Preparation method of fiber reinforced high-strength high-thermal shock resistance zirconia-based refractory material
By introducing zirconia fibers into zirconia materials and optimizing the sintering process, high-strength and highly thermally shock zirconia-based refractories were prepared, solving the problem of thermal shock resistance of zirconia materials under high-temperature environments and improving the stability and service life of the materials under extreme conditions.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SINOSTEEL LUOYANG INSTITUTE OF REFRACTORIES RESEARCH CO LTD
- Filing Date
- 2026-04-02
- Publication Date
- 2026-06-05
AI Technical Summary
Zirconia materials have insufficient thermal shock resistance under rapid temperature changes or high mechanical impact loads, which affects their structural stability and service life.
By introducing zirconia fibers as reinforcement, combined with specific ratios and optimized sintering processes, high-strength and thermally shock zirconia-based refractories reinforced with fibers are prepared. The bridging and pull-out effects of fibers during crack propagation are utilized to improve the material's tolerance to thermal shock damage.
It significantly improves the mechanical strength and thermal shock resistance of the material, making it suitable for high-temperature and extreme environments in aerospace, metallurgical industry and specialty chemical fields.
Abstract
Description
Technical Field
[0001] This invention belongs to the field of inorganic non-metallic refractory materials technology, specifically relating to a method for preparing fiber-reinforced high-strength, high-thermal-shock-resistant zirconia-based refractory materials. Background Technology
[0002] Zirconia is considered a promising high-temperature structural material due to its high melting point, excellent high-temperature stability, good chemical inertness, high hardness, and outstanding mechanical strength. It has shown great application potential in aerospace, metallurgy, new energy, and specialty chemicals.
[0003] However, the inherently poor thermal shock resistance of bulk zirconia severely limits its reliability and service life under harsh environments such as rapid temperature changes or high mechanical impact loads. The phase transformation that occurs during the preparation and high-temperature use of zirconia is one of the core factors affecting its structural stability and thermal shock resistance. Although adding stabilizers such as yttrium oxide and magnesium oxide can stabilize the tetragonal or cubic phase to some extent, excessive addition may lead to deterioration of the material's high-temperature performance, and relying solely on stabilizers cannot fundamentally solve the problem of insufficient thermal shock resistance.
[0004] Fiber reinforcement has proven to be an effective way to improve the thermal shock resistance of zirconia materials. By introducing zirconia fibers, alumina fibers, silicon carbide fibers, etc., as reinforcements, the debonding, bridging, and pull-out effects generated by the fibers during crack propagation can significantly consume fracture energy and improve the material's thermal shock damage tolerance. Summary of the Invention
[0005] To address the shortcomings of existing technologies, the present invention aims to provide a method for preparing fiber-reinforced, high-strength, and highly thermally shock zirconia-based refractory materials, thereby enhancing the thermal shock resistance of the original materials.
[0006] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing fiber-reinforced high-strength, high-thermal-shock-resistant zirconia-based refractory material involves introducing zirconia fibers as reinforcements into a zirconia matrix, YSZ. The specific preparation steps are as follows: 1) Mixing: Mix 60-30 parts of 0.5-2mm YSZ, 20-30 parts of 325-mesh YSZ, and 30-50 parts of M-ZrO2, and add 5-13% of Y2O3 by total mass. Mix at high speed to obtain a uniformly mixed composite powder. 2) Adding binder and fiber: Add polyvinyl alcohol (PVA) aqueous solution as binder to the composite powder obtained in step 1), and add 4%-5% of zirconium oxide fiber by total mass. Mix at high speed to make the PVA aqueous solution uniformly coat the powder and the fiber uniformly dispersed to obtain a mixture. 3) Let the material stand still and be trapped; 4) Compression molding: The mixture is placed in a mold and pressed under a certain pressure; 5) Drying: Dry the pressed blank at a certain temperature for a certain period of time; 6) Firing: The dried blanks are placed in a sintering furnace for sintering.
[0007] The M-ZrO2 and Y2O3 have a particle size of less than 10 μm.
[0008] The fiber has a diameter of 5-20 μm and an aspect ratio of 20-50.
