A ceramic target solid solution particle and a preparation method of a gadolinium ytterbium zirconate ceramic target

Abstract

This invention relates to the field of electron beam physical vapor deposition (EBPD) for preparing thermal barrier coatings, and discloses a method for preparing ceramic target solid solution particles and a gadolinium ytterbium zirconate ceramic target. The ceramic target solid solution particles used to prepare the gadolinium ytterbium zirconate ceramic target are composed of the following components by mass: 31-55 parts zirconium oxide, 40-60 parts gadolinium oxide, 4-8 parts ytterbium oxide, 0.3-0.5 parts dispersant, and 0.5-0.7 parts binder. The gadolinium ytterbium zirconate ceramic target prepared from such ceramic target solid solution particles not only meets the requirements for EBPD, but also produces a thermal barrier coating with a higher operating temperature, lower thermal conductivity, and longer service life compared to traditional thermal barrier coatings.

Description

Technical Field

[0001] This invention relates to the field of preparing thermal barrier coatings by electron beam physical vapor deposition, and discloses a method for preparing ceramic target solid solution particles and gadolinium zirconate ytterbium ceramic target. Background Technology

[0002] Electron beam physical vapor deposition (EB-PVD) technology, as a core process for preparing high-performance thermal barrier coatings, is widely used in the protection of turbine blades in high-temperature equipment such as aero-engines and gas turbines. It primarily involves bombarding a target with an electron beam to vaporize the material and deposit it onto the substrate surface. The resulting coating has a columnar crystalline structure, exhibiting excellent thermal insulation performance and thermal shock resistance, making it a key technology for ensuring the long-term reliable operation of high-temperature components. In current EB-PVD processes, 8YSZ (yttrium oxide-stabilized zirconia) ceramic targets are the most mature and widely used target type. Due to the stabilizing effect of yttrium oxide on zirconia, coatings prepared with 8YSZ targets can maintain a stable fluorite structure in environments below 1200℃, and possess low thermal conductivity and good mechanical strength, meeting the protection requirements of high-temperature components under medium and low temperature conditions. For example, 8YSZ coatings have achieved large-scale application in scenarios such as low-pressure turbine blades of civil aero-engines and small and medium-sized gas turbine blades, providing important support for improving the safety and lifespan of equipment.

[0003] However, with the increasing demands for thrust-to-weight ratio and thermal efficiency in aerospace and energy sectors, the service environment temperature of high-temperature components continues to rise, exceeding 1300℃ in some scenarios. The limitations of traditional 8YSZ ceramic sputtering targets are becoming increasingly apparent, hindering EB-PVD development. The core bottlenecks in upgrading the performance of thermal barrier coatings are: First, 8YSZ is prone to phase transformation in high-temperature environments above 1250℃, changing from a tetragonal phase to a monoclinic phase. This is accompanied by volume expansion, leading to coating cracking and peeling, which significantly shortens the coating's service life. Second, the long-term high-temperature stability of the 8YSZ coating is insufficient. Under continuous high-temperature oxidation and thermal cycling, the coating is prone to phenomena such as zirconia grain growth and sintering densification, resulting in an increase in thermal conductivity, which can reach above 3.5 W / (m·K) at high temperatures, significantly reducing its thermal insulation performance. Third, 8YSZ has weak resistance to CMAS (calcium magnesium aluminum silicate) erosion. In dusty conditions such as gas turbines, high-temperature molten CMAS can easily penetrate into the coating and react chemically with 8YSZ, generating a low-melting-point phase that blocks the coating pores, destroys the integrity of the coating structure, and further exacerbates the risk of coating failure.

[0004] To overcome the performance bottleneck of 8YSZ targets, the industry urgently needs to develop a new generation of high-performance ceramic targets adapted to EB-PVD processes. Gadolinium ytterbium zirconate (GdYbZrO) ceramic materials, with their unique crystal structure and thermophysical properties, show great potential for application and have become one of the core directions for replacing 8YSZ targets. Compared to 8YSZ, the future advantages of gadolinium ytterbium zirconate ceramic targets are mainly reflected in the following aspects: First, by using rare earth elements such as gadolinium and ytterbium to dope zirconium oxide, a stable fluorite or pyrochlore structure can be formed, increasing the phase transition temperature to above 1400℃, enabling it to withstand higher service temperatures and meet the protection requirements of new-generation high-temperature equipment; second, the lattice vibration mode of gadolinium ytterbium zirconate materials is regulated by rare earth element doping, significantly reducing thermal conductivity, which can be as low as 1-2 W / (m²·K) at 1200K. Furthermore, it exhibits superior thermal insulation performance due to its high thermal expansion coefficient (10-12K-1) and low reactivity with CMAS, effectively inhibiting CMAS penetration and erosion and enhancing the coating's durability under complex operating conditions. Finally, the thermal expansion coefficient of gadolinium zirconate (10-12K-1) is more compatible with the high-temperature alloy substrates commonly used in aero-engines (such as nickel-based high-temperature alloys), reducing thermal stress between the coating and the substrate and lowering the risk of coating cracking during thermal cycling.

