A method for preparing high-entropy zirconate PVD ceramic thin films

Abstract

This invention discloses a method for preparing high-entropy zirconate PVD ceramic films. The method involves first spray-granulating five rare earth oxides—nano-Sm₂O₃, nano-Eu₂O₃, nano-Tb₂O₃, nano-Dy₂O₃, nano-Lu₂O₃, and nano-ZrO₂—with zirconium oxide to obtain target raw material powder. After sieving, spherical powders with different particle size ratios are obtained. These powders are then used to fabricate target green bodies using cold isostatic pressing, followed by sintering. Finally, the high-entropy zirconate EB-PVD target is deposited onto a smooth and glossy PVD substrate using PVD technology to form a high-entropy zirconate PVD ceramic film. The high-entropy ceramic film prepared using PVD technology exhibits significantly improved high-temperature stability, capable of withstanding environments exceeding 1500℃, enhanced interfacial adhesion, and adaptability to repeated thermal cycling requirements.

Description

Technical Field

[0001] This invention belongs to the field of high-temperature thermal protection coatings and relates to a method for preparing a high-entropy ceramic film, specifically a method for preparing a high-entropy zirconate PVD ceramic thin film. Background Technology

[0002] High-temperature ceramic thin films refer to ceramic-based thin film materials that possess excellent thermal and mechanical properties at high temperatures. Due to their superior high-temperature resistance, oxidation resistance, corrosion resistance, and high hardness, high-temperature ceramic thin films have significant application value in high-end manufacturing. For example, in the aerospace field, ceramic thin films are used as thermal barrier coatings in turbine blades to improve their heat resistance and oxidation resistance; in energy and industrial equipment, ceramic thin films can be used in key components of gas turbines and internal combustion engines to extend equipment lifespan; in the electronics industry, ceramic thin films possess excellent dielectric properties and thermal stability, making them suitable for high-performance electronic devices. However, traditional preparation methods (such as chemical vapor deposition and wet chemical methods) often suffer from environmental pollution, high preparation temperatures, and insufficient film uniformity, making it difficult to meet the needs of high-temperature ceramic thin films in practical applications.

[0003] Physical vapor deposition (PVD) is an advanced thin film preparation technology that transfers materials to the substrate surface through physical means to form a dense and uniform thin film layer. Its advantages include low preparation temperature, strong process controllability, flexible adjustment of thin film chemical composition, and low environmental pollution, making it an important technology in the preparation of high-temperature ceramic thin films. PVD includes processes such as evaporation deposition, sputtering deposition, and ion plating, and ceramic thin films with different chemical compositions and structures can be obtained by controlling deposition parameters. However, in existing technologies, the preparation of high-temperature ceramic thin films by PVD still faces the following technical challenges: (1) High-temperature stability of the film: The film needs to maintain excellent mechanical properties and chemical stability under high-temperature conditions. (2) Adhesion between the film and the substrate: During thermal cycling, the film is prone to peeling, requiring further optimization of the bonding interface.

[0004] In recent years, significant progress has been made in the preparation of nanostructured thin films and multi-component ceramic thin films using PVD technology. These novel coatings have shown promising application prospects in improving the high-temperature performance, thermal shock resistance, and adhesion of thin films. However, the preparation techniques for high-temperature ceramic thin films still need further optimization for different application scenarios to overcome the limitations of existing processes.

[0005] High-entropy ceramic thin films are novel materials developed based on the theory of high-entropy alloys. Unlike traditional single or binary systems, they are composed of multiple principal elements (metals or non-metals), and their complex structures are typically stabilized by entropy effects. These films exhibit significant advantages in high-temperature stability, oxidation resistance, corrosion resistance, and radiation resistance, and are considered an important solution for meeting the demands of extreme operating conditions. However, the complex composition and microstructure design requirements of high-entropy ceramic thin films place extremely high demands on the fabrication process.