[0009] The high-speed mixing medium is ZrO2 balls, and the ball-to-material ratio is 1.5-3:1.
[0010] The high-speed mixing time is 1 hour.
[0011] The binder is a PVA aqueous solution with a concentration of 3.5% and an addition amount of 8% of the total mass.
[0012] The settling time for the material is 12 hours.
[0013] The specified pressure is 80-120 MPa.
[0014] The drying temperature is 200℃.
[0015] The drying time is 5 hours.
[0016] The sintering heating regime is as follows: heating at 4℃ / min to 600℃ and holding for 2 hours, heating at 3℃ / min to 1200℃, heating at 2℃ / min to 1500℃, heating at 1℃ / min to the firing temperature, the firing temperature is 1650-1750℃, and holding for 3 hours.
[0017] The bulk density of the material is 4.6-5.2 g / cm³. 3 The porosity is 10%-20%, the flexural strength at room temperature is 30-50 MPa, the flexural strength at 1400℃ is 25-35 MPa, the compressive strength at room temperature is 120-160 MPa, the compressive strength at 1400℃ is 40-60 MPa, the tensile strength at room temperature is 15-35 MPa, the tensile strength at 1400℃ is 10-15 MPa, the elastic modulus at room temperature is 80-400 GPa, and the thermal conductivity at 0-1100℃ is less than 0.6 W∙m. -1 ∙K -1 The number of thermal shocks is more than 10.
[0018] This invention significantly improves the mechanical strength and thermal shock resistance of materials by combining fiber reinforcement with an optimized sintering process. The resulting material is suitable for high-temperature and extreme environments such as aerospace thermal protection components, key refractory components for the metallurgical industry, and high-temperature reactor linings in the specialty chemical industry.
[0019] This invention achieves full densification of the matrix and good bonding of the fiber-matrix interface through a specific ratio of multi-component powder composites and the introduction of zirconia fibers, under an optimized sintering process. When the material is under stress, the fibers can effectively dissipate energy through bridging and pull-out mechanisms, thereby increasing strength; simultaneously, the presence of fibers can inhibit crack propagation and alleviate thermal stress, thus significantly improving thermal shock resistance. Detailed Implementation
[0020] The embodiments of the present invention will be described in further detail below. Example 1:
[0021] A mixture of 60 parts of 0.5-2mm YSZ, 20 parts of 325-mesh YSZ, and 30 parts of M-ZrO2, along with 12% Y2O3 by mass, was prepared using ZrO2 balls as the grinding medium at a ball-to-powder ratio of 2:1. The mixture was stirred for 1 hour to obtain a homogeneous composite powder. An 8% (by mass) 3.5% (by mass) polyvinyl alcohol aqueous solution was added to the composite powder as a binder, along with 4% (by mass) zirconium oxide fibers. The mixture was stirred at high speed for 1 hour until the PVA solution uniformly coated the powder and the fibers were uniformly dispersed in the mixture. The mixture was then filled into a mold and pressed under a uniaxial pressure of 120 MPa for 60 seconds to form standard-sized strip blanks. The blanks were placed in a drying oven and dried at 200°C for 5 hours to completely remove moisture. The dried blanks were then placed in a high-temperature sintering furnace and sintered in air. The sintering process is as follows: the temperature is increased to 600°C at a rate of 4°C / min and held for 2 hours to completely remove the PVA binder. Then, the temperature is increased to 1200°C at a rate of 3°C / min, to 1500°C at a rate of 2°C / min, and to 1750°C at a rate of 1°C / min and held for 3 hours. The material is then allowed to cool naturally to room temperature in the furnace to obtain the final material product.