[0005] However, the preparation of gadolinium ytterbium zirconate ceramic targets still faces technical challenges. On the one hand, the molding and sintering of large-sized gadolinium ytterbium zirconate targets (e.g., length ≥ 300 mm, diameter ≥ 50 mm) are difficult. Traditional sintering processes easily lead to defects such as porosity, cracking, and uneven composition within the target, affecting the vaporization stability of the target and the consistency of the coating composition during EB-PVD deposition. On the other hand, existing preparation methods struggle to balance the high density and good thermophysical properties of the target. While some processes can increase the target density, they can lead to excessive grain growth, which in turn reduces the material's fracture toughness and thermal shock resistance. Therefore, developing a method for stably preparing large-sized, high-performance gadolinium ytterbium zirconate ceramic targets is of great significance for promoting the upgrading of EB-PVD thermal barrier coating technology and meeting the high-performance protection requirements of high-temperature equipment. Summary of the Invention

[0006] The present invention aims to provide a method for preparing large-size, high-performance ceramic target solid solution particles and gadolinium zirconate ceramic targets that can be stably prepared.

[0007] To achieve the above objectives, the present invention adopts the following specific technical solution:

[0008] A ceramic target solid solution particle, by mass parts, is composed of the following components: 31-55 parts of zirconium oxide, 40-60 parts of gadolinium oxide, 4-8 parts of ytterbium oxide, 0.3-0.5 parts of dispersant, and 0.5-0.7 parts of binder.

[0009] A method for preparing a gadolinium ytterbium zirconate ceramic target includes the following steps:

[0010] Mixing of solid solution particles for ceramic target materials: By mass, take 31-55 parts of zirconium oxide, 40-60 parts of gadolinium oxide, 4-8 parts of ytterbium oxide, 0.3-0.5 parts of dispersant, and 0.5-0.7 parts of binder, and feed them into a sand mill. At the same time, add 45-55 parts of water to prepare a slurry, mix evenly and refine it.

[0011] Spray granulation: The mixed slurry is fed into a spray granulation tower, spray-dried to prepare powder, and then aged.

[0012] Blank forming: The aged powder is fed into an isostatic pressing mold and formed into a blank by isostatic pressing under high pressure;

[0013] Raw material drying and sintering: After drying the isostatically pressed high-pressure formed raw material, it is sent into a high-temperature furnace and sintered at high temperature to form a uniform gadolinium ytterbium zirconate solid solution.

[0014] Mechanical crushing and mechanical sieving: The gadolinium ytterbium zirconate solid solution after high-temperature sintering is sieved to particle sizes of 1-3 mm, 0.5-1 mm and below 0.5 mm respectively;

[0015] Air jet milling and air jet classification: Gadolinium ytterbium zirconate solid solution particles smaller than 0.5 mm are fed into an air jet mill for refinement, and particles with a particle size D50 of 50 μm and particles with a particle size D50 of 5 μm are selected by air jet classification.

[0016] Secondary raw material mixing: The gadolinium ytterbium zirconate solid solution particles after mechanical sieving and air classification are mixed in the following mass proportions: 20-30 parts of 1-3mm particles, 5-15 parts of 0.5-1mm particles, 25-30 parts of particles with a D50 of 50μm, 35-45 parts of particles with a D50 of 5μm, 18-23 parts of acidic zirconium sol, 0.3-0.5 parts of ammonia, and 0.5-0.8 parts of dispersant to prepare a gadolinium ytterbium zirconate solid solution slurry.

[0017] Slurry degassing and casting: After the mixed gadolinium ytterbium zirconate solid solution slurry is degassed in a vacuum mixer, it is slowly poured into a silicone mold and solidified. After demolding, it forms a gadolinium ytterbium zirconate ceramic target blank.

[0018] Target drying, sintering and heat treatment: After drying the gadolinium ytterbium zirconate ceramic target blank in a drying oven, it is sent to a high-temperature kiln for sintering. After reaching the sintering temperature and completing the heat preservation, it is quickly transferred to a low-temperature kiln for slow cooling, and finally the gadolinium ytterbium zirconate ceramic target is obtained.

[0019] Furthermore, in the ceramic target solid solution particle raw material mixing step, the D50 of zirconium oxide is 1 μm, the D50 of gadolinium oxide is 1 μm, the D50 of ytterbium oxide is 0.5 μm, the dispersant is D-134 type dispersant, and the binder is polyvinyl alcohol.

[0020] Furthermore, in the spray granulation step, the moisture content of the spray granulation powder needs to be controlled at 3-5%, and the particle size needs to be controlled below 30 mesh.

[0021] Furthermore, in the blank forming step, the isostatic pressing pressure is 200-250 MPa, and the holding time is 10-20 minutes.