[0006] PVD, with its low pollution, precise control, and ability to design various structures, has become the preferred method for preparing high-entropy ceramic thin films. By controlling the deposition process parameters, PVD technology can achieve fine-tuning of the film's microstructure, phase composition, and chemical composition, providing an effective means for optimizing the performance of high-entropy ceramic thin films.

[0007] High-entropy ceramic thin films prepared using PVD technology have attracted significant attention in the field of materials science due to their multifunctional properties and broad application prospects. High-performance thin films can be achieved through rational material design, process optimization, and structural control. However, further collaborative innovation combining multidisciplinary technologies is needed to address the challenges of designing complex systems and scaling up production. In the future, with continuous advancements in materials technology and fabrication processes, high-entropy ceramic thin films are expected to play an even more important role in high-end manufacturing, energy, and extreme environment applications. Summary of the Invention

[0008] To address the problems of insufficient high-temperature stability, poor interfacial adhesion, and difficulties in functional design of thin films in existing technologies, this invention provides a method for preparing high-entropy zirconate PVD ceramic thin films. This method, through specific system optimization and parameter control, prepares ceramic thin films with high density, high adhesion, and high-temperature and corrosion resistance, suitable for various high-temperature applications.

[0009] The objective of this invention is achieved through the following technical solution:

[0010] A method for preparing a high-entropy zirconate PVD ceramic thin film includes the following steps:

[0011] Step 1: Add zirconia grinding balls and an appropriate amount of deionized water to a vertical ball mill. Then add a certain mass of dispersant to the deionized water. After the dispersant is completely dissolved, proceed according to (Sm... 0.2 Eu 0.2 Tb 0.2 Dy 0.2 Lu 0.2The mixture of Zr2O7 (SETDL) in the indicated proportions was ball-milled with nano-Sm2O3 powder, nano-Eu2O3 powder, nano-Tb2O3 powder, nano-Dy2O3 powder, nano-Lu2O3 powder, and nano-ZrO2 powder for a period of time. After adding a certain amount of binder, the mixture was ball-milled again for a period of time to obtain a uniform slurry.

[0012] The particle size of the nano-Sm2O3 powder is 5-90 nm;

[0013] The particle size of the nano-Eu2O3 powder is 5-90 nm;

[0014] The particle size of the nano-Tb2O3 powder is 5-90 nm;

[0015] The particle size of the nano-Dy2O3 powder is 5-90 nm.

[0016] The particle size of the nano-Lu2O3 powder is 5-90 nm.

[0017] The particle size of the nano-ZrO2 powder is 5–90 nm;

[0018] The nano Sm2O3 powder, nano Eu2O3 powder, nano Tb2O3 powder, nano Dy2O3 powder, nano Lu2O3 powder, and nano ZrO2 powder raw materials are of 4N purity.

[0019] The amount of deionized water used is 0.5 to 3 times the total mass of the nanopowder;

[0020] The dispersant is sodium tripolyphosphate (Na5P3O4). 10 The dispersant consists of one or more of the following: sodium hexametaphosphate ((NaPO3)6), sodium pyrophosphate (Na4P2O7), ammonium citrate (C6H5O7(NH4)3), sodium citrate (C6H5Na3O7), polyvinyl alcohol (PVA), and polyethylene glycol (PEG). The amount of dispersant used is 0.03 to 6% of the total mass of the nanoparticles.

[0021] The diameter of the zirconia grinding balls is 2-10 mm, the amount of zirconia grinding balls used is 1-5 times the total mass of the nanopowder, the total grinding time is 6-24 h, and the rotation speed is 300-1000 rpm.

[0022] The binder is one of the following: gum arabic (Acacia), polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), ethyl silicate (TEOS), etc., and the amount of binder used is 0.1-10% of the total mass of the nanoparticles;

[0023] Step 2: The slurry obtained in Step 1 is spray-granulated to obtain micron-sized nanostructured spherical rare earth oxide powder, wherein:

[0024] The parameters for the spray granulation are as follows: the inlet air temperature is set to 200-250℃, the outlet air temperature is set to 100-130℃, the peristaltic pump speed is set to 30-45r / min, and the needle speed is set to 10-15t / min.