[0022] The fired product has a bulk density of 5.15 g / cm³. 3 The porosity is 10.5%, the flexural strength at room temperature is 48.6 MPa, the flexural strength at 1400℃ is 34.3 MPa, the compressive strength at room temperature is 150.53 MPa, the compressive strength at 1400℃ is 59.786 MPa, the tensile strength at room temperature is 34.8 MPa, the tensile strength at 1400℃ is 14.354 MPa, the elastic modulus at room temperature is 384.239 GPa, and the thermal conductivity from 0 to 1100℃ is 0.58 × 10⁻⁶. -6 W∙m -1 ∙K-1 12 thermal shocks. Example 2:
[0023] 50 parts of 0.5-2mm YSZ, 20 parts of 325-mesh YSZ, and 40 parts of M-ZrO2, along with 9% Y2O3 by weight, were mixed using ZrO2 balls as the grinding medium at a ball-to-powder ratio of 2:1 for 1 hour to obtain a uniformly mixed composite powder. 8% (by weight) of a 3.5% (by weight) polyvinyl alcohol aqueous solution was added to the composite powder as a binder, along with 4.5% (by weight) of zirconium oxide fibers. The mixture was stirred at high speed for 1 hour until the PVA solution uniformly coated the powder and the fibers were uniformly dispersed in the mixture. The mixture was filled into a mold and pressed under a uniaxial pressure of 100 MPa for 60 seconds to form standard-sized strip blanks. The blanks were placed in a drying oven and dried at 200°C for 5 hours to completely remove moisture. The dried blanks were then placed in a high-temperature sintering furnace and sintered in air. The sintering process is as follows: the temperature is increased to 600°C at a rate of 4°C / min and held for 2 hours to completely remove the PVA binder. Then, the temperature is increased to 1200°C at a rate of 3°C / min, to 1500°C at a rate of 2°C / min, and to 1700°C at a rate of 1°C / min and held for 3 hours. The material is then allowed to cool naturally to room temperature in the furnace to obtain the final material product.
[0024] The fired product has a bulk density of 4.92 g / cm³. 3 The porosity is 14.7%, the flexural strength at room temperature is 41.7 MPa, the flexural strength at 1400℃ is 30.4 MPa, the compressive strength at room temperature is 141.69 MPa, the compressive strength at 1400℃ is 51.953 MPa, the tensile strength at room temperature is 25.9 MPa, the tensile strength at 1400℃ is 11.784 MPa, the elastic modulus at room temperature is 242.427 GPa, and the thermal conductivity at 0-1100℃ is 0.5 × 10⁻⁶. -6 W∙m -1 ∙K -1 18 thermal shocks were recorded. Example 3:
[0025] A mixture of 40 parts 0.5-2mm YSZ, 20 parts 325-mesh YSZ, and 50 parts M-ZrO2, along with 7.5% Y2O3 by mass, was prepared using ZrO2 balls as the grinding medium at a ball-to-powder ratio of 2:1. The mixture was stirred for 1 hour to obtain a homogeneous composite powder. An 8% (by mass) 3.5% (by mass) polyvinyl alcohol aqueous solution was added to the composite powder as a binder, along with 5% (by mass) zirconium oxide fibers. The mixture was stirred at high speed for 1 hour until the PVA solution uniformly coated the powder and the fibers were uniformly dispersed in the mixture. The mixture was then filled into a mold and pressed under a uniaxial pressure of 80 MPa for 60 seconds to form standard-sized strip blanks. The blanks were placed in a drying oven and dried at 200°C for 5 hours to completely remove moisture. The dried blanks were then placed in a high-temperature sintering furnace and sintered in air. The sintering process is as follows: the temperature is increased to 600°C at a rate of 4°C / min and held for 2 hours to completely remove the PVA binder. Then, the temperature is increased to 1200°C at a rate of 3°C / min, to 1500°C at a rate of 2°C / min, and to 1650°C at a rate of 1°C / min and held for 3 hours. The material is then allowed to cool naturally to room temperature in the furnace to obtain the final material product.
