Electrospun flexible calcium zirconate fiber membrane with excellent thermal stability and alkali resistance

Ceramic fibrous membranes have promising application in gas solid filtration and in areas requiring high thermal insulation, as well as catalyst supports, owing to their high porosity and low thermal conductivity. However, achieving flexible ceramic fibrous membranes that are stable at high temperatures remains a challenge. In the present work, a CaZrO₃ fibrous membrane with excellent stability at 1200 °C and good flexibility at 1100 °C was achieved using a combination of sol-gel and electrospinning methods. The thermal decomposition process and microstructure evolution of CaZrO₃ precursor fibers at high temperatures were discussed. The single orthorhombic phase of CaZrO₃ fibers was stable up to 1400 °C. Furthermore, the CaZrO₃ fibrous membrane exhibited excellent alkaline resistance. The excellent thermal stability and flexibility of the CaZrO₃ fibrous membrane make it a promising candidate for high-temperature applications.     

Effect of hafnium oxide on continuous aluminum oxide-mullite-hafnium oxide composite ceramic fibers

The Al₂O₃-mullite-HfO₂ (AMH) ceramic fiber with a 20 wt% of HfO₂ has demonstrated good tensile strength and good high-temperature stability due to the tiny diameter and small grains even at high temperatures. To investigate the effect of HfO₂ on crystal behavior and high-temperature performance, continuous AMH ceramic fibers with different HfO₂ contents (0 wt%, 10 wt%, and 50 wt%) were prepared by melt-spinning of polymer precursors. The effect of HfO₂ on the crystal form transition process, mechanical properties, and high-temperature resistance of AMH fibers was studied by in-situ XRD and STEM. The AMH fibers with 50 wt% HfO₂ had the highest strength retention rate of 78.33% after heat treatment at 1200 °C for 0.5 h. After 0.5 h of heat treatment at 1500 °C, the grain size of the AMH fibers with 50 wt% HfO₂ was still less than 200 nm.     

Phase transformation and thermal conductivity of the APS Y2O3 doped HfO2 coating with hybrid structure

Hafnia-based materials are very promising to serve as thermal protecting coatings at temperature above 1200 °C. In this work, two kinds of 8 mol% Y₂O₃ stabilized HfO₂ ceramic coatings (YSH-SN and YSH-MX) with conventional and hybrid structures were prepared by air plasma spray (APS) method. The microstructure, thermal conductivity and the mechanical properties of the coatings before and after thermal exposure at 1300 °C were compared in detail. Results show that the as-sprayed YSH-MX has a hybrid laminated structure of monoclinic HfO₂ and cubicY₂O₃ splats, and transforms to monoclinic HfO₂ and cubic YSH after thermal exposure, while the YSH-SN is composed of major tetragonal YSH phase and transforms to monoclinic HfO₂ and cubic YSH afterward. Thermal conductivities at ultra-high temperature (1600 °C) before and after thermal exposure for those two coatings are close, and the fracture toughness in the direction parallel to the interface exceeds 2.1 MPa m^0.5. The YSH-MX coating with a hybrid structure provides insights to conveniently prepare gradient coating or other coatings with complex structures.     

Microstructure evolution and mechanical behavior of a mullite fiber heat-treated from 1100 to 1300°C

In this paper, the effect of phase transformation on microstructure evolution and mechanical behaviors of mullite fibers was well investigated from 1100 to 1300°C. In such a narrow temperature range, the microstructure and mechanical properties showed great changes, which were significant to be studied. The temperature of the alumina phase transformation started at below 1100°C. The main phases in fibers were γ-Al₂O₃ and δ-Al₂O₃ with amorphous SiO₂ at 1150°C. The stable α-Al₂O₃ formed at 1200°C. Then the mullite phase reaction occurred. As the alumina phase reaction took place, the tensile strength increased with the increasing temperature. In particular, the filaments achieved the highest strength at 1150°C with 1.98 ± 0.17 GPa, and the Young's modulus was 163.08 ± 4.69 GPa, showing excellent mechanical performance. After 1200°C, the mullite phase reaction went on with the crystallization of orthorhombic mullite. The density of surface defects increased rapidly due to thermal grooving, which led to mechanical properties degrade sharply. The strength at 1200°C was 1.01 ± 0.15 GPa with a strength retention of 63.13%, and the Young's modulus was 184.14 ± 10.36 GPa. While at 1300°C, the tensile strength was 0.64 ± 0.14 GPa with a strength retention of only 40.00%.     