[0025] Step 3: The rare earth oxide powder obtained in Step 2 is sieved according to particle size. The spherical powders of different particle sizes are then proportioned and pressed using a cold isostatic pressing method to obtain target green bodies with different porosities.

[0026] The sieving specifications are 50-150 mesh, 150-300 mesh, and 300-400 mesh, with a mass ratio of 2-6:1-3:1-5, and are used according to the particle size distribution of the granulated powder and its different porosity requirements;

[0027] During the pressing process, the pressure is controlled at 150-250 MPa, and the holding time is controlled at 120-300 s.

[0028] The cold isostatic pressing method can use forming methods such as wet bag cold isostatic pressing, dry bag cold isostatic pressing, and press pre-pressing. Preferably, the cold isostatic pressing method is wet bag cold isostatic pressing.

[0029] Step 4: Sinter the target green material to obtain SETDL high-entropy zirconate EB-PVD target material, wherein:

[0030] The sintering mechanism is as follows: First, the temperature is increased to 350℃ (removal temperature) at a rate of 1-10℃ / min and held for 300-420 min. Then, the temperature is increased to 1100℃ at a rate of 1-10℃ / min and held for 180-250 min. Subsequently, the temperature is increased to 1400℃ (synthesis temperature) at a rate of 1-10℃ / min and held for 480-600 min. Finally, the temperature is reduced to room temperature.

[0031] The discharge temperature is related to the type of dispersant and glue used in granulation, and the synthesis temperature is related to different high-entropy systems.

[0032] Step 5: Using physical vapor deposition (PVD) technology, high-entropy zirconate EB-PVD target material is deposited on a smooth and glossy PVD substrate surface to form a SETDL high-entropy zirconate PVD ceramic thin film, wherein:

[0033] The PVD substrate can be one of a single crystal silicon board, a polished alloy substrate, etc.

[0034] The parameters for preparing the SETDL high-entropy zirconate PVD ceramic thin film are as follows: the substrate temperature is heated from room temperature to 50–200°C; the distance between the substrate and the evaporation target (target-substrate distance) and the angle between the substrate plane normal and the incident vapor particles (incident angle) can be adjusted according to actual needs, with a maximum target-substrate distance of 500 mm and an incident angle set at 45°; during coating preparation, the electron gun high voltage is -10–-4 kV, and the electron gun beam current is 80–110 W / cm. 2 The scanning position (X-axis, Y-axis) current variation range is ±0.7A-±1.3A. The deposition rate is controlled by controlling the electron beam current and adjusting the size of the evaporation target molten pool. The deposition rate can reach up to 1-5nm / min, and the deposition coating thickness is 10-500nm.

[0035] Compared with the prior art, the present invention has the following advantages:

[0036] 1. This invention utilizes nanoparticle regranulation technology and cold isostatic pressing technology to prepare SETDL high-entropy zirconate into a target material suitable for electron beam physical vapor deposition, providing a method for implementing this high-performance high-entropy material on thermal spray coatings.

[0037] 2. This invention utilizes particle size classification and distribution technology to press rare earth oxide spherical powder into green bodies. To ensure that the overall volume shrinkage rate of the target material is minimized and that it meets the requirements of a certain porosity, the solid-phase synthesis sintering route is combined with the target material sintering route. This allows for strict control of porosity and volume shrinkage, solving the problems of unstable dimensions and poor toughness of ceramic target materials after sintering. It also simplifies the target material preparation process and reduces production costs.

[0038] 3. The SETDL target material prepared by this invention has high purity, excellent mechanical properties, and a smooth coating surface structure. It can be used to replace traditional EB-PVD coating materials as high-performance thermal barrier coating materials for aero-engines and gas turbines.