[0026] The fired product has a bulk density of 4.68 g / cm³. 3 The porosity is 18.3%, the flexural strength at room temperature is 33.6 MPa, the flexural strength at 1400℃ is 26.4 MPa, the compressive strength at room temperature is 124.53 MPa, the compressive strength at 1400℃ is 42.351 MPa, the tensile strength at room temperature is 16.8 MPa, the tensile strength at 1400℃ is 10.687 MPa, the elastic modulus at room temperature is 96.384 GPa, and the thermal conductivity at 0-1100℃ is 0.5 × 10⁻⁶. -6 W∙m -1 ∙K -1 15 thermal shocks. Example 4:
[0027] 55 parts of 0.5-2mm YSZ, 20 parts of 325-mesh YSZ, and 35 parts of M-ZrO2, along with 10% Y2O3 by weight, were mixed using ZrO2 balls as the grinding medium at a ball-to-powder ratio of 2:1 for 1 hour to obtain a uniformly mixed composite powder. 8% (by weight) of a 3.5% (by weight) polyvinyl alcohol aqueous solution was added to the composite powder as a binder, along with 4% (by weight) of zirconium oxide fibers. The mixture was stirred at high speed for 1 hour until the PVA solution uniformly coated the powder and the fibers were uniformly dispersed in the mixture. The mixture was filled into a mold and pressed under a uniaxial pressure of 100 MPa for 60 seconds to form standard-sized strip blanks. The blanks were placed in a drying oven and dried at 200°C for 5 hours to completely remove moisture. The dried blanks were then placed in a high-temperature sintering furnace and sintered in air. The sintering process is as follows: the temperature is increased to 600°C at a rate of 4°C / min and held for 2 hours to completely remove the PVA binder. Then, the temperature is increased to 1200°C at a rate of 3°C / min, to 1500°C at a rate of 2°C / min, and to 1700°C at a rate of 1°C / min and held for 3 hours. The material is then allowed to cool naturally to room temperature in the furnace to obtain the final material product.
[0028] The fired product has a bulk density of 5.02 g / cm³. 3 The porosity is 12.5%, the flexural strength at room temperature is 44.1 MPa, the flexural strength at 1400℃ is 31.5 MPa, the compressive strength at room temperature is 147.37 MPa, the compressive strength at 1400℃ is 55.641 MPa, the tensile strength at room temperature is 29.4 MPa, the tensile strength at 1400℃ is 12.741 MPa, the elastic modulus at room temperature is 314.857 GPa, and the thermal conductivity at 0-1100℃ is 0.5 × 10⁻⁶. -6 W∙m -1 ∙K -1 20 thermal shocks. Example 5:
[0029] 45 parts of 0.5-2mm YSZ, 20 parts of 325-mesh YSZ, and 45 parts of M-ZrO2, along with 8.5% Y2O3 by mass, were mixed using ZrO2 balls as the grinding medium at a ball-to-powder ratio of 2:1 for 1 hour to obtain a uniformly mixed composite powder. 8% (by mass) of a 3.5% (by mass) polyvinyl alcohol aqueous solution was added to the composite powder as a binder, along with 5% (by mass) of zirconium oxide fibers. The mixture was stirred at high speed for 1 hour until the PVA solution uniformly coated the powder and the fibers were uniformly dispersed in the mixture. The mixture was filled into a mold and pressed under a uniaxial pressure of 80 MPa for 60 seconds to form standard-sized strip blanks. The blanks were placed in a drying oven and dried at 200°C for 5 hours to completely remove moisture. The dried blanks were then placed in a high-temperature sintering furnace and sintered in air. The sintering process is as follows: the temperature is increased to 600°C at a rate of 4°C / min and held for 2 hours to completely remove the PVA binder. Then, the temperature is increased to 1200°C at a rate of 3°C / min, to 1500°C at a rate of 2°C / min, and to 1650°C at a rate of 1°C / min and held for 3 hours. The material is then allowed to cool naturally to room temperature in the furnace to obtain the final material product.
[0030] The fired product has a bulk density of 4.78 g / cm³. 3 The porosity is 16.7%, the flexural strength at room temperature is 36.3 MPa, the flexural strength at 1400℃ is 28.3 MPa, the compressive strength at room temperature is 137.63 MPa, the compressive strength at 1400℃ is 49.428 MPa, the tensile strength at room temperature is 24.7 MPa, the tensile strength at 1400℃ is 12.387 MPa, the elastic modulus at room temperature is 193.211 GPa, and the thermal conductivity at 0-1100℃ is 0.5 × 10⁻⁶. -6 W∙m -1 ∙K -1 22 thermal shocks.
