High temperature ceramic radomes (HTCR) – A review

An electromagnetically transparent, structurally robust and environmentally resistant enclosure of radar antenna for ground based systems to modern avionics in military aircraft and missiles is called as radome. Radome materials are classified based on: (i) type of function - surface-based or flight-mode and (ii) speed of operation - subsonic, supersonic to hypersonic. The desired properties of these materials are low dielectric constant and low loss factor in addition to its capacity to withstand the high temperature of operation. Composite laminates of glass or aramid fibre reinforced polymeric resins are radome material candidates for applications in subsonic range. However, ceramics are the only viable option for military aerospace applications such as a fighter jet travelling at Mach 3 or an advanced hypersonic missile speeding up to Mach 5. This review outlines the hand-full of ceramic materials already in application as radome materials like high-purity-alumina, pyroceram, slip-cast-fused-silica, their processing technology, electromagnetic and mechanical properties, advantages and disadvantages with respect to advanced military vehicles. Use of silicon nitride based radome materials, that has exceptional mechanical strength and thermal stability up to 1400 °C is illustrated with respect to reaction bonded silicon nitride, hot pressed silicon nitride, silicon oxynitride, sialon and their composites. Design of new generation radome materials was conceptualized and discussed as applicable to silicon nitride and related ceramics, wherein incorporation of varied degree of porosity improves electromagnetic properties, simultaneously, maintaining the required mechanical strength. Multilayer and graded porosity and its influence on electromagnetic properties were briefly discussed. Si₃N₄ ceramics having controlled porosity leading to optimum electromagnetic and mechanical properties produced through systematic processing is proposed as the futuristic high temperature radome material for supersonic applications.     

High temperature stiffening of ferroelastic LaCoO3

The cyclic ferroelastic hysteretic behavior of pure LaCoO₃ perovskite ceramic has been studied at different temperatures in four point bending. The stress-strain deformation behavior of LaCoO₃ was analyzed both in the term of the maximum stress in the cycle and in terms of the temperature used when the cyclic testing was performed. The characteristics of the stress-strain hysteresis loops, such as hysteresis loop area and irreversible strain, as well as effective Young’s modulus, were analyzed, and it was established that both the loading and the temperature history have a significant influence on the mechanical behavior of LaCoO₃. Young’s modulus values are reported to be much higher in the 700–900 °C temperature range as compared to the measurements performed in the RT-400 °C temperature range.     

High temperature properties of ZnO ceramics studied by the impulse excitation technique

This study reports on impulse excitation technique (IET) measurements up to 900 °C in air performed on various grades of ZnO ceramics, containing bismuth and antimony oxides as dopants. The IET provides dynamic elastic (E-modulus) and damping properties as a function of temperature. In order to correlate the IET behaviour with the microstructure and phase evolution, SEM and high temperature XRD (HT-XRD) analysis were carried out. Damping peaks related to phase transitions were observed in the samples containing Bi₂O₃ intergranular phase. Three other peaks are tentatively interpreted as point defect relaxations.     

Cesium Release From Tungstate and Titanate Waste Form Materials in Simulated Canister Corrosion Product-Containing Solutions

The leaching of two potential ¹³⁷Cs waste form ceramics (Cs-containing hexagonal tungsten bronze (HTB) and hollandite) has been investigated in Fe(NO₃)₃ solutions of increasing concentration at 150°C over a period of 4 days. These ceramics contain within their structures reduced Mo⁵⁺/W⁵⁺ and Ti³⁺ species for the HTB and hollandite, respectively, which therefore might render them susceptible to oxidation-induced leaching. Elucidation of the extent and the mechanism of leaching of the Cs from these ceramics in the REDOX active iron nitrate medium has been investigated. Cesium (Cs) leached severely from both the Cs-loaded HTB and hollandite materials in iron nitrate solutions with virtually all of the immobilized Cs being extracted from both waste form materials in a period of 4 days at 150°C. In the case of hollandite, conversion to ilmenite and hematite was observed at low concentrations and was virtually complete in 0.5 mol/L Fe(NO₃)₃ over 4 days. In the case of the HTB, all of the Cs was extracted presumably by an ion-exchange mechanism because the structure of this oxide remained intact and iron was found in the composition. Iron oxide with a hematite structure was also easily observed in the reacted sample at high solution iron concentrations. It is shown that the leach resistance of the Cs-containing HTB can be improved by substitution of up to 20% Ti for W.     