[0039] 4. The high-entropy ceramic thin film prepared by the present invention using PVD technology has significantly improved high-temperature stability, can withstand environments up to 1500℃ and above, has enhanced interfacial bonding, and can meet the requirements of multiple thermal cycles. Attached Figure Description

[0040] Figure 1 This is a process flow diagram for the preparation of high-entropy zirconate PVD ceramic thin films;

[0041] Figure 2 This is a macroscopic structural diagram of the target material after sintering in Example 1;

[0042] Figure 3 This is a cross-sectional structural diagram of the target material in Example 1;

[0043] Figure 4 This is the surface morphology and energy spectrum of the molten pool after the target material evaporates in Example 1;

[0044] Figure 5 These are the surface morphology diagram and energy dispersive spectroscopy (EDS) of the coating in Example 2;

[0045] Figure 6 These are the cross-sectional morphology diagram and energy spectrum diagram of the coating in Example 2;

[0046] Figure 7 This is the XRD pattern of the high-entropy ceramic film prepared by PVD in Example 2. Detailed Implementation

[0047] The technical solution of the present invention will be further described below with reference to the embodiments, but it is not limited thereto. Any modifications or equivalent substitutions to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be covered within the protection scope of the present invention.

[0048] Example 1:

[0049] This embodiment provides a method for preparing high-entropy zirconate PVD ceramic films. The method involves first obtaining target material powder by spray granulation of five rare earth oxides—nano-Sm₂O₃ powder, nano-Eu₂O₃ powder, nano-Tb₂O₃ powder, nano-Dy₂O₃ powder, nano-Lu₂O₃ powder, and nano-ZrO₂ powder—with zirconium oxide. After sieving, spherical powders with different particle size ratios are obtained. A target green body is then fabricated using cold isostatic pressing, followed by sintering. Finally, the high-entropy zirconate EB-PVD target is deposited onto a smooth and glossy PVD substrate using physical vapor deposition (PVD) technology to form a high-entropy zirconate PVD ceramic film. Figure 1 As shown, this is achieved through the following steps:

[0050] Step 1: According to (Sm) 0.2 Eu 0.2 Tb 0.2 Dy 0.2 Lu 0.2 According to the proportions shown in 2Zr2O7, nano-Sm2O3 powder, nano-Eu2O3 powder, nano-Tb2O3 powder, nano-Dy2O3 powder, nano-Lu2O3 powder, and nano-ZrO2 powder were weighed, wherein: the particle size of the nano-Sm2O3 powder is 20nm; the particle size of the nano-Eu2O3 powder is 20nm; the particle size of the nano-Tb2O3 powder is 20nm; the particle size of the nano-Dy2O3 powder is 20nm; the particle size of the nano-Lu2O3 powder is 20nm; and the particle size of the nano-ZrO2 powder is 20nm.

[0051] Step 2: Add deionized water to a vertical ball mill jar, then add ammonium citrate dispersant, nano-Sm2O3 powder, nano-Eu2O3 powder, nano-Tb2O3 powder, nano-Dy2O3 powder, nano-Lu2O3 powder, nano-ZrO2 powder, and zirconia grinding balls. Ball mill for 12 hours to obtain a uniform slurry. The amount of deionized water is twice the total mass of the nano-powder, the amount of ammonium citrate is 0.5% of the total mass of the nano-powder, the diameter of the zirconia grinding balls is 3 mm and 5 mm, the mass ratio is 6:4, and the mass of the zirconia grinding balls is 2.5 times the total mass of the nano-powder.

[0052] Step 3: Add the binder gum arabic to the uniform slurry obtained in Step 2 and ball mill for 0.5 hours to obtain a uniform slurry. The amount of gum arabic is 1.0% of the total mass of the nanoparticles.

[0053] Step 4: Add the slurry obtained in Step 3 to the mixer and spray granulate to obtain agglomerated powder. The mixer parameters are 15 rpm, and the spray granulation parameters are: inlet air temperature of 245℃, outlet air temperature of 120℃, needle frequency of 10 times per minute, and peristaltic pump speed of 40 rpm.