[0022] Furthermore, in the billet drying and sintering steps, the drying temperature is 70-105℃, the drying time is 24-36 hours, the high-temperature sintering temperature is 1450-1650℃, and the holding time is 24-48 hours.

[0023] Furthermore, in the mechanical crushing and screening steps: the high-temperature sintered gadolinium ytterbium zirconate solid solution is crushed by a jaw crusher and a roller crusher, and then fed into a ternary vibrating screen for screening. The gadolinium ytterbium zirconate solid solution is screened to particle sizes of 1-3mm, 0.5-1mm and below 0.5mm respectively. The working parts of the jaw crusher and roller crusher must be made of zirconium oxide material to avoid impurities from being mixed in.

[0024] Furthermore, in the secondary raw material mixing step, the zirconium sol is a 20% content nano-acidic zirconium sol, the ammonia concentration is 3%, and the dispersant is 540P dispersant.

[0025] Furthermore, in the slurry degassing and casting steps, the vacuum mixing time is 15-20 minutes, the vacuum degree of the vacuum mixer is -0.1Mpa, the silicone hardness is Shore hardness 36A, and the overall casting time must be completed within 30 minutes.

[0026] Furthermore, in the target material drying, sintering and heat treatment steps, the drying temperature is 70-105℃, the drying time is 24-36 hours, the high-temperature sintering temperature is 1150-1300℃, the holding time is 4-8 hours, the temperature of transferring to the low-temperature furnace is 550-850℃, and the cooling rate is 0.2-0.5℃ / min.

[0027] The present invention has the following beneficial effects:

[0028] This invention patent provides a method for preparing large-size, high-performance gadolinium ytterbium zirconate ceramic targets and ceramic target solid solution particles for preparing gadolinium ytterbium zirconate ceramic targets. The gadolinium ytterbium zirconate ceramic targets or ceramic target solid solution particles use gadolinium ytterbium zirconate as the main raw material. Compared to traditional 8YSZ ceramic targets, due to the difference in ionic radius between rare earth elements and Zr⁴⁺, doping will create distortions and defects in the crystal lattice, suppressing the transformation from tetragonal to monoclinic phase at low temperatures, while enhancing lattice stability, thereby increasing the phase transition temperature. Therefore, its phase transition temperature is higher, enabling it to withstand higher service temperatures; simultaneously, it has a lower thermal conductivity, stronger corrosion resistance, and a coefficient of thermal expansion that is more compatible with the substrate, meeting the protection requirements of next-generation high-temperature equipment. Meanwhile, the traditional process of pressing ceramic targets under isostatic pressure and then sintering them at high temperature has been abandoned. Instead, innovative methods have been proposed for solid-state sintering, casting, and slow stress relief after high-temperature sintering. These methods solve the problems of defects such as pores, cracks, and uneven composition that are easily caused by traditional sintering processes, and further balance the high density and good thermophysical properties of the targets. Attached Figure Description

[0029] Figure 1 The X-ray diffraction pattern of the gadolinium ytterbium zirconate ceramic target disclosed in this invention;

[0030] Figure 2 The scanning electron microscope image of the gadolinium ytterbium zirconate ceramic target disclosed in this invention;

[0031] Figure 3 Scanning electron microscopy of the gadolinium ytterbium zirconate ceramic target material disclosed in this invention after coating preparation;

[0032] Figure 4 This is a flowchart of the preparation method of the gadolinium ytterbium zirconate ceramic target disclosed in this invention. Detailed Implementation

[0033] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. These embodiments are implemented based on the technical solution of the present invention, and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments.

[0034] A ceramic target solid solution particle, wherein 100 parts by weight of the ceramic target solid solution particle is composed of the following components: 31-55 parts of zirconium oxide, 40-60 parts of gadolinium oxide, 4-8 parts of ytterbium oxide, 0.3-0.5 parts of dispersant, and 0.5-0.7 parts of binder.

[0035] The gadolinium ytterbium zirconate ceramic target material, made from the solid solution particles of this ceramic target material, has a higher phase transition temperature than the traditional 8YSZ ceramic target material. This is because the ionic radius of rare earth elements differs from that of Zr4+, and the doping will form distortions and defects in the crystal lattice, suppressing the transformation from tetragonal to monoclinic phase at low temperatures and enhancing lattice stability, thereby increasing the phase transition temperature. Therefore, it can withstand higher service temperatures, while having a lower thermal conductivity, stronger corrosion resistance, and a coefficient of thermal expansion that is more compatible with the substrate, which can meet the protection requirements of the next generation of high-temperature equipment.

[0036] Example 1:

[0037] like Figure 4 The method for preparing a gadolinium zirconate ytterbium ceramic target includes the following steps:

[0038] Mixing of ceramic target solid solution particles: By mass, take 31-55 parts of zirconium oxide, 40-60 parts of gadolinium oxide, 4-8 parts of ytterbium oxide, 0.3-0.5 parts of dispersant, and 0.5-0.7 parts of binder, and feed them into a sand mill to form 100 parts by mass of ceramic target solid solution particles. At the same time, add 45-55 parts of water to prepare a slurry, mix evenly and refine.