Continuous aluminum oxide-mullite-hafnium oxide composite ceramic fibers with high strength and thermal stability by melt-spinning from polymer precursor

Continuous aluminum oxide-mullite-hafnium oxide (AMH) composite ceramic fibers were obtained by melt-spinning and calcination from polymer precursor that synthesized by hydrolysis of the aluminum isopropoxide, dimethoxydimethylsilane and hafnium alkoxide. Due to the fine diameter of 8–9 µm, small grain size of less than 50 nm and the composite crystal texture, the highest tensile strength of AMH ceramic fibers was 2.01 GPa. And the AMH ceramic fibers presented good thermal stability. The tensile strength retention was 75.48% and 71.49% after heat treatment at 1100 °C and 1200 °C for 0.5 h respectively, and was 61.57% after heat treatment at 1100 °C for 5 h. And the grain size of AMH ceramic fibers after heat treatment was much smaller than that of commercial alumina fibers even when the heat treatment temperature was elevated to 1500 °C, benefited by the grain size inhibition of monoclinic-HfO₂ (m-HfO₂) grains distributed on the boundary of alumina and mullite grains.     

Fabrication of lightweight ZrO2 fiberboards using hollow ZrO2 fibers

ZrO₂ fiberboards with ultra-low densities (0.34–0.40 g/cm³) were fabricated using biomorphic ZrO₂ hollow fibers, which have a lower density and better thermal insulation than traditional ZrO₂ solid fibers. The effects of sol binder content, sintering temperature, and proportion of solid fibers on the density, microstructure, compressive strength, linear shrinkage, and thermal conductivity of lightweight ZrO₂ fiberboards were investigated. The results showed that the hollow features of biomorphic ZrO₂ fibers were successfully maintained after they were made into ZrO₂ fiberboards, which made them less dense and thermally conductive. The best conditions were found to be a sol binder content of 30 vol%, sintering temperature of 1400 °C, and 20 wt% sintered solid fibers to balance thermal insulation and compressive strength. The results show that the density and thermal conductivity of lightweight ZrO₂ fiberboard gives it obvious advantages as a heat-insulating ceramic. Specifically, when the sintering temperature was 1400 °C, the sample had an ultra-low density of 0.34–0.40 g/cm³, a thermal conductivity of 0.101–0.116 W/(m·K) (at 500 °C), a compressive strength of 0.05–0.24 MPa, and a linear shrinkage of 9.4–13%.     

Ultra-flexible Al2O3 fibers: A novel catalyst support material for sustainable catalysis

Flexible aluminum oxide (Al₂O₃) fibers were prepared by the blow spinning method and their potential as a high-temperature catalyst support was investigated. The synthesized Al₂O₃ fibers exhibited remarkable flexibility in both mechanical compression and recovery tests, which remained intact in a wide temperature range from −196 °C to 1200 °C. Moreover, their low thermal conductivity of 0.030 W K⁻¹∙m⁻¹, demonstrated an outstanding thermal insulation. Subsequently, nickel nanoparticles were uniformly distributed on the surface of the Al₂O₃ fibers as a self-supporting catalyst using a conventional impregnation method. The resulting self-supporting Ni/Al₂O₃ catalyst demonstrated remarkable thermo-catalytic performance and re-activation capability at high temperatures for thermocatalytic reaction of dry reforming of methane (DRM). Our findings highlight the potential of pure Al₂O₃ flexible fibers as a versatile material for various industrial applications, including high-temperature catalysis.     

Effect of the HfO2/SiO2 pre-mixing ratio and heating temperature on the formation of HfSiO4 as a bond coat of environmental barrier coatings