[0054] Step 5: The agglomerated powder obtained after spray granulation in Step 4 is sieved using 400 mesh, 200 mesh, and 100 mesh sieves. The resulting powders of these three specifications are mixed in a mass ratio of 2:2:6 and then subjected to wet bag cold isostatic pressing at 200 MPa for 120 seconds. This reduces the need for pre-pressing and molding in the early stages, resulting in a target green with a diameter of 80 mm and a height of 110 mm. The particle size distribution can be adjusted appropriately according to different process requirements.

[0055] Step 6: Sinter the target green material using a box sintering furnace. Increase the temperature to 350℃ (removal temperature) at 5℃ / min and hold for 300 min. Then increase the temperature to 1100℃ at 5℃ / min and hold for 180 min. Finally, increase the temperature to 1400℃ (synthesis temperature) at 5℃ / min and hold for 480 min before slowly cooling to room temperature to obtain SETDL high-entropy zirconate target material.

[0056] Step 7: Select a monocrystalline silicon substrate as the base material, which has a clean and glossy surface.

[0057] Step 8: The high-entropy target material sintered in Step 6 is deposited onto the surface of the single-crystal silicon substrate from Step 7 using physical vapor deposition (PVD) to obtain the SETDL PVD ceramic thin film. The parameters for preparing the SETDL high-entropy zirconate ceramic thin film are as follows: substrate temperature is heated from room temperature to 120°C, target-substrate distance is 300 mm, incident angle is set to 45°, and during coating preparation, the electron gun high voltage is -7.92 kV, and the electron gun beam current is 102 W / cm².2 The maximum current along the X-axis at the scanning position is -0.54A, the maximum current along the Y-axis at the scanning position is -0.23A, the deposition rate is 1nm / min, and the thickness of the deposited coating is 100nm.

[0058] In this embodiment, the macroscopic structure diagram of the target material after sintering is as follows: Figure 2 As shown, by Figure 2 It can be seen that the macroscopic dimensions meet the requirements and the surface quality is good; the cross-sectional structure diagram of the target material is as follows. Figure 3 As shown, by Figure 3 It can be seen that the pores are uniformly distributed, the pore size is uniformly distributed, and there are no obvious internal defects; the surface morphology and energy dispersive spectroscopy of the molten pool after target evaporation are shown in the figure. Figure 4 As shown, by Figure 4 It can be seen that the melting pool has a good melting effect after electron beam melting, the molten droplets are uniform without obvious cracks, and the element distribution is uniform; the target density and volume shrinkage rate are shown in Table 1.

[0059] Table 1

[0060]

[0061] Example 2:

[0062] This embodiment provides a method for preparing high-entropy zirconate PVD ceramic films. The method involves first obtaining target material powder by spray granulation of five rare earth oxides—nano-Sm₂O₃ powder, nano-Eu₂O₃ powder, nano-Tb₂O₃ powder, nano-Dy₂O₃ powder, nano-Lu₂O₃ powder, and nano-ZrO₂ powder—with zirconium oxide. After sieving, spherical powders with different particle size ratios are obtained. A target green body is then fabricated using cold isostatic pressing, followed by sintering. Finally, the high-entropy zirconate EB-PVD target is deposited onto a smooth and glossy PVD substrate using physical vapor deposition (PVD) technology to form a high-entropy zirconate PVD ceramic film. Figure 1 As shown, this is achieved through the following steps:

[0063] Step 1: According to (Sm) 0.2 Eu 0.2 Tb 0.2 Dy 0.2 Lu 0.2According to the proportions shown in 2Zr2O7, nano-Sm2O3 powder, nano-Eu2O3 powder, nano-Tb2O3 powder, nano-Dy2O3 powder, nano-Lu2O3 powder, and nano-ZrO2 powder were weighed, wherein: the particle size of the nano-Sm2O3 powder is 20nm; the particle size of the nano-Eu2O3 powder is 20nm; the particle size of the nano-Tb2O3 powder is 20nm; the particle size of the nano-Dy2O3 powder is 20nm; the particle size of the nano-Lu2O3 powder is 20nm; and the particle size of the nano-ZrO2 powder is 20nm.