[0039] Spray granulation: The mixed slurry is fed into a spray granulation tower, spray-dried to prepare powder, and then aged.

[0040] Blank forming: The aged powder is fed into an isostatic pressing mold and formed into a blank by isostatic pressing under high pressure.

[0041] Raw material drying and sintering: After drying the isostatically pressed and high-pressure formed raw material, it is sent to a high-temperature furnace and sintered at high temperature to form a uniformly structured gadolinium ytterbium zirconate solid solution.

[0042] Mechanical crushing and mechanical sieving: The gadolinium ytterbium zirconate solid solution after high-temperature sintering is sieved to particle sizes of 1-3 mm, 0.5-1 mm and below 0.5 mm respectively.

[0043] Air jet milling and air jet classification: Gadolinium ytterbium zirconate solid solution particles smaller than 0.5 mm are fed into the air jet mill for refinement. Particles with a particle size D50 of 50 μm and particles with a particle size D50 of 5 μm are selected by air jet classification. The working parts of the air jet mill and air jet classifier must be made of zirconium oxide to avoid impurities from being mixed in.

[0044] Secondary raw material mixing: The gadolinium ytterbium zirconate solid solution particles after mechanical sieving and air classification are mixed in the following proportions by weight: 20-30 parts of 1-3mm particles, 5-15 parts of 0.5-1mm particles, 25-30 parts of particles with a D50 of 50μm, and 35-45 parts of particles with a D50 of 5μm, to form 100 parts by weight of gadolinium ytterbium zirconate solid solution particles. 18-23 parts of acidic zirconium sol, 0.3-0.5 parts of ammonia, and 0.5-0.8 parts of dispersant are added and mixed evenly to prepare a gadolinium ytterbium zirconate solid solution slurry.

[0045] Slurry degassing and casting: After the mixed gadolinium ytterbium zirconate solid solution slurry is degassed in a vacuum mixer, it is slowly poured into a silicone mold and solidified. After solidification, it is demolded to form a gadolinium ytterbium zirconate ceramic target blank. Specifically, the size of the silicone mold is made according to the design size of the gadolinium ytterbium zirconate ceramic target at a 1:1 scale. The gadolinium ytterbium zirconate ceramic target has a cylindrical appearance.

[0046] Target drying, sintering and heat treatment: After drying the gadolinium ytterbium zirconate ceramic target blank in a drying oven, it is sent to a high-temperature kiln for sintering. After reaching the sintering temperature and completing the heat preservation, it is quickly transferred to a low-temperature kiln for slow cooling, and finally the gadolinium ytterbium zirconate ceramic target is obtained.

[0047] The gadolinium zirconate ceramic target not only meets the requirements of EB-PVD, but also the thermal barrier coating prepared using the gadolinium zirconate ceramic target has a higher operating temperature, lower thermal conductivity and longer service life than traditional thermal barrier coatings. The performance of the thermal barrier coating is shown in Table 1. Figure 1 The X-ray diffraction pattern of the gadolinium ytterbium zirconate ceramic target is shown. Figure 2 The scanning electron microscope (SEM) image of the gadolinium ytterbium zirconate ceramic target is shown. Figure 3 The image shows a scanning electron microscope (SEM) image of a gadolinium ytterbium zirconate ceramic target after coating preparation. The scale bar is 20 micrometers.

[0048] Table 1. Performance Test Table of Gadolinium Ytterbium Ceramic Target After Coating

[0049]

[0050] Preferably, in the ceramic target solid solution particle raw material mixing step, the D50 of zirconium oxide is 1 μm, the D50 of gadolinium oxide is 1 μm, the D50 of ytterbium oxide is 0.5 μm, the dispersant is D-134 type dispersant, and the binder is polyvinyl alcohol.

[0051] Preferably, in the spray granulation step, the moisture content of the spray granulation powder needs to be controlled at 3-5%, and the particle size needs to be controlled at less than 30 mesh.

[0052] Preferably, the isostatic pressing pressure in the blank forming step is 200-250 MPa, and the holding time is 10-20 minutes.

[0053] Preferably, in the billet drying and sintering steps, the drying temperature is 70-105℃, the drying time is 24-36 hours, the high-temperature sintering temperature is 1450-1650℃, and the holding time is 24-48 hours.

[0054] Preferably, in the mechanical crushing and screening step: the high-temperature sintered gadolinium ytterbium zirconate solid solution is crushed by a jaw crusher and a roller crusher, and then fed into a ternary vibrating screen for screening. The gadolinium ytterbium zirconate solid solution is screened to particle sizes of 1-3mm, 0.5-1mm and below 0.5mm respectively. The working parts of the jaw crusher and roller crusher must be made of zirconium oxide material to avoid impurities from being mixed in.

