced by 62.29%compared with that on the HfC monocarbide surface.The dramatic improvement in oxidation resistance is attributed to the unique oxide layer structure consisting of various crystalline oxycarbides,HfO_(2),and carbon.The Ti-rich oxycarbide((Ti,Hf)C_(x)O_(y))dispersed within HfO_(2) formed the major structure of the oxide layer.A coherent boundary with lattice distortion existed at the HfO2/(Ti,Hf)C_(x)O_(y) interface along the(111)crystal plane direction,which served as an effective oxygen diffusion barrier.The Hfrich oxycarbide((Hf,Ti)CxOy)together with(Ti,Hf)C_(x)O_(y),HfO_(2),and precipitated carbon constituted a dense transition layer,ensuring favorable bonding between the oxide layer and the matrix.The Ti content affects the oxidation resistance of(Hf,Ti)C by determining the oxide layer's phase distribution and integrity.

Ablation behaviour of(Hf-Ta-Zr-Nb)C high entropy carbide ceramic at temperatures above 2100℃

The ablation behaviour of(Hf-Ta-Zr-Nb)C high entropy carbide(HEC4)was studied at temperatures above 2100℃using a plasma flame gun in air.The microstructures,phase and chemical compositions of the HEC4 samples were investigated after ablation.The mass ablation rate of the HEC4 samples increased with increasing ablation time from 0.21 mg cm^(−2)s^(−1)for 60 s to 0.45 mg cm^(−2)s^(−1)for 120 s.Com-pared to the mono-and binary carbides with commonly decreased mass and thickness after ablation,the HEC4 samples with the increased mass and thickness after ablation showed good resistance to mechan-ical scouring at such high temperatures and an oxidation controlled ablation mechanism.The ablation processes mainly include the oxidation of the carbide,the phase separation of the oxides,the melting of oxides,and the diffusion of oxygen.A composition gradient in the oxide layer was detected due to the different melting temperatures of the different oxides;Nb-Ta rich oxides formed at the front surface melted and became enriched at the edge of the samples,and the Zr-Hf rich oxides were enriched in the centre of the samples.The oxide layer with complex compositions and phase distributions acted as an effective ablation barrier.

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.