[0064] Step 2: Add deionized water to a vertical ball mill jar, then add ammonium citrate dispersant, nano-Sm2O3 powder, nano-Eu2O3 powder, nano-Tb2O3 powder, nano-Dy2O3 powder, nano-Lu2O3 powder, nano-ZrO2 powder, and zirconia grinding balls. Ball mill for 12 hours to obtain a uniform slurry. The amount of deionized water is twice the total mass of the nano-powder, the amount of ammonium citrate is 0.5% of the total mass of the nano-powder, the diameter of the zirconia grinding balls is 3 mm and 5 mm, and the mass of the zirconia grinding balls is 2.5 times the total mass of the nano-powder.

[0065] Step 3: Add the binder gum arabic to the uniform slurry obtained in Step 2 and ball mill for 0.5 hours to obtain a uniform slurry. The amount of binder is 1.0% of the mass of the raw material powder.

[0066] Step 4: Add the slurry obtained in Step 3 to the mixer and spray granulate to obtain agglomerated powder. The mixer parameters are 15 rpm, and the spray granulation parameters are: inlet air temperature of 245℃, outlet air temperature of 120℃, needle frequency of 10 times per minute, and peristaltic pump speed of 45 rpm.

[0067] Step 5: The agglomerated powder obtained after spray granulation in Step 4 is sieved using 400 mesh, 150 mesh, and 100 mesh sieves. The resulting powders of these three sizes are mixed in a mass ratio of 5:3:2 and then subjected to wet bag cold isostatic pressing: a pressure of 200 MPa is maintained for 120 seconds to obtain the target green body. The particle size distribution can be adjusted appropriately according to different process requirements.

[0068] Step 6: Sinter the target green material using a box sintering furnace. Increase the temperature to 350℃ (removal temperature) at 5℃ / min and hold for 300 min. Then increase the temperature to 1100℃ at 5℃ / min and hold for 180 min. Finally, increase the temperature to 1400℃ (synthesis temperature) at 5℃ / min and hold for 480 min before slowly cooling to room temperature to obtain SETDL high-entropy zirconate target material.

[0069] Step 7: Select a monocrystalline silicon substrate as the base material, which has a clean and glossy surface.

[0070] Step 8: The high-entropy target material sintered in Step 6 is deposited onto the surface of the single-crystal silicon substrate from Step 7 using physical vapor deposition (PVD) to obtain the SETDL PVD ceramic thin film. The parameters for preparing the SETDL high-entropy zirconate ceramic thin film are as follows: substrate temperature is heated from room temperature to 120°C, target-substrate distance is 300 mm, incident angle is set to 45°, and during coating preparation, the electron gun high voltage is -7.92 kV, and the electron gun beam current is 102 W / cm². 2 The maximum current along the X-axis at the scanning position is -0.54A, the maximum current along the Y-axis at the scanning position is -0.23A, the deposition rate is 1nm / min, and the thickness of the deposited coating is 100nm.

[0071] In this embodiment, the surface morphology diagram and energy spectrum diagram of the coating are as follows: Figure 5 As shown, by Figure 5 It can be seen that the coating surface is smooth, with good surface quality, uniform element distribution, and no segregation or diffusion; the coating cross-sectional morphology and energy dispersive spectroscopy are as follows. Figure 6 As shown, by Figure 6 It can be seen that the coating has high overall density, good quality, uniform element distribution, and no segregation or diffusion. The XRD pattern of the PVD-prepared high-entropy ceramic film is shown below. Figure 7 As shown, by Figure 7 It can be seen that the phase structure is stable and there is no phase transition.

