Reinforcement of silica-based ceramic cores based on amorphous and polycrystalline mullite fibers

In the investment casting of turbine blades, ceramic cores are key components to form complex hollow structures. Superior mechanical property and leaching rate are demanded for ceramic cores. Herein, ceramic cores were fabricated using fused silica powders as the matrix, and amorphous and polycrystalline mullite fibers as the reinforcement phases, respectively. The microstructure and property evolution of ceramic cores rely on the crystallization degree of mullite fibers are explored. Both of the mullite fibers lead to improved crystallization of cristobalite, reduced sintering shrinkage, increased apparent porosity, and benefited bending strength, creep resistance, and leaching rate of the cores. Compared to the polycrystalline mullite fibers, the amorphous fibers are metastable with large quantities of structural defects, promoting the diffusion mass transfer and forming strong interface between fibers and matrix. Therefore, the amorphous fibers have larger promotion on the bending strength and resistance to creep deformation of ceramic cores. Moreover, the structural defects of amorphous fibers ensures the high chemical activity in alkaline solutions and exhibits excellent leaching rate. The ceramic core with 4.5 wt% of amorphous mullite fibers exhibits excellent comprehensive performance with bending strengths of 28.9 MPa and 23.8 MPa at room temperature and 1550 °C, creep deformation of 0.3 mm, and leaching rate of 1.4 g/min, well meeting the casting requirements of hollow blades.     

Effect of synergism of solid loading and sintering temperature on microstructural evolution and mechanical properties of 60 vol% high solid loading ceramic core obtained through stereolithography 3D printing

Solid loading has a significant effect on the curing behavior of slurry and the microstructure and properties of the ceramic core. A high-solid loading slurry can effectively improve the sintering densification of ceramic particles and improve the interlayer bonding strength and mechanical properties at both 25 °C room and higher temperatures. Herein, based on the photopolymerization theory of ceramic slurry, the solid loading was increased from 45 to 60 vol% by adjusting the composition ratio of the resin ceramic powder. Additionally, the optimal sintering temperature of the 60 vol% solid loading ceramic core was 1200 °C. The synergistic effect of the solid loading and sintering temperature controls the sintering shrinkage of the sample within 3.2%; the porosity, high temperature, and room temperature flexural strength were approximately 30%, 24 MPa, and 10 MPa, respectively. The printing preparation of high-solid loading ceramic cores can be used to guide optimizing process parameters on an industrial scale.     

Enhanced thermal properties of silica-based ceramic cores prepared by coating alumina/mullite on the surface of fused silica powders

In this study, an alumina/mullite coating was synthesized on the surface of fused silica powders to form an alumina/mullite-silica core-shell structure. The effects of the alumina/mullite coating on the cristobalite crystallization, thermal properties, and leachability of the silica-based ceramic cores were investigated using the simulated casting process. The X-ray diffraction results indicated that the crystallization of cristobalite was significant at the simulated casting temperature of approximately 1400 °C. An increase in the cristobalite content during this stage resulted in a large thermal expansion because of its higher coefficient of thermal expansion compared with that for fused silica. The addition of optimum amounts of the alumina/mullite powders resulted in an increase in the initial shrinkage temperature and a decrease in the shrinkage of the specimens. When the coating powders were added at 43 wt%, the initial shrinkage temperature increased from 1092 °C to 1200 °C and the shrinkage decreased sharply. Leaching tests showed that the silica-based ceramic cores were removed in the form of stripped layers. The washing and shaking process accelerated the disintegration of the ceramic core and improved its leachability.     