Coupled Thermomechanical Multiscale Modeling of Alumina Ceramics to Predict Thermally Induced Fractures Under Laser Heating

This study is concerned with thermally induced fractures and failure of high weight percentage alumina ceramics. A 3D coupled thermomechanical multiscale model has been developed to simulate thermally induced fractures. In laser heating of alumina ceramics, the temperature and stress distributions have been predominantly correlated with the interfacial glass phase within alumina microstructure. A coupled thermomechanical analysis with traction–separation law has been implemented in the finite element framework as a cohesive zone model (CZM). The alumina grains are modeled as thermomechanical continuum elements separated by CZM. A thermal and mechanical analysis has been conducted using Molecular Dynamics methods to obtain the thermal conductivities and parameterize traction–separation laws for the interface of alumina ceramics at different temperatures. The coupled thermal‐mechanical analysis achieved through a finite element model in Abaqus is compared with experimental results in laser‐heating tests. The model is successful in predicting temperature distributions and thermal fractures, which could help assist in selecting proper conditions in alumina applications and fabrication processes.     

2-D Hydro-Viscoelastic Model for Convective Drying of Highly Deformable Saturated Product

The aim of this work was to simulate in two-dimensions the spatio-temporal evolution of the moisture content, the temperature, and the mechanical stress within a highly deformable and water saturated product during convective drying. The material under study was an elongated potato sample with a square section placed in hot air flow. A comprehensive hydro-thermal model had been merged with a mechanical model, assuming a viscoelastic material, a plane deformation, and an isotropic linear hydric-shrinkage of the sample. This model was validated on the basis of the average water content and core temperature curves for drying trials under different operating conditions. The material viscoelastic properties were measured by means of stress relaxation tests at different water contents. The viscoelastic behavior was described by a generalized Maxwell model whose parameters were correlated to water content. The simulations of the spatio-temporal distributions of mechanical stress were performed and interpreted in terms of product potential damage. The sample shape was also predicted all aver the drying process with reasonable accuracy.     

Modeling of Thermo-Hydro-Viscoelastic Behavior of a Partially Saturated Ceramic Material During Drying

A mathematical model to simulate the drying of a partially saturated ceramic material has been developed. The investigated problem involves coupling equations considering heat, mass, and mechanical aspects. Transport in unsaturated porous medium includes two mean mechanisms: convection for liquid and gases, and molecular diffusion in the gas mixture.

Viscoelastic rheology is applied by using the generalized Maxwell model in which the relaxation modulus depends on time and moisture content. The numerical resolution is performed to foresee the variation of moisture content, shrinkage, liquid pressure, gas pressure, temperature, and mechanical stresses during drying. The model was validated partially for porcelain material in classical convective drying. Simulation results showed the importance of using a viscoelastic model with two dependent variables in evaluating the developed mechanical stresses. The Von Mises criterion is used as a crack initiation criterion, which allows localizing the area of risk of the material's fracture.     

High Bipolar Fatigue Resistance of BCTZ Lead‐Free Piezoelectric Ceramics

(Ba, Ca)(Ti, Zr)O₃ ceramics have been considered as a potential lead‐free alternative to commonly used lead‐based piezoelectric ceramics due to their high piezoelectric performance at room temperature. In this study, the bipolar fatigue behavior of this material is investigated at room temperature. Two compositions were cycled with a bipolar electric field signal at 10 Hz with a maximum of three times the coercive field for up to approximately 10⁷ cycles. Both investigated compositions exhibited high bipolar fatigue resistance compared to other ceramics reported in the literatures. The high fatigue resistance originates from the lack of mechanical damage and a weak domain wall pinning effect due to their location in the phase transition region. It was also found that pore morphology affected bipolar fatigue behavior.     

