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%.     

Influences of mullite fibers on mechanical and thermal properties of silica-based ceramic cores

Mullite fibers composite silica-based ceramic cores were successfully prepared by injection molding. The effects of mullite fibers on the mechanical and thermal properties of ceramic cores were investigated. The results indicated that the linear shrinkage was significantly decreased and the porosity was gradually increased with the increase of mullite fibers. In addition, the flexural strength for the room temperature and the simulated casting temperature of 1500°C was increased to a maximum value when the content of mullite fibers was about 1 wt.%, and then decreased with the increase of mullite fibers. The mullite fibers of 1 wt.% presented excellent mechanical properties with a linear shrinkage of .65%, a porosity of 6.96%, and a flexural strength of 17 MPa at room temperature and 34.83 MPa at the simulated casting temperature of 1500°C. Besides, the change in microstructure and properties in various contents of mullite fibers were analyzed.     

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.     

Effect of different fiber orientations on compressive creep behavior of siC fiber-reinforced mullite matrix composites

The compressive creep behavior of monolithic mullite and a composite made of mullite reinforced by 40 vol% SiC fiber were investigated at temperatures from 1100 to 1200°C and under stresses from 5 to 55 MPa in air with a loading direction parallel and perpendicular to the fiber direction. For both situations the composite exhibits better creep resistance than monolithic mullite, although there is a creep anisotropy. The improvement in creep resistance when the fibers are parallel to the loading directions is due to the shedding of the applied stress on the SiC fibers, and the improvement in creep resistance when the fibers are perpendicular to the loading direction occurs because the fibers inhibit the lateral deformation of the mullite matrix along the fibers. The improvement mechanisms of the composites were confirmed further by their creep-recovery study, which indicated that the two types of composite specimens exhibit both an apparent creep-recovery behavior on load removal, due to the relaxation of the residual stress state between the mullite matrix and the SiC fibers after unloading. ©     

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.     

Anisotropy management on microstructure and mechanical property in 3D printing of silica-based ceramic cores

Ceramic core is an essential component in the precise casting of hollow turbine blades, and the investigation on 3D printing of silica-based ceramic cores is crucial to the development of aviation industry; however, they are suffered from difficulty in high-temperature strength and structural anisotropy. In present work, silica-based ceramic cores were prepared via DLP stereolithography 3D printing, and the anisotropy management on microstructures and properties were explored based on the particle size of fused silica powders. In 3D printed ceramic cores with coarse powders, significant anisotropy was displayed exhibiting multilayer structure with large gaps in horizontal printing and uniform porous microstructure in the vertical direction, which was further explained by the particle deposition in printing. With finer silica powders, the uniformity in the microstructures was highly improved, attributed to the enhanced particle dispersion in ceramic slurries and promoted interlayer particle rearrangement during sintering. To evaluate the anisotropy in mechanical property, the ratio of vertical strength to horizontal strength (σ_V/σ_H) was proposed, which rose from 0.48 to 0.86 as the particle size decreased from 35 µm to 5 µm, suggesting enhanced mechanical uniformity. While the average particle size of silica powders was 5 µm, the flexure strengths of ceramic cores in different directions were up to 18.5 MPa and 16.3 MPa at 1540 °C with σ_V/σ_H ratio of 0.88, which well satisfied the demands for the casting of turbine blades. This work inspires new guidance on the anisotropy management in ceramic cores prepared by 3D printing, and provides new technology for fabrication of silica-based ceramic cores with superior high temperature mechanical properties.     

Silica-based ceramic core for aviation applications: Facile pore filling and flexural strength improvement

The effect of alumina addition on the pore filling process, crystallization behavior and mechanical properties of silica-based ceramic cores was investigated. The sintered samples at 1250°C were treated at 1550°C for 0.5 hour in order to simulate a casting process condition. The microstructure analysis indicated that an appropriate alumina addition enhanced the pore filling process by supplying a substantial liquid viscous flow. With an increase in the liquid viscous flow, smaller pores were filled first, and larger pores were filled later. The results also indicated that the pore filling process could be enhanced by adding small powder additives to decrease the pore size between the particles in the ceramic material. However, an excessive alumina addition in the silica-based ceramic cores had a negative effect on the flexural strength and leaching rate. As the alumina content increased from 8 to 12 wt%, the flexural strength of the ceramic core decreased from 16.37 to 4.60 MPa, respectively, and the leaching rate also decreased obviously. These results were explained by an acceleration in crystallization trend of the fused silica particle surface and the merging of connected pores in the sintered body.     

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.     