Improved mechanical properties of SiB6 reinforced silica-based ceramic cores fabricated by 3D stereolithography printing

Silica-based ceramic core is an extremely critical component in the manufacture of hollow blades during investment casting. However, the traditional preparation methods rely more on the molds, and the manufacturing costs are relatively high. In this study, silica-based ceramics with silicon hexaboride (SiB₆) addition were prepared via 3D stereolithography printing. And the effects of the SiB₆ content on mechanical properties of the obtained ceramic samples were explored. As the SiB₆ content increased to 2.0 wt%, the linear shrinkage gradually decreased, while the room temperature and high temperature flexural strength were enhanced at the SiB₆ content from 0 to 1.0 wt% and reduced as the SiB₆ content further rose. As the SiB₆ content increased to 1.0 wt%, the linear shrinkage was reduced to 1.86% resulting from the oxidation reaction of SiB₆. Furthermore, with 1.0 wt% SiB₆ addition, the flexural strength of the samples at room temperature was enhanced from 6.75 MPa to 14.63 MPa due to the sintering promotion of oxidation product B₂O₃, and the flexural strength at 1550 °C was improved from 7.68 MPa to 13.08 MPa because of the enhanced β-cristobalite content, which is suitable for high temperature casting of ceramic cores. Therefore, it demonstrates the capability of fabricating SiB₆ reinforced silica-based ceramic cores with high performance via stereolithography.     

Effects of micro-sized mullite on cristobalite crystallization and properties of silica-based ceramic cores

Silica-based ceramic cores are extensively used in investment casting process, during which they must exhibit sufficient flexural strength and deformation resistance. In this study, micro-sized mullite was used as an additive to silica-based ceramic cores to optimize their high temperature properties. To investigate the effects of micro-sized mullite on cristobalite crystallization, mechanical and thermal properties of silica-based ceramic cores, ceramic cores with different amounts of micro-sized mullite were fabricated. The XRD results showed that additional micro-sized mullite diminished the crystallization of cristobalite at high temperatures, primarily caused by the mullite related compressive stresses on the surface regions of fused silica particles. Three-point bending tests and SEM results showed that micro-sized mullite had a more significant effect on the flexural strength of ceramic cores compared with conventional additives. Particularly, the fracture mechanism of silica-based ceramic cores had been changed from intergranular fracture into a mixed fracture consisting of both intergranular and transgranular fracture. The mechanical and thermal properties of ceramic cores were all reduced slightly as the mullite content exceed 4.6 wt%. Hence, to optimize the properties of silica-based ceramic cores, the micro-sized mullite content should not exceed 4.6 wt%.     

Substitution of quartz and clay with fly ash in the production of architectural ceramics: A mechanistic study

Quartz and clay are substituted gradually by fly ash using a triaxial ceramic formulation under simulated industrial conditions and the effects of fly ash substitution on the macroscopic properties and microstructures of the sintered ceramics are evaluated systematically. With the substitution of 35 wt% (1250 °C), the ceramic sample exhibited optimal properties, including linear shrinkage of 15.61%, bulk density of 2.39 g cm^-3, water absorption of 0.62% and flexural strength of 41.70 MPa, due to the accelerated densification and fly ash-spurred needle-shaped mullite. The microstructure analysis shows that the sintered matrix consists of three types of particles, quartz-, clay- and feldspar-like particles showing sintering behavior with respect to filling the glassy matrix with preserved morphology, precipitating mullite crystals, and fusing with the surrounding glassy matrix, respectively. The strength of the fly ash - containing ceramics is analyzed by the dispersion-strengthening mechanism and porosity and the results indicate that the fly ash particles affect the mechanical strength due to Griffith flaws when the total porosity is less than 25% and pores at higher total porosity. This study provides a viable strategy to recycle industrial fly ash in the production of architectural ceramics.     

Improved collapse properties of silica-based ceramic cores via flexibly regulating cristobalite content