As the operating temperature of advanced gas turbines typically exceeds 1400 °C, it has been required to replace conventional Si bond coat in environmental barrier coatings (EBCs) with materials possessing higher thermal stability. Since HfSiO₄ has excellent thermal properties such as a high melting point, phase stability over 1400 °C, and CTE matches with that of the SiC-based ceramic matrix composites, it has attracted much attention as a next-generation bond coat material. In this study, HfSiO₄ bond coat was successfully formed by atmospheric plasma spray with pre-mixed HfO₂-SiO₂ powders (molar ratios: 7:3 and 5:5) followed by heat treatment. Effect of molar ratios of the HfO₂-SiO₂ and post-heat treatment temperature (1375 and 1475 °C) on the formation of HfSiO₄ were studied. An oxidation test of the HfSiO₄ coating was carried out at 1475 °C with the conventional Si bond coat to verify whether the new bond coat was suitable for use in a thermal environment of 1400 °C or higher. From the results, the HfO₂/SiO₂ ratio of 5:5 was suitable for the formation of HfSiO₄ than that of 7:3. After heat treatment at 1475 °C, the ratio of HfSiO₄ phase was 84.35%. The higher content of HfSiO₄ formed under 1475 °C, meaning the higher heat treatment temperature accelerated the HfSiO₄ formation. In the oxidation test at 1475 °C, the new HfSiO₄ bond coat showed no cracks and maintained its integrity, but the Si bond coat was oxidized and cracked severely. Therefore, it can be concluded that the new HfSiO₄ bond coat formed from 5HfO₂–5SiO₂ coating is a potential candidate as a next-generation bond coat material in EBCs.     

Flexible TiO2 ceramic fibers near-infrared reflective membrane fabricated by electrospinning

Titanium oxide is a potential high temperature reflective material due to its high melting point, large refractive index, and suitable band gap. The flexible TiO₂ ceramic fibers membrane was successfully fabricated by sol–gel method using the polyacetylacetonetitanium (PAT) as the precursor. In order to obtain high-quality TiO₂ fibers, the PAT precursor with good stability and good spinnability was optimized by adjusting the molar ratio of acetylacetone to Ti to 1:1. The TiO₂ fibers heat-treated at 700?°C had a diameter of 400–500?nm. The crystal phase of TiO₂ fibers was anatase, and the surface of fibers was smooth without obvious defects. In addition, the TiO₂ ceramic fibers membrane heat-treated at 700?°C had good flexibility and tensile strength, and the average reflectance in the wavelength range of 500–2500?nm was up to 91.3%. The fibers membrane exhibits a significant reflection effect in the practical experiments and maintained good morphology of the fibers after 1200?°C test.     

Novel synthesis of ZrO2-SiCw-C insert ring materials for slide plates

To reduce the cost and firing temperature of traditional ZrO₂ insert rings, the new ZrO₂-SiC_w-C (w-whisker) insert ring materials were successfully synthesized using ZrO₂, Si, graphite powders as starting materials, and phenolic resin as binder. The effects of amount of Si powder addition (5, 8 and 11 wt%) and firing temperatures (1100 °C, 1200 °C and 1400 °C) on the phase composition, microstructure and properties of as-obtained products have been investigated. The results show that Si reacts with C or CO at high temperature to form SiC_w, which intersperses in the ZrO₂ material to develop an interlocking network structure, resulting in strengthening effect and leading to an increase in the strength of the composites. The composites have good oxidation resistance due to the formation of some glass film on the sample surface. The optimum firing temperature is 1200 °C, which is much lower than that of pure ZrO₂ material (>1700 °C). The as-prepared ZrO₂-SiC_w-C materials possess good properties, making good prospects for fabricating insert rings of slide plates.     

Oxidation resistance and thermal stability of the SiC-ZrB2 composite ceramic fibers

In this study, continuous SiC-ZrB₂ composite ceramic fibers were synthesized from a novel pre-ceramic polymer of polyzirconocenecarbosilane (PZCS) via melt spinning, electron beam cross-linking, pyrolysis, and finally sintering at 1800°C under argon. The ZrB₂ particles with an average grain size of 30.7 nm were found to be uniformly dispersed in the SiC with a mean size of 59.7 nm, as calculated using the Scherrer equation. The polycrystalline fibers exhibit dense morphologies without any obvious holes or cracks. The tensile strength of the fibers was greater than 2.0 GPa, and their elastic modulus was ~380 GPa. After oxidation at 1200°C for 1 hour, the strength of the fibers did not decrease despite a small loss of elastic modulus. Compared to the advanced commercial SiC fibers of Tyranno SA, the fibers exhibited improved high-temperature creep resistance in the temperature range 1300-1500°C.     