Claims
1. A method for preparing a fiber-reinforced, high-strength, and thermally shock-resistant zirconia-based refractory material, characterized in that, The specific preparation steps for introducing zirconia fibers as reinforcements into a zirconia matrix, YSZ, are as follows: 1) Mixing: Mix 60-30 parts of 0.5-2mm YSZ, 20-30 parts of 325-mesh YSZ, and 30-50 parts of M-ZrO2, and add 5-13% of Y2O3 by total mass. Mix at high speed to obtain a uniformly mixed composite powder. 2) Adding binder and fiber: Add polyvinyl alcohol (PVA) aqueous solution as binder to the composite powder obtained in step 1), and add 4%-5% of zirconium oxide fiber by total mass. Mix at high speed to make the PVA aqueous solution uniformly coat the powder and the fiber uniformly dispersed to obtain a mixture. 3) Let the material stand still and be trapped; 4) Compression molding: The mixture is placed in a mold and pressed under a certain pressure; 5) Drying: Dry the pressed blank at a certain temperature for a certain period of time; 6) Firing: The dried blanks are placed in a sintering furnace for sintering.
2. The method for preparing a fiber-reinforced, high-strength, and thermally shock-resistant zirconia-based refractory material as described in claim 1, characterized in that: The M-ZrO2 and Y2O3 have a particle size of less than 10 μm.
3. The method for preparing a fiber-reinforced, high-strength, and thermally shock-resistant zirconia-based refractory material as described in claim 1, characterized in that: The fiber has a diameter of 5-20 μm and an aspect ratio of 20-50.
4. The method for preparing a fiber-reinforced high-strength, high-thermal-shock-resistant zirconia-based refractory material as described in claim 1, characterized in that... The high-speed mixing process uses ZrO2 balls as the grinding medium, with a ball-to-material ratio of 1.5-3:
1.
5. The method for preparing a fiber-reinforced high-strength, high-thermal-shock-resistant zirconia-based refractory material as described in claim 1, characterized in that: The high-speed mixing time is 1 hour.
6. The method for preparing a fiber-reinforced, high-strength, and thermally shock-resistant zirconia-based refractory material as described in claim 1, characterized in that: The binder is a PVA aqueous solution with a concentration of 3.5% and an addition amount of 8% of the total mass.
7. The method for preparing a fiber-reinforced high-strength, high-thermal-shock-resistant zirconia-based refractory material as described in claim 1, characterized in that... The settling time for the material is 12 hours.
8. The method for preparing a fiber-reinforced high-strength, high-thermal-shock-resistant zirconia-based refractory material as described in claim 1, characterized in that: The specified pressure is 80-120 MPa.
9. The method for preparing a fiber-reinforced high-strength, high-thermal-shock-resistant zirconia-based refractory material as described in claim 1, characterized in that: The drying temperature is 200℃.
10. The method for preparing a fiber-reinforced high-strength, high-thermal-shock-resistant zirconia-based refractory material as described in claim 1, characterized in that: The drying time is 5 hours.
11. The method for preparing a fiber-reinforced high-strength, high-thermal-shock-resistant zirconia-based refractory material as described in claim 1, characterized in that... The sintering heating regime is as follows: heat up to 600℃ at 4℃ / min and hold for 2 hours, then heat up to 1200℃ at 3℃ / min, then heat up to 1500℃ at 2℃ / min, and finally heat up to the firing temperature at 1650-1750℃ at 1℃ / min, and hold for 3 hours.
12. The method for preparing a fiber-reinforced high-strength, high-thermal-shock-resistant zirconia-based refractory material as described in claim 1, characterized in that... The bulk density of the material is 4.6-5.2 g / cm³. 3 The porosity is 10%-20%, the flexural strength at room temperature is 30-50 MPa, the flexural strength at 1400℃ is 25-35 MPa, the compressive strength at room temperature is 120-160 MPa, the compressive strength at 1400℃ is 40-60 MPa, the tensile strength at room temperature is 15-35 MPa, the tensile strength at 1400℃ is 10-15 MPa, the elastic modulus at room temperature is 80-400 GPa, and the thermal conductivity at 0-1100℃ is less than 0.6 W∙m. -1 ∙K -1 The number of thermal shocks is more than 10.