Although silica-based ceramic cores have important applications in the precision casting of metallic devices, their high-temperature stability and removal performances are seriously affected by the liquid phase sintered fused silica. Herein, we develop a manufacturing strategy of high-collapse silica-based ceramic core via using cristobalite crystals as the sintering inhibitor, waterglass as the binder, and injection moulding at 100°C and 80 MPa, followed by heat treatment simulating the casting process for sintering at 1200°C and 1500°C. The results demonstrated that the addition of cristobalite crystals could effectively form the core skeleton to ensure high-temperature performance. Meanwhile, it inhibited the liquid flow during sintering and induced the crytsallization from fused SiO₂ glass into cristobalite crystals, and the resulting plenty of micropores and microcracks within the microstructure effectively improve the removal performance. Especially, the porosity was highest up to 35.36% and the flexural strength was only 6.74 MPa when the addition of cristobalite reached 45%, realizing a 100% removing by high-frequency and fast-speed specific mechanical vibration. And, the casting is guaranteed to be flat and free of defects. This work provides a simple and flexible strategy to manufacture high-collapse silica-based ceramic cores, which can be removed by specific mechanical vibration without immersion in acid or alkali solutions after casting.     

Electrospun mullite nanofibers derived from diphasic mullite sol

Fine‐grained mullite nanofibers derived from the diphasic mullite sol were successfully fabricated by electrospinning and subsequent pyrolysis at 1500°C. Polymethylsiloxane and aluminum tri‐sec‐butoxide were selected as the silicon and aluminum source to synthesize the diphasic sol. Results show that the weight loss of mullite precursor fibers in our work was about 60 wt.%, which is similar with that of fibers fabricated using the monophasic sol. This low weight loss was mainly attributed to the high ceramic yield of polymethylsiloxane and low introduced polyvinylpyrrolidone content, which ensures the integrity of fiber morphology during the sintering process. Mullite fibers with 216 nm average diameter were fabricated after sintered at 1500°C and the corresponding grain size was only ~100 nm, much smaller than that in mullite fibers derived from monophasic sols. Therefore, it can be predicated that mullite fibers in this work should possess a higher mechanical strength than those derived from monophasic sols when the sintering temperature was higher than 1400°C and therefore was an ideal starting materials for the fabrication of mullite nanofibrous ceramics used as the high‐temperature thermal insulation materials.     

Microstructure and mechanical properties of 3D-printed nano-silica reinforced alumina cores

Ceramic cores are an important component in the preparation of hollow turbine blades for aero-engines. Compared with traditional hot injection technology, 3D printing technology overcomes the disadvantages of a long production cycle and the difficulty in producing highly complex ceramic cores. The ceramic cores of hollow turbine blades require a high bending strength at high temperatures, and nano-mineralizers greatly improve their strength. In this study, nano-silica-reinforced alumina-based ceramic cores were prepared, and the effects of nanopowder content on the microstructure and properties of the ceramic cores were investigated. Alumina-based ceramic cores contained with nano-silica were prepared using the vat photopolymerization 3D printing technique and sintered at 1500 °C. The results showed that the linear shrinkage of ceramic cores first increased and then decreased as the nano-silica powder content increased, and the bending strength showed the same trend. The fracture mode changed from intergranular to transgranular. The open porosity and bulk density fluctuated slightly. The weight loss rate was approximately 20%. When the nano-silica content was 3%, the bending strength reached a maximum of 46.2 MPa and 26.1 MPa at 25 °C and 1500 °C, respectively. The precipitation of the glass phase, change in the fracture mode of the material, pinning crack of nanoparticles, and reduction of fracture energy due to the interlocking of cracks, were the main reasons for material strengthening. The successful preparation of 3D printed nano-silica reinforced alumina-based ceramic cores is expected to promote the preparation of high-performance ceramic cores with complex structures of hollow turbine blades.     

Effects of ZrSiO4 content on properties of SiO2-based ceramics prepared by digital light processing

SiO₂-based ceramic cores are widely used in the preparation of gas turbine engine hollow blades due to their excellent chemical stability and easy removal after casting. In this paper, ZrSiO₄ reinforced SiO₂-based ceramics were fabricated using digital light processing (DLP) technology. The results showed that the addition of ZrSiO₄ reduced the cure depth due to its high UV light absorptivity and refractive index. When the content of ZrSiO₄ increased to 15 wt%, the cristobalite content reached the maximum, and radial shrinkage reached the minimum of 1.4%. ZrSiO₄ grains could hinder the propagation of cracks, enhancing the room-temperature flexural strength. At 1550 °C, fracturing across SiO₂ grains in SiO₂-based ceramics led to the great improvement of high-temperature flexural strength. When the content of ZrSiO₄ reached 15 wt%, the flexural strength at room temperature and high temperature was 11.5 MPa and 36.7 MPa, respectively. Therefore, the SiO₂-based ceramics prepared using DLP technology have good room temperature and high temperature properties, and are expected to be used for hollow blade casting.     