Processing,Mechanical Characterization,and Alkali Resistance of SiliconBoronOxycarbide (SiBOC) Glass Fibers

A borosilicate sol–gel solution is synthesized using a mixture of methyltriethoxysilane, dimethyldiethoxysilane, and boric acid. SiBOC gel fibers are produced from the as‐synthesized sol–gel solution using a spinning apparatus. Subsequently, SiBOC glass fibers are prepared through pyrolysis under argon atmosphere at 1000°C and 1200°C. Mechanical properties of the SiBOC glass fibers are studied by measuring the tensile strength and the elastic modulus. The results show a high tensile strength ?1300 and 1058 MPa, and a high Young modulus ?79 and 95.5 GPa, for the fibers prepared at 1000°C and 1200°C, respectively. Furthermore, alkali resistance of the SiBOC fibers is investigated by measuring the tensile strength after soaking them for 20 h in NaOH and Ca(OH)₂ solutions at 100°C. For comparison, the same measurements are performed on commercial AR and E glass fibers. The SiBOC fibers show excellent alkaline resistance and perform better than commercial AR fibers. Indeed, SiBOC fibers retain 80%–90% of the initial strength after Ca(OH)₂ attack.     

High-temperature performances of Si-HfO2-based environmental barrier coatings via atmospheric plasma spraying

To improve high-temperature bearing capability of coatings, novel agglomerated Si-HfO₂ powders were prepared by adding HfO₂ powders into original Si powders by spray drying method. Three-layer environmental barrier coatings (EBCs) with Si-HfO₂ bond layer, Yb₂Si₂O₇ intermediate layer and Yb₂SiO₅ surface layer were prepared on SiC ceramic substrates by atmospheric plasma spraying (APS). The high temperature properties of coatings were systematically investigated. The results indicated that the coatings had good high temperature oxidation resistance, and remained intact after being oxidized or steam corrosion at 1400 °C for 500 h, so the addition of HfO₂ improved the thermal cycling performances of the coating. The HfO₂ in Si bond coating could effectively inhibit the growth of thermal grown oxide at high temperatures. This work indicates that the high temperature properties of the coatings are improved by this novel EBCs using the novel agglomerated Si-HfO₂ powders.     

Preparation,properties and high-temperature oxidation resistance of MoSi2-HfO2 composite coating to protect niobium using spent MoSi2-based materials

Industrial spent MoSi₂-based materials and HfO₂ were recycled as raw materials to fabricate MoSi₂-HfO₂ composite coating by spark plasma sintering (SPS). The microstructural evolution of the coatings was characterized and the 1500 °C oxidation behavior was explored. Cracks penetrated through the MoSi₂ coating while no cracks can be found in the HfO₂-containing composite coating owing to the reduction of the mismatch of thermal expansion coefficient (CTE). Good metallurgical bonding was exhibited since (Mo,Nb)₅Si₃ diffusion layer was found in the HfO₂-containing coating by the diffusion of Nb and Si across the interface without gaps. After 1500 °C oxidation of 20 h, cracks appeared in the surface of SiO₂ layer on MoSi₂ coating while the HfO₂-containing composite coating possessed crack-free oxide scale. HfSiO₄ with high temperature (>2900 °C) is formed during oxidation and it inlays in the silica oxide scale to improve the stability. Compared to MoSi₂ coating, Nb coated MoSi₂-HfO₂ has thinner oxide scale with lower mass gain during oxidation, thus presenting better high-temperature anti-oxidation properties.     

Optical and mechanical properties of amorphous bulk and eutectic ceramics in the HfO2–Al2O3–Y2O3 system

Bulk glasses containing HfO₂ nano-crystallites of 20–50 nm were prepared by hot-pressing of HfO₂–Al₂O₃–Y₂O₃ glass microspheres at 915 °C for 10 min. By annealing at temperatures below 1200 °C, the bulk glasses were converted into transparent glass-ceramics with HfO₂ nano-crystallites of 100–200 nm, which showed the maximum transmittance of ～70% in the infrared region. An increase of annealing temperature (>1300 °C) resulted in opaque YAG/HfO₂/Al₂O₃ eutectic ceramics. The eutectic ceramics contained fine Al₂O₃ crystallites and showed a high hardness of 19.8 GPa. The fracture toughness of the eutectic ceramics increased with increasing annealing temperature, and reached the maximum of 4.0 MPa m^1/2.     