[0055] Preferably, in the secondary raw material mixing step, the zirconium sol is a 20% content nano-acidic zirconium sol, the ammonia concentration is 3%, and the dispersant is 540P dispersant.

[0056] Preferably, in the slurry degassing and casting steps, the vacuum mixing time is 15-20 minutes, the vacuum degree of the vacuum mixer is -0.1 MPa, the silicone hardness is Shore A 36A, and the overall casting time should be completed within 30 minutes. Specifically, the silicone mold is made at a 1:1 scale according to the design dimensions of the gadolinium ytterbium zirconate ceramic target, and the gadolinium ytterbium zirconate ceramic target has a cylindrical shape.

[0057] Preferably, in the target material drying, sintering and heat treatment steps, the drying temperature is 70-105℃, the drying time is 24-36 hours, the high-temperature sintering temperature is 1150-1300℃, the holding time is 4-8 hours, the temperature of transferring to the low-temperature furnace is 550-850℃, and the cooling rate is 0.2-0.5℃ / min.

[0058] Example 2:

[0059] A method for preparing a gadolinium ytterbium zirconate ceramic target material, comprising the following steps:

[0060] a) Raw material mixing: By weight, take 55 parts of high-purity zirconium oxide with a D50 of 1μm, 40 parts of high-purity gadolinium oxide with a D50 of 1μm, 4 parts of high-purity ytterbium oxide with a D50 of 0.5μm, 0.3 parts of D134 dispersant, and 0.7 parts of polyvinyl alcohol binder, and feed them into a sand mill. At the same time, add 45 parts of water to prepare the raw materials into a slurry. Mix evenly and refine the slurry before use.

[0061] b) Spray granulation: The mixed slurry is fed into a spray granulation tower and spray-dried to prepare powder. The moisture content of the spray granulated powder needs to be controlled at 3% and the particle size needs to be controlled below 30 mesh. After aging, it is ready for use.

[0062] c) Blank forming: The aged powder is fed into an isostatic pressing mold. The isostatic pressing pressure is 200MPa, and the holding time is 20 minutes. After being formed into a blank by isostatic pressing, it is ready for use.

[0063] d) Blank drying and sintering: After the high-pressure formed blank is dried in a drying oven at 70°C for 36 hours, it is sent into a high-temperature furnace and sintered at 1450°C for 48 hours to form a uniform gadolinium zirconate solid solution, which is ready for use.

[0064] e) Mechanical crushing and screening: The high-temperature sintered gadolinium ytterbium zirconate solid solution is crushed by a jaw crusher and a roller crusher, and then fed into a ternary vibrating screen for screening. The gadolinium ytterbium zirconate solid solution is screened to particle sizes of 1-3mm, 0.5-1mm and below 0.5mm, respectively, for later use.

[0065] f) Air jet milling and classification: Gadolinium ytterbium zirconate solid solution particles smaller than 0.5 mm are fed into an air jet mill for further refinement. Particles with a particle size D50 of 50 μm and particles with a particle size D50 of 5 μm are selected by air jet classification and set aside for later use.

[0066] g) Secondary raw material mixing: The gadolinium ytterbium zirconate solid solution particles after mechanical sieving and air classification are mixed according to the following mass percentages: 20 parts of 1-3mm particles, 15 parts of 0.5-1mm particles, 25 parts of particles with a D50 of 50μm, 40 parts of particles with a D50 of 5μm, 18 parts of 20% nano-acidic zirconium sol, 0.3 parts of 3% ammonia water, and 0.8 parts of 540P dispersant. The mixture is mixed evenly to prepare a gadolinium ytterbium zirconate solid solution slurry for later use.

[0067] h) Slurry degassing and casting: The mixed gadolinium ytterbium zirconate solid solution slurry is fed into a vacuum mixer for 15 minutes. The vacuum degree of the vacuum mixer is -0.1 MPa. After degassing, the slurry is slowly poured into a silicone mold of specified size. After the slurry solidifies, it is demolded to form a gadolinium ytterbium zirconate ceramic target blank.

[0068] i) Target drying, sintering and heat treatment: After demolding, the ceramic target is dried in a drying oven at 70℃ for 36 hours and then sent to a high-temperature kiln for sintering. After sintering at 1150℃ and holding for 8 hours, it is quickly transferred to a low-temperature kiln at 550℃ and slowly cooled at a rate of 0.5℃ / min to finally obtain gadolinium zirconate ceramic target.

[0069] Example 3:

[0070] A method for preparing a gadolinium ytterbium zirconate ceramic target material, comprising the following steps:

[0071] a) Raw material mixing: By weight, take 43 parts of high-purity zirconium oxide with a D50 of 1μm, 50 parts of high-purity gadolinium oxide with a D50 of 1μm, 6 parts of high-purity ytterbium oxide with a D50 of 0.5μm, 0.5 parts of D134 dispersant, and 0.5 parts of polyvinyl alcohol binder, and put them into a sand mill. At the same time, add 50 parts of water to prepare the raw materials into a slurry. After mixing evenly and refining, it is ready for use.