Low-cost porous mullite ceramic membrane supports fabricated from kyanite by casting and reaction sintering

Porous mullite supports are firstly fabricated by casting and reaction sintering based on kyanite with Al(OH)₃ as porogenic agent. The effects of composition and sintering temperature on phase evolution, microstructure, apparent porosity, pore size distribution, linear shrinkage, gas permeation flux and mechanical property of supports are systematically investigated. Results show that the mullitization of kyanite generates needle-like mullite crystals, which form skeleton structures and improve the apparent porosity and strength of supports. Al(OH)₃ addition not only promotes the formation of needle-like mullite but also enhances the apparent porosity of supports. Temperature promotes the development of mullite, from 1450 to 1500 °C, the amount and size of needle-like mullite crystals increase, ≥1500 °C, they reveal columnar morphology. The support prepared with kyanite+40 wt%Al(OH)₃ sintered at 1500–1550 °C exhibits high apparent porosity, good gas permeation flux, excellent mechanical performance and interlocked network structure composed of well development needle-like mullite.     

Effects of particle size distribution and sintering temperature on properties of alumina mold material prepared by stereolithography

Alumina mold materials prepared by stereolithography usually have considerable sintering shrinkage, and their properties related to casting have been rarely studied. In this study, alumina molds materials were prepared by stereolithography, and the effects of particle size distribution and sintering temperature on the properties of the materials were investigated. Results show that the viscosity of the slurries decreases as the fraction of fine powder increases, and the particle size distribution affects the curing behaviors slightly. Sintering shrinkage increases as the fraction of fine powder or the sintering temperature increases. Although lower sintering shrinkage can be achieved by sintering at 1350 °C or 1450 °C, the mold materials sintered at lower temperatures would continue to shrink under the service temperature of 1550 °C, and thus 1550 °C is determined as the optimal sintering temperature. As the fraction of fine powder increases, the creep resistance first increases and then decreases, and specimens prepared with 0.1 fraction of fine powder exhibit the best creep resistance with the droop distance of 4.44 ± 0.45 mm. Specimens prepared with 0.1 fraction of fine powder and sintered at 1550 °C exhibit linear shrinkage of 6.36% along the X/Y direction and 11.39% along the Z direction, and have a flexural strength of 78.15 ± 3.50 MPa and porosity of 30.12 ± 0.08%. The resulting material possesses relatively low sintering shrinkage, proper mechanical strength, porosity and high-temperature properties that meet the requirements for casting purposes.     

Evolution of the microstructure and mechanical properties of stereolithography formed alumina cores sintered in vacuum

Stereolithography (SL) was used to form alumina ceramic cores. The effect of sintering temperature on the microstructure and mechanical properties of the alumina ceramics are investigated, which were sintered in vacuum. The results indicate that, as the sintering temperature increased the particle size of alumina slightly increased, and the interlayer spacing first decreased and then increased. The open porosity of alumina ceramics significantly decreased as the sintering temperature in vacuum increased. The flexural strength and hardness increased as the sintering temperature increased. When sintered at 1150 °C, the flexural strength was found to be 33.7 MPa, the shrinkage was 2.3 %, 2.4 %, and 5.3 % in the X, Y, and Z directions, respectively, and the open porosity was 37.9 %. These results are similar to those found from sintering at 1280 °C in air.     