Improving low temperature degradation of 3Y-TZP ceramics via high temperature carburizing

3Y-TZP ceramics are prepared by solid state method and surface carburization process, and the effect of surface carburization on its the low temperature degradation is studied. The conventional sintered samples completely lost its mechanical properties after aging for 15 h, while the failure time of the surface carburized samples are 300 h. In addition, the nuclear growth rate of the surface carburized samples (αd) and the nucleation rate (Nr) is lower than that of sintered samples, αd plays a dominant role in the degradation process at low temperature and is the key factor determining the aging rate. At the same time, it is found that carbon is dissolved in zirconia lattice in the form of electrically neutral atoms, which will not destroy the original charge balance and produce new oxygen vacancies when entering the interstitial site. More importantly, the precipitation rate of Y³⁺ from zirconia lattice is the key factor to determine the low-temperature phase transition of tetragonal-monoclinic(T-M). The treatment method of surface carburization has significantly improved the low-temperature degradation performance of 3Y-TZP ceramics, which provides a basis for the application of zirconia ceramics in low-temperature and humid environment.     

High mechanical quality factor and piezoelectricity in potassium sodium niobate ceramics

Plenty of works have done to enhance the piezoelectricity of potassium-sodium niobate (KNN), aiming to replace lead-zirconate titanate (PZT) in the consideration of eco-friendly requirement. However so far, KNN ceramics with high piezoelectric performances tend to have a low mechanical quality factor (Q_m), which could result in excessive dielectric loss, especially when working in high frequencies. Thus, increasing Q_m is a crucial task in KNN-based ceramics. By constructing phase boundaries together with inducing oxygen vacancies, a new KNN ceramic system is built by using conventional solid-state method with high Q_m (>250), high piezoelectric performance as well as outstanding temperature stability. Optimum overall properties of KNN-based ceramics can be as large as d₃₃ = 231 pC/N, Q_m = 355, T_C = 366 °C. This work provides a deeper insight to KNN-based ceramics with high mechanical quality factor and makes a progress on the high frequency application of lead-free ceramics.     

Theoretical and experimental investigations on high temperature mechanical and thermal properties of BaZrO3

The perovskite BaZrO₃ has high phase stability from room temperature to its melting point and therefore is regarded as a promising candidate for various high-temperature applications. In this work, the mechanical and thermal properties of BaZrO₃ at high temperatures are investigated by combining first-principles calculations and experimental approaches. BaZrO₃ has moderate mechanical properties and low thermal conductivity, being comparable to other zirconium-based and silicate structural ceramics. Its remaining Young's modulus of 174.4?GPa at 1523?K is 81.6% of 213.8?GPa at room temperature. The residual flexural strength of 127.8?MPa at 1273?K is 74% of 172.4?MPa at room temperature, while the residual value at 1673?K is still 53.4?MPa. The thermal conductivity of BaZrO₃ is 5.75?W?m^?1 K^?1 at 298?K and decreases to 2.81?W?m^?1 K^?1 at 1473?K. The good high temperature mechanical and thermal properties ensure the potential high temperature applications of BaZrO₃ and our results are expected to arouse the design of BaZrO₃-based ceramics in the near future.     

Ultra-high temperature ceramics melting temperature prediction via machine learning

Melting temperature has great influence on the high temperature properties and working temperature limits of ultra-high temperature ceramics (UHTCs) In order to bypass the challenge in the measurement of ultra-high melting points, this paper proposed a novel method to predict UHTCs melting temperature via machine learning. A dataset including more than ten thousand melting temperature data has been established, which covers 8 elements and most of the known non-oxide UHTCs. We built up an element to ceramic system framework by back propagation artificial neural network (BPANN) with the accuracy approaching to 90% and the correlation coefficients approaching to 0.95. Our work provides a probability to get the high accuracy melting temperature of UHTCs, and a more convenient way to develop novel materials with higher working temperature. The given case of melting temperature prediction of Hf-C-N ceramics proves the generality of the artificial neural network (ANN). An inter-validation of melting temperature prediction using our network with materials thermodynamics and density functional theory (DFT) has been demonstrated, indicating that our network is of powerful prediction ability.     