[0072] b) Spray granulation: The mixed slurry is fed into a spray granulation tower and spray-dried to prepare powder. The moisture content of the spray granulated powder needs to be controlled at 4%, and the particle size needs to be controlled below 30 mesh. After aging, it is ready for use.

[0073] c) Blank forming: The aged powder is fed into an isostatic pressing mold. The isostatic pressing pressure is 230MPa, and the holding time is 15 minutes. After being formed into a blank by isostatic pressing, it is ready for use.

[0074] d) Blank drying and sintering: After the high-pressure formed blank is dried in a drying oven at 95°C for 30 hours, it is sent into a high-temperature furnace and sintered at 1500°C for 36 hours to form a uniform gadolinium zirconate solid solution, which is ready for use.

[0075] e) Mechanical crushing and screening: The high-temperature sintered gadolinium ytterbium zirconate solid solution is crushed by a jaw crusher and a roller crusher, and then fed into a ternary vibrating screen for screening. The gadolinium ytterbium zirconate solid solution is screened to particle sizes of 1-3mm, 0.5-1mm and below 0.5mm, respectively, for later use.

[0076] f) Air jet milling and classification: Gadolinium ytterbium zirconate solid solution particles smaller than 0.5 mm are fed into an air jet mill for further refinement. Particles with a particle size D50 of 50 μm and particles with a particle size D50 of 5 μm are selected by air jet classification and set aside for later use.

[0077] g) Secondary raw material mixing: The gadolinium ytterbium zirconate solid solution particles after mechanical sieving and air classification are mixed according to the following mass percentages: 25 parts of 1-3mm particles, 10 parts of 0.5-1mm particles, 20 parts of particles with a D50 of 50μm, 45 parts of particles with a D50 of 5μm, plus 20 parts of 20% nano-acidic zirconium sol, 0.4 parts of 3% ammonia water, and 0.6 parts of 540P dispersant. Mix evenly to prepare gadolinium ytterbium zirconate solid solution slurry for later use.

[0078] h) Slurry degassing and casting: The mixed gadolinium ytterbium zirconate solid solution slurry is fed into a vacuum mixer for 18 minutes. The vacuum degree of the vacuum mixer is -0.1 MPa. After degassing, the slurry is slowly poured into a silicone mold of specified size. After the slurry solidifies, it is demolded to form a gadolinium ytterbium zirconate ceramic target blank.

[0079] i) Target drying, sintering and heat treatment: After demolding, the ceramic target is dried in a drying oven at 95℃ for 30 hours and then sent to a high-temperature kiln for sintering. After sintering at 1200℃ and holding for 6 hours, it is quickly transferred to a low-temperature kiln at 700℃ and slowly cooled at a rate of 0.3℃ / min to finally obtain gadolinium zirconate ceramic target.

[0080] Example 4:

[0081] A method for preparing a gadolinium ytterbium zirconate ceramic target material, comprising the following steps:

[0082] a) Raw material mixing: By weight, take 31 parts of high-purity zirconium oxide with a D50 of 1μm, 60 parts of high-purity gadolinium oxide with a D50 of 1μm, 8 parts of high-purity ytterbium oxide with a D50 of 0.5μm, 0.4 parts of D134 dispersant, and 0.6 parts of polyvinyl alcohol binder, and feed them into a sand mill. At the same time, add 55 parts of water to prepare the raw materials into a slurry. After mixing evenly and refining, it is ready for use.

[0083] b) Spray granulation: The mixed slurry is fed into a spray granulation tower and spray-dried to prepare powder. The moisture content of the spray granulated powder needs to be controlled at 5%, and the particle size needs to be controlled below 30 mesh. After aging, it is ready for use.

[0084] c) Blank forming: The aged powder is fed into an isostatic pressing mold. The isostatic pressing pressure is 250MPa and the holding time is 10 minutes. After being formed into a blank by isostatic pressing, it is ready for use.

[0085] d) Blank drying and sintering: After the high-pressure formed blank is dried in a drying oven at 105℃ for 24 hours, it is sent into a high-temperature furnace and sintered at 1650℃ for 24 hours to form a uniform gadolinium zirconate solid solution, which is ready for use.

[0086] e) Mechanical crushing and screening: The high-temperature sintered gadolinium ytterbium zirconate solid solution is crushed by a jaw crusher and a roller crusher, and then fed into a ternary vibrating screen for screening. The gadolinium ytterbium zirconate solid solution is screened to particle sizes of 1-3mm, 0.5-1mm and below 0.5mm, respectively, for later use.

[0087] f) Air jet milling and classification: Gadolinium ytterbium zirconate solid solution particles smaller than 0.5 mm are fed into an air jet mill for further refinement. Particles with a particle size D50 of 50 μm and particles with a particle size D50 of 5 μm are selected by air jet classification and set aside for later use.