Additive manufacturing of Al2O3 ceramic core with applicable microstructure and mechanical properties via digital light processing of high solid loading slurry

Ceramic cores are essential intermediate mediums in casting superalloy hollow turbine blades. The developing of additive manufacturing (AM) technology provides a new approach for the preparation of ceramic cores with complex structure. In this study, alumina oxide (Al₂O₃) ceramic cores with fine complex geometric shapes were fabricated by digital light processing (DLP) in high resolution. The maximum solid content of 70 vol% of ceramic slurry was adopted in the printing process, which is important for the regulation of deformations and mechanical properties. The effects of the printing parameters, including exposure intensity, printing layer thickness and sintering temperature on the microstructures and mechanical properties of printed samples were investigated. The decrease of residual stress and similar shrinkage in X, Y, and Z directions could be obtained by adjusting the printing parameters, which are crucial to prepare complex ceramic cores with high quality. Besides, the flexure strength and open porosity of ceramic cores reached 34.84 MPa and 26.94%, respectively, which were supposed to meet the requirement of ceramic cores for the fabrication of superalloy blades.     

Cost‐effective porous ceramic tubes fabricated through a phase inversion/casting process using calcined bauxite

Cost‐effective ceramic tubes based on low‐price commercial calcined bauxite for economical separation were fabricated by a new phase‐inversion casting method. The thermal shrinkage and weight loss during heating of the green tubes were characterized by dilatometric analysis and TG, respectively. Three shrinkage stages appear successively, corresponding to the viscous deformation of polymeric binder at 200‐300°C, significant combustion loss of ~5.2 wt% at 500‐620°C and sintering shrinkage over 800°C, respectively. However, due to high enough viscosity of the casting suspension that can guarantee the green tube against collapse or deformation during the phase inversion/casting process, the sintered tubes display nearly uniform microstructure instead of characteristic asymmetrical structure of the phase inversion process. The influence of sintering temperature on the pore property (including pore size and porosity) and mechanical strength was investigated. As the sintering temperature increases from 1200 to 1400°C, the porosity and average pore size decrease from 46.4% to 37.0% and from 0.98 to 0.81 μm, respectively, and the flexural strength increases from 25.8 to 65.1 MPa. The cost‐effective ceramic tube sintering at the range of 1250‐1400°C can be capable of functioning as a microfiltration membrane or an ultrafiltration membrane support.     

Ultra-low cost porous mullite ceramics with excellent dielectric properties and low thermal conductivity fabricated from kaolin for radome applications

Near-net-shape mullite ceramics with high porosity were prepared from ultra-low cost natural aluminosilicate mineral kaolin as raw material and polystyrene micro-sphere (PS) as pore-forming agent. Microstructure, flexural strength, thermal conductivity and dielectric properties of the ceramics were systematically researched. Results show that the porous mullite ceramics possess fibrous skeleton structure formed by a large quantity of interlocked mullite whiskers, which results in good mechanical properties and low-to-zero sintering shrinkage. Flexural strength of the porous mullite ceramics can be up to 41.01 ± 1.12 MPa, even if the porosity is as high as 62.44%. The dielectric constant and loss tangent of the porous mullite ceramics at room temperature are lower than 2.61 and 5.9 × 10⁻³, respectively. Besides, dielectric constant is very stable with the rising of temperature, and the dielectric loss can be consistently lower than 10⁻² when the temperature is not higher than 800 °C. In addition, thermal conductivity at room temperature is as low as 0.163 W/m/K when the porosity of mullite ceramics is 80.05%. The infiltration of SiO₂ aerogels (SiO₂ AGs) can further decrease the thermal conductivity to 0.075 W/m/K, while has just little effects on the dielectric properties. Excellent mechanical, thermal and dielectric properties show that the porous mullite ceramics have potential applications in radome fields. The porous mullite ceramics prepared from kaolin not only have low cost, but also can achieve near-net-shape.     