High-toughness silicate ceramic

A silicate ceramic that is similar to porcelain and exhibits a maximum toughness of 4.6 MPa m^1/2 was obtained by tape casting from kaolin and 3 vol% of alumina fibers. Improved toughness and strength are achieved with the organized micro-composite microstructure that results from preferential orientation during the shaping of kaolinite particles and fibers in-plane of layers. During sintering, typical nucleation and growth processes of mullite produce specific microstructural characteristics, such as bulk zones, oriented fibers and large interfacial zones between the fibers and the bulk. Toughening is attributed to the decreased crack energy in the bulk ceramic, in which a dense and organized network of short mullite occurs, and in interfacial zones containing a superimposed network of large mullite. The silicate ceramic that is reinforced by only 3 vol% of the alumina fibers is strong (95 MPa) and tough (4.6 MPa m^1/2); although these properties are often mutually exclusive.     

Additive manufacturing of low-shrinkage alumina cores for single-crystal nickel-based superalloy turbine blade casting

We prepare bimodal particle size photo-curable ceramic pastes with high solid loadings (up to 65 vol %) and fabricate porous alumina ceramic cores with complex shapes via ceramic stereolithography (Cer-SLA) 3D printing technique. The sintering temperature is carefully selected, ranging from 1500 °C to 1650 °C, and a high holding time (>4 h) is applied to guarantee that the materials can withstand the subsequent high temperature (>1500 °C) casting process for single-crystal nickel-based superalloy hollow turbine blades. Herein, the originally spherical fine particles are found to become platelet-like after sintering, and the forming mechanism is discussed in detail. In addition, we explore the influence of platelet-like particles, coarse particles and sintering process on the microstructural evolution of alumina particles, and reveal the relationship between microstructure and properties of ceramic cores. These results illustrate that the proposed materials for SLA 3D printing exhibit a great potential in the fabrication of complex-shaped alumina ceramic cores for high-precision investment casting, e.g., manufacturing single-crystal nickel-based superalloy hollow turbine blades for an advanced aircraft engine.     

High-temperature elasticity of fibrous ceramics with a bird's nest structure

New fibrous ceramics with polycrystalline mullite fibers as the matrix and silica–boron sols as the high temperature binder, which was inspired by the bird's nest structure in nature, were synthesized. The most important structure characteristic of this fibrous material is that the silica–boron binder only fixed the fibers at the crossing points rather than filled the pores among the fibers. The elastic behavior was investigated, both at room temperature and elevated temperature. Compared to conventional ceramic matrix composites, the samples show a much higher degree of elasticity because of the bending of the fibers. The rebound resilience decreased slowly with the increase of the temperature, but it still remained 86% of that at ambient temperature at 1000 °C. The sample exhibits good elasticity performance, relatively high strength (2.25 MPa) and high porosity (83%) indicating it is a potential high-temperature seal material.     

Development of microstructure during creep of polycrystalline mullite and a nanocomposite mullite/5 vol.% SiC

The microstructures of as-sintered and creep tested polycrystalline mullite and mullite reinforced with 5 vol.% nano-sized SiC particles have been characterized by scanning and transmission electron microscopy. The dislocation densities after tensile creep testing at 1300 and 1400 °C were virtually unchanged as compared to the as-sintered materials which indicates diffusion-controlled deformation. Mullite matrix grain boundaries bending around intergranular SiC particles suggest that grain boundary pinning, in addition to a reduced mullite grain size, contributed to the increased creep resistance of the mullite/5 vol.% SiC nanocomposite. Both materials showed pronounced cavitation at multi-grain junctions after creep testing at 1400 °C which suggests that unaccommodated grain boundary sliding, facilitated by softening of the intergranular glass, occurred at this temperature. This is consistent with the higher stress exponents at 1400 °C.     

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.     

Creep in Interlaminar Shear of a Nextel™720/aluminosilicate Composite at 1100°C in Air and in Steam

Creep in interlaminar shear of an oxide–oxide ceramic composite was evaluated at 1100°C in air and in steam. Composite consists of a porous aluminosilicate matrix reinforced with mullite/alumina (Nextel^?720) fibers, has no interface between fibers and matrix, and relies on the porous matrix for flaw tolerance. The interlaminar shear strength was 7.6 MPa. Creep behavior was examined for shear stresses of 2–6 MPa. Creep run‐out of 100 h was not achieved. Larger creep strains and higher creep strain rates were produced in steam. However, steam had a beneficial effect on creep lifetimes. Composite microstructure, damage, and failure mechanisms were investigated.     

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.     