[0088] g) Secondary raw material mixing: The gadolinium ytterbium zirconate solid solution particles after mechanical sieving and air classification are mixed according to the following mass percentages: 30 parts of 1-3mm particles, 5 parts of 0.5-1mm particles, 30 parts of particles with a D50 of 50μm, 35 parts of particles with a D50 of 5μm, 23 parts of 20% nano-acidic zirconium sol, 0.5 parts of 3% ammonia water, and 0.5 parts of 540P dispersant. The mixture is mixed evenly to prepare a gadolinium ytterbium zirconate solid solution slurry for later use.

[0089] h) Slurry degassing and casting: The mixed gadolinium ytterbium zirconate solid solution slurry is fed into a vacuum mixer for 20 minutes. The vacuum degree of the vacuum mixer is -0.1 MPa. After degassing, the slurry is slowly poured into a silicone mold of specified size. After the slurry solidifies, it is demolded to form a gadolinium ytterbium zirconate ceramic target blank.

[0090] i) Target drying, sintering and heat treatment: After demolding, the ceramic target is dried in a drying oven at 105℃ for 24 hours and then sent to a high-temperature kiln for sintering. After being heated to 1300℃ and held for 4 hours, it is quickly transferred to a low-temperature kiln at 850℃ and cooled slowly at a rate of 0.2℃ / min to finally obtain gadolinium zirconate ceramic target.

[0091] Example 5:

[0092] A method for preparing a large-size, high-performance gadolinium zirconate ytterbium ceramic target material is as follows:

[0093] a) Raw material mixing: By weight, take 46 parts of high-purity zirconium oxide with a D50 of 1μm, 48 parts of high-purity gadolinium oxide with a D50 of 1μm, 5 parts of high-purity ytterbium oxide with a D50 of 0.5μm, 0.5 parts of D134 dispersant, and 0.5 parts of polyvinyl alcohol binder, and put them into a sand mill. At the same time, add 50 parts of water to prepare the raw materials into a slurry. Mix evenly and refine the slurry before use.

[0094] b) Spray granulation: The mixed slurry is fed into a spray granulation tower and spray-dried to prepare powder. The moisture content of the spray granulated powder needs to be controlled at 4%, and the particle size needs to be controlled below 30 mesh. After aging, it is ready for use.

[0095] c) Blank forming: The aged powder is fed into an isostatic pressing mold. The isostatic pressing pressure is 240MPa and the holding time is 15 minutes. After being formed into a blank by isostatic pressing, it is ready for use.

[0096] d) Blank drying and sintering: After the high-pressure formed blank is dried in a drying oven at 95°C for 30 hours, it is sent into a high-temperature furnace and sintered at 1550°C for 36 hours to form a uniform gadolinium zirconate solid solution, which is ready for use.

[0097] e) Mechanical crushing and screening: The high-temperature sintered gadolinium ytterbium zirconate solid solution is crushed by a jaw crusher and a roller crusher, and then fed into a ternary vibrating screen for screening. The gadolinium ytterbium zirconate solid solution is screened to particle sizes of 1-3mm, 0.5-1mm and below 0.5mm, respectively, for later use.

[0098] f) Air jet milling and classification: Gadolinium ytterbium zirconate solid solution particles smaller than 0.5 mm are fed into an air jet mill for further refinement. Particles with a particle size D50 of 50 μm and particles with a particle size D50 of 5 μm are selected by air jet classification and set aside for later use.

[0099] g) Secondary raw material mixing: The gadolinium ytterbium zirconate solid solution particles after mechanical sieving and air classification are mixed according to the following mass percentages: 28 parts of 1-3mm particles, 7 parts of 0.5-1mm particles, 23 parts of particles with a D50 of 50μm, 42 parts of particles with a D50 of 5μm, 19 parts of 20% nano-acidic zirconium sol, 0.4 parts of 3% ammonia water, and 0.7 parts of 540P dispersant. The mixture is then thoroughly mixed to prepare a gadolinium ytterbium zirconate solid solution slurry for later use.

[0100] h) Slurry degassing and casting: The mixed gadolinium ytterbium zirconate solid solution slurry is fed into a vacuum mixer for 18 minutes. The vacuum degree of the vacuum mixer is -0.1 MPa. After degassing, the slurry is slowly poured into a silicone mold of specified size. After the slurry solidifies, it is demolded to form a gadolinium ytterbium zirconate ceramic target blank.

[0101] i) Target drying, sintering and heat treatment: After demolding, the ceramic target is dried in a drying oven at 95°C for 30 hours and then sent to a high-temperature kiln for sintering. After being heated to 1250°C and held for 6 hours, it is quickly transferred to a low-temperature kiln at 750°C and cooled slowly at a rate of 0.3°C / min to finally obtain gadolinium zirconate ceramic target.