A non-sintering fabrication method for porous Si3N4 ceramics via sol hydrothermal process

A non-sintering fabrication method for porous Si₃N₄ ceramics with high porosity and high mechanical strength was proposed. Strength of the porous ceramics can be obtained by silica sol mass transfer process in hydrothermal conditions rather than a traditionally controlled high temperature sintering process. Under hydrothermal circumstances, silica sol is continuously transferred to the necks of Si₄N₃ powder compact, depositing there and thus consolidating the ceramic skeleton. The key of the method to obtain homogeneous microstructure and mechanical strength is how to keep the silica sol from gelatin during hydrothermal procedure. The stabilization of silica sol and its affecting factors were studied. The results indicated that ultrasonic treatment makes alkali-catalyzed silica sol remain stable even in 200?℃ hydrothermal condition, which insures consecutive silica transportation. The effect of hydrothermal time on open porosity/mechanical strength of the porous Si₄N₃ ceramics were also thoroughly investigated. The porous Si₄N₃ ceramics with open porosity above 42% and flexural strength of 45?MPa were obtained without any high temperature sintering process. This method can be widely employed for the preparation of other porous ceramics as well.     

Dynamic mechanical properties of polymer melts: The effect of molecular weight distribution on the temperature dependence of viscoelastic properties

An experimental investigation of the dynamic mechanical response of molten polymers was performed using the Maxwell Orthogonal Reheometer. One purpose of the study was to evaluate the effect of molecular weight distribution on the temperature dependence of viscoelastic properties. Data were obtained over a range of temperatures for both monodisperse and polydisperse materials which indicate that viscoelasticity is highly temperature dependent only for monodisperse polymers. On a molecular basis the reduction in temperature sensitivity for polydisperse materials logically can be attributed to the influence of the low molecular weight species present in a distribution on the relaxation spectrum. Since the relaxation spectrum largely determines all viscoelastic functions, the observations made from th dynamic data shown in this paper can be generalized to all viscoelastic experiments.     

Analysis of high temperature reduction process of Na0.5Bi0.5TiO3-based ceramics

Lead-free metamaterials with enormous effective apparent piezoelectric response has been fabricated by applying an asymmetric chemical reduction to Na_0.5Bi_0.5TiO₃ (NBT)-based ceramics. To achieve high performance, optimization of the reduction conditions is required. In this study, we analyzed the effect of reduction temperature and time on the reduction thickness of NBT-based ceramics. We found that the reduction reaction between NBT-based ceramics and graphite is an interface reaction rate-controlled process. The reduction thickness has a linear relationship with the reaction time at a fixed reduction temperature. The lower activation energy of NBT-based ceramics than that of lead-based materials indicates the lead-free ceramics are easier to be reduced. The effect of the reduction on the flexoelectric-like response was further explored, and the maximum response (?>1 mC/m) was measured in the ceramics having a reduction-thickness-to-total-thickness ratio of around 0.28. This study provides a guideline to optimize the fabrication conditions of the NBT-based metamaterials.     

High temperature shape memory polyimide ionomer

In this work, a high temperature shape memory polymer based on polyimide (PI) ionomer is prepared by introducing ionic crosslinked interaction. The ionic crosslinked points are introduced to polymer networks through the reaction between polyamic acid and calcium hydroxide before thermal imidization. The crosslinked reaction, microtopography, mechanical, thermal, and shape memory properties of PI ionomers are systematically investigated. The results show the introduction of ionic crosslinked interaction could enhance the glass transition temperature, mechanical, and shape recovery performance of ODA‐ODPA, a PI. The prepared ionomers exhibit good high temperature shape memory properties around 270 °C. The shape fixation and shape recovery ratio are over 99% and 90%, respectively. This method provided a new sight of preparing high temperature shape memory polymer, which could be used in severe conditions, like aerospace industry field. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43630.     