Mullite (Nextel™ 720) fibre-reinforced mullite matrix composites exhibiting favourable thermomechanical properties

A mullite matrix containing homogeneously distributed ultra-fine (70–350 nm) pores was reinforced with NdPO₄-coated woven mullite fibre mats (Nextel™ 720) leading to damage-tolerant composites with good high temperature (1300 °C) strength and thermal cycling resistance. Electrophoretically deposited fibre preforms were placed in a high-load pressure filtration assembly, leading to formation of consolidated compacts with high green densities. After sintering at 1200 °C for 3 h, the compacts had a density of 86.4% of theoretical density and showed damage-tolerant behaviour up to 1300 °C, with flexural strength values of 235 MPa and 224 MPa at room temperature and 1300 °C, respectively. No significant microstructural damage was detected after thermal cycling the samples between room temperature and 1150 °C for up to 300 cycles. The thermomechanical test results combined with detailed electron microscopy observations indicate that the overall composite behaviour in terms of damage-tolerance, thermal capability and thermal cycling resistance is mainly controlled by two microstructural features: (1) the presence of a dense NdPO₄ interphase but weak bonding with the matrix or fibre and (2) the presence of homogeneously distributed nano pores (<350 nm) within the mullite matrix.     

High-temperature properties of 2.5D SiO2f/SiO2 composites by sol–gel

2.5D SiO_2f/SiO₂ composites were fabricated by sol–gel process. The mechanical and fracture behavior of SiO_2f/SiO₂ composites under higher temperature were discussed. The oxidation behavior at 1200 °C and 1500 °C was investigated. The results showed that SiO_2f/SiO₂ composites had high flexural strength, and the fracture mechanism was a combination of brittle and ductile fracture. After higher temperature oxidation, the fracture mechanism changed to typical brittle/sudden fracture. For long time usage at higher temperature, it was necessary to stabilize SiO₂ fibers and SiO₂ matrix of SiO_2f/SiO₂ composites.     

Dynamic oxidation resistance and residual mechanical strength of ZrB2-CrSi2-SiC-Si/SiC coated C/C composites

To improve oxidation resistance of carbon/carbon (C/C) composites, a multiphase double-layer ZrB₂-CrSi₂-SiC-Si/SiC coating was prepared on the surface of C/C composites by pack cementation. Thermogravimetry analysis showed that the as-prepared coating could provide effective oxidative protection for C/C composites from room temperature to 1490 °C. After thermal cycling between 1500 °C and room temperature, the fracture behaviors of the as-prepared specimens changed and their residual flexural strengths decreased as thermal cycles increased. The specimen after 20 thermal cycles presented pseudo-plastic fracture characteristics and relatively high residual flexural strength (83.1%), while the specimen after 30 thermal cycles failed catastrophically without fiber pullout due to the severe oxidation damage of C/C substrate especially the brittleness of the reinforcement fibers.     

Strength retention in hot-pressed ZrB2–SiC composite after thermal cycling exposure in air at 1200 and 1400°C

The effect of thermal cycling exposure on room temperature flexural strength was examined in hot-pressed ZrB₂–SiC composite undergone cyclic heating-cooling test at 1200 and 1400°C in air for up to 1000 or 500 cycles. For the post-tested samples at 1200°C, the flexural strength of the composite initially increased and subsequently degraded with increase of number of thermal cycles (N). The strength retention displayed by the composite after N = 1000 cycles was approximately 80%. For the post-tested samples at 1400°C, however, the flexural strength decreased with increase of N. After N = 500 cycles, the strength retention was approximately 45%. The strength decrease was associated with the formation and coarsening of defects in the oxidized reactive layer and the delamination of the outermost thinner dense oxide layer.     

Porous ceramics based on high-thermal-stability Al2O3–ZrO2 nanofibers for thermal insulation and sound absorption applications

Al₂O₃ fibers are promising candidates for porous ceramics, but the sudden growth of grains in the fibers above 1200 °C will limit their applications for high temperature. Herein, we reported the successful fabrication of the Al₂O₃–ZrO₂ nanofibers by electrospinning and the nanofiber-based porous ceramics by a combination of gel-casting, freeze-drying and high-temperature sintering. Results show that the addition of Zr could greatly improve the thermal stability (up to 1400 °C) of the Al₂O₃-based nanofibers, owing to the inhibition of the sudden growth of the grains in the fibers at high temperature. The Al₂O₃–ZrO₂ nanofiber-based porous ceramics after sintering at 1100–1400 °C possessed a multi-level pore structure and exhibited high thermal stability, ultra-high porosity (97.79–98.04%), ultra-low density (0.075–0.091 g/cm³) and thermal conductivity (0.0474–0.0554 W/mK), and excellent sound absorption performance with the average sound absorption coefficient of 0.598–0.770. These porous ceramics are expected to be employed in the fields of high-temperature thermal insulation and sound absorption.