[0102] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method of producing a gadolinium ytterbium zirconate ceramic target material, characterized by, Includes the following steps: Mixing of solid solution particles for ceramic target materials: By mass, take 31-55 parts of zirconium oxide, 40-60 parts of gadolinium oxide, 4-8 parts of ytterbium oxide, 0.3-0.5 parts of dispersant, and 0.5-0.7 parts of binder, and feed them into a sand mill. At the same time, add 45-55 parts of water to prepare a slurry, mix evenly and refine it. Spray granulation: The mixed slurry is fed into a spray granulation tower, spray-dried to prepare powder, and then aged. Blank forming: The aged powder is fed into an isostatic pressing mold and formed into a blank by isostatic pressing under high pressure; Raw material drying and sintering: After drying the isostatically pressed high-pressure formed raw material, it is sent into a high-temperature furnace and sintered at high temperature to form a uniform gadolinium ytterbium zirconate solid solution. Mechanical crushing and mechanical sieving: The gadolinium ytterbium zirconate solid solution after high-temperature sintering is sieved to particle sizes of 1-3 mm, 0.5-1 mm and below 0.5 mm respectively; Air jet milling and air jet classification: Gadolinium ytterbium zirconate solid solution particles smaller than 0.5 mm are fed into an air jet mill for refinement, and particles with a particle size D50 of 50 μm and particles with a particle size D50 of 5 μm are selected by air jet classification. Secondary raw material mixing: The gadolinium ytterbium zirconate solid solution particles after mechanical sieving and air classification are mixed in the following mass proportions: 20-30 parts of 1-3mm particles, 5-15 parts of 0.5-1mm particles, 25-30 parts of particles with a D50 of 50μm, 35-45 parts of particles with a D50 of 5μm, 18-23 parts of acidic zirconium sol, 0.3-0.5 parts of ammonia, and 0.5-0.8 parts of dispersant to prepare a gadolinium ytterbium zirconate solid solution slurry. Slurry degassing and casting: After the mixed gadolinium ytterbium zirconate solid solution slurry is degassed in a vacuum mixer, it is slowly poured into a silicone mold and solidified. After demolding, it forms a gadolinium ytterbium zirconate ceramic target blank. Target drying, sintering and heat treatment: After drying the gadolinium ytterbium zirconate ceramic target blank in a drying oven, it is sent to a high-temperature kiln for sintering. After reaching the sintering temperature and completing the heat preservation, it is quickly transferred to a low-temperature kiln for slow cooling, and finally the gadolinium ytterbium zirconate ceramic target is obtained; In the mixing step of the solid solution particle raw materials for ceramic targets, the D50 of zirconium oxide is 1 μm, the D50 of gadolinium oxide is 1 μm, the D50 of ytterbium oxide is 0.5 μm, the dispersant is D-134 type dispersant, and the binder is polyvinyl alcohol; In the mechanical crushing and screening steps: the high-temperature sintered gadolinium ytterbium zirconate solid solution is crushed by a jaw crusher and a roller crusher, and then fed into a ternary vibrating screen for screening. The gadolinium ytterbium zirconate solid solution is screened to particle sizes of 1-3mm, 0.5-1mm, and below 0.5mm. The working parts of the jaw crusher and roller crusher must be made of zirconium oxide to avoid impurities from being mixed in. In the secondary raw material mixing step, the zirconium sol is a 20% content nano-acidic zirconium sol, the ammonia concentration is 3%, and the dispersant is 540P dispersant.

2. The method of claim 1, wherein the gadolinium ytterbium zirconate ceramic target is prepared by the steps of: In the spray granulation step, the moisture content of the spray granulation powder needs to be controlled at 3-5%, and the particle size needs to be controlled below 30 mesh. ​ 3. The method of claim 1, wherein the method further comprises the step of: In the blank forming step, the isostatic pressing pressure is 200-250MPa, and the holding time is 10-20 minutes. ​ 4. The method of claim 1, wherein the gadolinium ytterbium zirconate ceramic target is prepared by the steps of: In the billet drying and sintering steps, the drying temperature is 70-105℃, the drying time is 24-36 hours, the high-temperature sintering temperature is 1450-1650℃, and the holding time is 24-48 hours. ​ 5. The method for preparing a gadolinium zirconate ytterbium ceramic target according to claim 1, characterized in that, In the slurry degassing and casting steps, the vacuum mixing time is 15-20 minutes, the vacuum degree of the vacuum mixer is -0.1Mpa, the silicone hardness is Shore hardness 36A, and the overall casting time must be completed within 30 minutes.

6. The method for preparing a gadolinium zirconate ytterbium ceramic target according to claim 1, characterized in that, In the target material drying, sintering and heat treatment steps, the drying temperature is 70-105℃, the drying time is 24-36 hours, the high-temperature sintering temperature is 1150-1300℃, the holding time is 4-8 hours, the temperature of transferring to the low-temperature furnace is 550-850℃, and the cooling rate is 0.2-0.5℃ / min.

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