Controlled anisotropy in 3D printing of silica-based ceramic cores through oxidization reaction of aluminum powders

Ceramic cores are key components to form inner hollow structures in aero-engine blades, and 3D printing is an ideal molding technology for ceramic cores. In this work, silica-based ceramic cores are fabricate via 3D printing of digital light processing (DLP) stereolithography, and the anisotropy in microstructure and property are controlled by aluminum powders. The ceramic cores without aluminum powders exhibit anisotropic microstructure with interlayer gaps, which get narrower and disappear with doping of 7.5–10 wt% of aluminum powders, due to the volume expansion during oxidization reaction of aluminum powders filling the interlayer gaps. The anisotropy in mechanical property is rely on the printing direction, and the ratio of strength in different directions (σ_V/σ_H) is put forward to value the mechanical anisotropy; the ratios rise from 0.40 to 0.92 at room temperature and 0.51 to 0.97 at 1540 °C, as 7.5 wt% of aluminum is doped, and the optimized ceramic cores show high-temperature strengths of 16.6 MPa and 16.1 MPa in different printing directions. Even though ceramic cores with 10 wt% of aluminum show uniform microstructure and higher σ_V/σ_H ratio, the weak particle bonding within printing layers limits their mechanical property, and the strengths decrease to 13.8 MPa and 13.4 MPa at 1540 °C. This work inspires a new technique to excellent high-temperature mechanical properties with anisotropy control in 3D printing of ceramic cores.     

Microstructure and high temperature 4-point bending creep of sol–gel derived mullite ceramics

Four-point bending creep behavior of mullite ceramics with monomodal and bimodal distribution of grain sizes was studied in the temperature range of 1320–1400 °C under the stresses between 40 and 160 MPa. Mullite ceramic with bimodal grain size distribution was prepared using aluminum nitrate nonahydrate as alumina precursor. When γ-Al₂O₃ or boehmite were used as alumina precursors, mullite grains are equiaxial with mean particle size of 0.6 μm for the former and 1.3 μm for the latter alumina precursor. The highest creep rate exhibited the sample with monomodal morphology and grains in size of 0.6 μm, which is about one order of magnitude greater than that for the monomodal morphology but with grains in size of 1.3 μm. The highest activation energy for creep (Q = 742 ± 33 kJ/mol) exhibits mullite with equiaxial grains of 1.3 μm, whereas for sample with smaller equiaxial grains the activation energy is much smaller and similar to mullite ceramics with bimodal grain morphology. Intergranular fracture is predominant near the tension surface, while transgranular more planar fracture is predominant near the compression surface zone.     

Preparation,mechanical, and leaching properties of CaZrO3 ceramic cores

The CaZrO₃ ceramic core materials with excellent mechanical and chemical properties were successfully prepared using single-phase CaZrO₃ powders. Effects of particle size ratio and sintering temperature on the mechanical and chemical properties of CaZrO₃ ceramic core materials were researched. The chemical property was analyzed by leaching research of core materials in 10 wt% and 20 wt% HNO₃ solution at the boiling point. Results showed that the suitable particle size ratio was important for the preparation of CaZrO₃ ceramic core materials with excellent comprehensive properties. The addition of fine particles in ceramic core materials promoted the densification process owing to the framework formed by coarser particles and sintering neck formed by fine particles between coarse particles, which was beneficial for further improving their bending strength. When the content of particles with 200 mesh size was 80wt%, the highest bending strength was obtained, 54.38 ± 5.28 MPa. The porosity was 17.45% and the volume density was 3.86 g/cm³. The increasing sintering temperature increased the densification of CaZrO₃ ceramic core materials by offering the sintering driving force, further leading to the improvement of bending strength. When the temperature was 1650℃, at the 20% content of particles with 200 mesh size, the highest bending strength of CaZrO₃ cores reached 51.01 ± 5.18 MPa. Meanwhile, the porosity was 18.65% and the volume density was 3.83 g/cm³. Additionally, the CaZrO₃ samples could be effectively leached in 10 wt% HNO₃ solution. Therefore, CaZrO₃ materials with good mechanical and leaching properties were believed to be a suitable candidate for ceramic core materials in the investment casting of alloys with high melting point.     

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.     

Investigation on cristobalite crystallization in silica-based ceramic cores for investment casting

In this work, cristobalite crystallization and its effects on mechanical and chemical behaviour of injection moulded silica-based ceramic cores were investigated. In order to simulate casting process condition, the sintered samples at 1220 °C were also heated up to 1430 °C. Flexural strength test was carried out on both sintered and heat treated samples. Chemical resistance of the cores was evaluated by leaching the samples inside 43 wt% KOH solution at its boiling point. Phase evolution and microstructure were investigated by thermal analyses (DTA and DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM) and optical microscopy (OM). Results showed that cristobalite was crystallized on the surface of fused silica grains at about 1380 °C. Flexural strength of the sintered cores was decreased after simulated casting heat treatment due to cristobalite phase transformation. The formed cristobalite on the surface of fused silica grains dramatically decreased the leachability of ceramic cores.