Preparation and properties of in-situ mullite whiskers reinforced aluminum chromium phosphate wave-transparent ceramics

In-situ mullite whisker reinforced aluminum chromium phosphate wave-transparent ceramics were designed and prepared. The phase transformation, microstructure, mechanical and electrical properties of the ceramics were investigated, and the mechanisms of in-situ growth and toughening were discussed. Results indicated that the in-situ growth of mullite whisker significantly improved the mechanical properties of the matrix, especially the high temperature flexural strength. The room temperature flexural strength, 1000 °C flexural strength and fracture toughness of the ceramics were 135.60 MPa, 121.71 MPa and 4.52 MPa m^1/2. After sintering at 1500 °C, the optimum properties of ε^'_r, tanδ and microwave transmittance at region 8–12 GHz were <3.6, <0.03 and>80%, respectively. The sinterability of ACP matrix was improved by the in-situ process of high mullization above 1450 °C. Using ACP binder as the raw material can avoid the phase transformation from B-AlPO₄ to T-AlPO₄. The synthesized mullite whiskers played a role in toughening by whiskers fracture, crack deflection and whisker pulling out.     

Preparation and characterization of porous mullite ceramics via foam-gelcasting

Porous mullite ceramics were prepared via foam-gelcasting using industrial grade mullite powder as the main raw materials, Isobam-104 as the dispersing and gelling agent, sodium carboxymethyl cellulose as the foam stabilizing agent, and triethanolamine lauryl sulfate as the foaming agent. The effects of processing parameters such as type and amount of additive, solid loading level and gelling temperature on rheological properties and gelling behaviors of the slurries were investigated. The green samples after drying at 100 °C for 24 h were fired at 1600 °C for 2 h, and the microstructures and properties of the resultant porous ceramic samples were characterized. Based on the results, the effects of foaming agent on the porosity level, pore structure and size and mechanical properties of the as-prepared porous mullite ceramics were examined. Porosity levels and pore sizes of the as-prepared samples increased with increasing the foaming agent content up to 1.0%, above which both porosity levels and pore sizes did not change. The compressive strength and flexural strength of the as-prepared sample with porosity of 76% and average pore size of 313 μm remained as high as 15.3±0.3 MPa and 3.7±0.2 MPa, respectively, and permeability increased exponentially with increasing the porosity.     

High‐Temperature Shear Strength and Bonding Mechanism of the Mullite Ceramic/Fiber Brick Component Joined by Phosphate Adhesive

The mullite ceramic/fiber brick system was bonded by two kinds of phosphate adhesives. The specimens were treated from 200 to 1400°C. The mechanical properties were tested at room temperature and at high temperature, and the relevant bonding mechanism was also discussed. The results show that the addition of silicon can greatly improve the adhesive's mechanical properties. The room‐temperature shear strength of the component bonded by adhesive with the silicon calcined at 800°C can reach 6.58 MPa. The shear strength of the adhesive with silicon tested at 800°C can reach 0.42 MPa.     

Silica strengthened alumina ceramic cores prepared by 3D printing

Ceramic cores based on alumina and silica are important in the manufacturing of hollow blades. However, obtaining good properties and precision is still challenging. In this research, alumina-based ceramics cores were obtained by 3D printing technology, and the effects of silica contents on the mechanical properties of the as-obtained alumina ceramic cores were evaluated. The results showed significant improvements in flexural strengths of the ceramics from 13.3 MPa to 46.3 MPa at silica contents from 0 wt% to 30 wt% due to formation of mullite phase (Al₆Si₂O₁₃). By contrast, the flexural strengths declined as silica content further increased due to the generation of massive liquid phase. Also, porous structures and cracks were observed by scanning electron microscopy due to the removal of cured photosensitive resin and the mullitization reaction between alumina and silica, respectively. The manufacturing process of hollow blades required ceramic cores with flexural strengths greater than 20 MPa to resist the strike of metal liquid, as well as open porosity above 20 % to provide space for alkali liquor to dissolve the ceramic cores. As a result, 10 wt% silica was determined as the optimal value to yield ceramics with improved properties in terms of flexural strength (35.6 MPa) and open porosity (47.5 %), thereby satisfy the application requirement for the fabrication of ceramic cores.