Claims

1. A method for preparing a high-entropy zirconate PVD ceramic thin film, characterized in that... The method includes the following steps: Step 1: Add zirconia grinding balls and an appropriate amount of deionized water to a vertical ball mill. Then add a dispersant to the deionized water. After the dispersant is completely dissolved, proceed according to (Sm... 0.2 Eu 0.2 Tb 0.2 Dy 0.2 Lu 0.2 The following mixture of nano-Sm2O3 powder, nano-Eu2O3 powder, nano-Tb2O3 powder, nano-Dy2O3 powder, nano-Lu2O3 powder, and nano-ZrO2 powder was added to Zr2O7 according to the specified ratio. After ball milling for a period of time, a binder was added, and ball milling continued for a period of time to obtain a uniform slurry. The amount of deionized water was 0.5 to 3 times the total mass of the nano-powders, the amount of dispersant was 0.03 to 6% of the total mass of the nano-powders, and the amount of binder was 0.1 to 10% of the total mass of the nano-powders. Step 2: The slurry obtained in Step 1 is spray-granulated to obtain nano-sized spherical rare earth oxide powder with nanostructures. Step 3: The YSZ agglomerated powder obtained in Step 2 is sieved according to particle size. The spherical powders of different particle sizes after sieving are proportioned and then pressed using cold isostatic pressing to obtain target green bodies with different porosities. The sieving specifications are 50~150 mesh, 150~300 mesh, and 300~400 mesh, and the mass ratio is 2~6:1~3:1~5. Step 4: Sinter the target green to obtain a high-entropy zirconate EB-PVD target. The sintering mechanism is as follows: First, the temperature is increased to 350℃ at 1~10℃ / min and held for 300~420min. Then, the temperature is increased to 1100℃ at 1~10℃ / min and held for 180~250min. Subsequently, the temperature is increased to 1400℃ at 1~10℃ / min and held for 480~600min. Finally, the temperature is reduced to room temperature. Step 5: Using PVD technology, high-entropy zirconate EB-PVD target material is deposited on a smooth and clean PVD substrate surface to form a SETDL high-entropy zirconate PVD ceramic thin film. The parameters in the preparation process of the high-entropy zirconate PVD ceramic thin film are as follows: heating the substrate temperature from room temperature to 50~200℃, electron gun high voltage of -10~-4kV, and electron gun beam current of 80~110W / cm. 2 The scanning position current variation range is ±0.7A to ±1.3A, the deposition rate is 1~5nm / min, and the deposition coating thickness is 10~500nm.

2. The method for preparing high-entropy zirconate PVD ceramic thin films according to claim 1, characterized in that... The particle size of the nano Sm2O3 powder, nano Eu2O3 powder, nano Tb2O3 powder, nano Dy2O3 powder, nano Lu2O3 powder, and nano ZrO2 powder is 5~90nm.

3. The method for preparing high-entropy zirconate PVD ceramic thin films according to claim 1, characterized in that... The dispersant is one or more of sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, ammonium citrate, sodium citrate, polyvinyl alcohol, and polyethylene glycol.

4. The method for preparing high-entropy zirconate PVD ceramic thin films according to claim 1, characterized in that... The adhesive is one of gum arabic, polyvinyl alcohol, carboxymethyl cellulose, and ethyl silicate.

5. The method for preparing high-entropy zirconate PVD ceramic thin films according to claim 1, characterized in that... The diameter of the zirconia grinding balls is 2-10 mm, the amount of zirconia grinding balls used is 1-5 times the total mass of the nanopowder, the total grinding time is 6-24 h, and the rotation speed is 300-1000 rpm.

6. The method for preparing high-entropy zirconate PVD ceramic thin films according to claim 1, characterized in that... The parameters for spray granulation are as follows: inlet air temperature is set to 200~250℃, outlet air temperature is set to 100~130℃, peristaltic pump speed is set to 30~45 r / min, and needle speed is set to 10~15 t / min.

7. The method for preparing high-entropy zirconate PVD ceramic thin films according to claim 1, characterized in that... During the pressing process, the pressure is controlled at 150~250MPa and the holding time is controlled at 120~300s.

8. The method for preparing high-entropy zirconate PVD ceramic thin films according to claim 1, characterized in that... The cold isostatic pressing method uses either wet bag cold isostatic pressing or dry bag cold isostatic pressing.

9. The method for preparing high-entropy zirconate PVD ceramic thin films according to claim 1, characterized in that... The PVD substrate is one of a single-crystal silicon board or a polished alloy substrate.

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