Rapidly fabricating Y2O3 transparent ceramics at low temperature by SPS with mesoporous powder

Fine-grained and dense highly transparent Y₂O₃ ceramics have been successfully prepared using high sintering activity mesoporous Y₂O₃ powders without any additive by spark plasma sintering (SPS). The influences of the sintering temperature on microstructure, density, optical, and mechanical properties of SPS-sintered Y₂O₃ ceramics were studied in detail. As results, the optimal Y₂O₃ ceramics with high relative density of 99.90% and fine average grain size of 140 nm were obtained at a low sintering temperature of 1140°C and a moderate load pressure of 60 MPa for 5 min. Meanwhile, the dense Y₂O₃ ceramics with 1 mm thickness after annealing show a high linear transmittance of 78% (close to 94% of the theoretical value) at 2.4–3 µm wavelength. In additions, the Vickers hardness and fracture toughness of samples can reach 8.48 GPa and 1.45 MPa m^1/2, respectively. This result proves that the high activity of mesoporous Y₂O₃ is considered to be an important means for preparing high-performance fine Y₂O₃ ceramics at low sintering temperature.     

Polymer-derived SiHfN ceramics: From amorphous bulk ceramics with excellent mechanical properties to high temperature resistant ceramic nanocomposites

Within the present work, additive-free amorphous bulk SiHfN ceramics with excellent mechanical properties were prepared by a resource-efficient low-temperature molding method, namely warm-pressing. As densification mechanism viscous flow has been identified based on cross-linking reaction. The critical problems concerning gas evolution and crystallization inducing bloating and cracking are addressed through controlled thermolysis and pressure. The microstructural evolution of the SiHfN ceramics indicates that the incorporation of Hf in perhydropolysilazane not only increases the ceramic yield (97.4 wt%) and crystallization resistance (1300 °C), but also suppresses the transformation from α-Si₃N₄ to β-Si₃N₄ at high temperatures (1700 °C). Especially, HfN/α-Si₃N₄ nanocomposites converted by the SiHfN ceramics at 1500 °C show a slight weight loss of 3.13 wt%, indicating the high temperature resistance of the ceramic nanocomposites. The method proposed in this work opens a new strategy to fabricate additive-free polycrystalline Si₃N₄- and amorphous Si₃N₄-based (nano)composites.     

Effects of oxidation temperature on microstructure and EMI shielding performance of layered SiC/PyC porous ceramics

Herein, the influence of oxidation temperature on the oxidation behavior, microstructure and electromagnetic shielding performance of layered porous ceramics has been systematically investigated. Layered SiC/PyC porous ceramics were prepared by using low-pressure chemical vapor infiltration (LPCVI) method. The oxidized SiC/PyC layered porous ceramics exhibited a negligible mass reduction of 11.94 mg·cm^?3, which indicates the excellent high-temperature oxidation resistance of porous ceramics. The electromagnetic shielding performance of SiC/PyC porous ceramics did not exhibit any obvious change even after oxidation at high temperature from 900 to 1300 °C for 10 h. The SE_T of the layered SiC/PyC porous ceramics was 24.1, 20.0, 19.5, 19.0, 19.8 dB after oxidation at 25 °C, 900 °C, 1000 °C, 1100 °C and 1300 °C, which corresponds to a decrease of 17.01%, 19.09%, 21.16% and 17.84%, respectively. The high-temperature oxidation has rendered a more significant influence on the reflection efficiency of the layered SiC/PyC porous ceramics.     

A viscoelastic–viscoplastic modeling approach for amorphous polymers in vacuum forming simulation

In this study, the simulation of a vacuum forming process employing a micromechanical inspired viscoelastic–viscoplastic model is investigated. In the vacuum forming process, a plastic sheet is heated above the glass transition temperature and subsequently forced into a mold by applying a vacuum. The model consists of a generalized Maxwell model combined with an dissipative element in series. Each Maxwell element incorporates a hyperelastic element in series with a viscous element based on a hyperbolical law. While the generalized Maxwell model considers the relaxation due to molecular alignment, the additional viscous element is a modification based on the approach of Bergström and thus considers molecular chain reptation. The model is designed with the aim to converge to the generalized linear Maxwell model in the limit of small deformation. Furthermore, the viscous modeling is temperature activated and follows the Williams–Landel–Ferry approach in the limit of linear viscoelasticity. To simulate rheological standard experiments, a physical-network-based implementation into Simscape is presented. To validate the performance of the model in thermoforming, it is implemented into Fortran programming language for finite element simulation with Abaqus/Explicit. It can be shown that the simulation is able to predict the thickness in high correlation with experimental results.