Zirconium boride target material, repairing method and application

Abstract

The invention provides a zirconium boride target material and a repairing method and application thereof, and the repairing method comprises the following steps: carrying out precision machining and ultrasonic cleaning on a residual zirconium boride waste target material after sputtering use to obtain a flaky zirconium boride target material meeting the size specification; the surface, needing to be bonded or repaired, of the flaky zirconium boride target material is subjected to sand blasting treatment, and a fresh bonded and repaired surface is provided; the preparation method comprises the following steps: loading a plurality of flaky zirconium boride target materials into a graphite mold, placing the graphite mold in a vacuum environment with the temperature of 1900-2000 DEG C and the pressure of 50-100 Mpa, and carrying out hot-pressing combination on the mutually contacted bonding and repairing surfaces of the flaky zirconium boride target materials to form a whole zirconium boride target material; machining to a required size after discharging; according to the method, under the condition that no additive is introduced, a plurality of residual zirconium boride waste target materials after sputtering use are combined to form a complete zirconium boride target material by means of a hot-pressing bonding process, and the repaired target material is uniform in organization structure, high in consistency and free of an obvious microstructure interface.

Description

Technical Field

[0001] This invention relates to the field of target preparation technology, and in particular to a zirconium boride target, its repair method, and its application. Background Technology

[0002] Zirconium boride (ZrB2) materials have wide applications in high-temperature structural ceramics due to their high melting point, high hardness, good electrical conductivity, and resistance to high-temperature oxidation. Their thin films also have significant applications in aerospace, solar energy, and nuclear energy. When the boron in ZrB2 is... 10 When ZrB2 is enriched, it exhibits excellent neutron absorption properties, enabling ZrB2 thin films to be used in nuclear reactors.

[0003] ZrB2 thin films are generally prepared using DC magnetron sputtering. In DC magnetron sputtering, a ZrB2 target is used as the cathode and the substrate as the anode. An ion beam bombards the surface of the target, causing the target surface to deposit as atomic clusters onto the substrate surface, forming a ZrB2 thin film. ZrB2 targets are a basic consumable material for preparing ZrB2 thin films, and the amount used is enormous. How to repair used ZrB2 targets and reuse them for magnetron sputtering to prepare ZrB2 thin films is the key to improving target utilization and has become a research focus. Summary of the Invention

[0004] To address the aforementioned problems in the existing technology, this invention provides a zirconium boride target, a repair method, and an application. This method repairs waste zirconium boride targets left over after sputtering, enabling them to be reused for magnetron sputtering to prepare ZrB2 thin films, thereby improving target utilization and reducing the preparation cost of ZrB2 thin films.

[0005] The specific details of the invention are as follows: In a first aspect, the present invention provides a method for repairing zirconium boride targets, the method comprising: The remaining zirconium boride waste target material after sputtering is precision machined and ultrasonically cleaned to obtain sheet-shaped zirconium boride target material that meets the size specifications. The surfaces of the sheet-like zirconium boride target that need to be bonded or repaired are sandblasted to provide a fresh bonding and repair surface; Multiple sheet-like zirconium boride targets are loaded into a graphite mold and placed in a vacuum environment at 1900 ℃-2000 ℃ and 50Mpa-100 Mpa. The bonding and repair surfaces of the sheet-like zirconium boride targets that are in contact with each other undergo thermo-press bonding to form a whole zirconium boride target. The zirconium boride target material, which forms a whole, is precision machined to ensure that the dimensions of the zirconium boride target material meet the usage requirements, and the repair is completed.

[0006] Optionally, the roughness Ra of the adhesive repair surface is 1 μm to 3 μm.

[0007] Optionally, the pressure at which the thermo-compression bonding occurs is 50 MPa-70 MPa, the temperature is 1950 ℃-1980 ℃, and the time is 3 h-5 h.

[0008] Optionally, the difference in relative density between the plurality of said sheet-like zirconium boride targets is no greater than 5%.

[0009] Secondly, the present invention provides a method for repairing zirconium boride targets, the method comprising: precision machining and ultrasonic cleaning of the waste zirconium boride targets remaining after sputtering to obtain sheet-shaped zirconium boride targets that meet the size specifications; The surfaces of the sheet-like zirconium boride target that need to be bonded or repaired are sandblasted to provide a fresh bonding and repair surface; The flake-shaped zirconium boride target and the highly active zirconium boride powder are loaded into a graphite mold and compacted to ensure a tight bond between the highly active zirconium boride powder and the bonding and repair surface of the flake-shaped zirconium boride target. Then, the mold is placed in a vacuum environment at 1900 ℃-2000 ℃ and 50 Mpa-100 Mpa. The highly active zirconium boride powder is densified and undergoes hot-press bonding with the flake-shaped zirconium boride target to form a whole zirconium boride target without obvious connection interfaces. The integral zirconium boride target is precision machined to ensure that its dimensions meet the requirements for use, and the repair is completed.

[0010] Optionally, the roughness Ra of the adhesive repair surface is 1 μm to 3 μm.

[0011] Optionally, the pressure at which the thermo-compression bonding occurs is 50 MPa-70 MPa, the temperature is 1950 ℃-1980 ℃, and the time is 4 h-6 h.

[0012] Optionally, the highly active zirconium boride powder is prepared by a self-propagating method, a sol-gel method, or a carbothermal reduction method; The defect density of the highly active zirconium boride powder is not less than 10. 14 ; The difference between the particle size D50 of the highly active zirconium boride powder and the grain size of the waste zirconium boride target is no greater than 30 micrometers.

[0013] Thirdly, the present invention provides a zirconium boride target material, which is obtained by the repair method described in the first aspect above, or by the repair method described in the second aspect above.

[0014] Fourthly, the present invention provides an application of a zirconium boride target, wherein the zirconium boride target is obtained by the repair method described in the first aspect above, or by the repair method described in the second aspect above; the zirconium boride target is used to prepare ZrB2 thin films by DC magnetron sputtering.

[0015] Compared with the prior art, the present invention has the following advantages: This invention provides a method for repairing zirconium boride targets. The method includes: precision machining and ultrasonic cleaning of the waste zirconium boride targets remaining after sputtering to obtain sheet-like zirconium boride targets that meet the required dimensions; sandblasting the surfaces of the sheet-like zirconium boride targets that need to be bonded or repaired to provide fresh bonding and repair surfaces; loading multiple sheet-like zirconium boride targets into a graphite mold and placing them in a vacuum environment at 1900-2000 °C and 50-100 MPa, where the bonding and repair surfaces of the sheet-like zirconium boride targets that are in contact with each other undergo thermo-pressing bonding to form a whole zirconium boride target; precision machining of the whole zirconium boride target to ensure that the dimensions of the zirconium boride target meet the usage requirements, thus completing the repair. This invention, without introducing any additives, uses a thermo-pressing bonding process to combine multiple waste zirconium boride targets remaining after sputtering to form a complete zirconium boride target. The repaired target has a uniform and consistent microstructure with no obvious microstructure interfaces. The repair method provided by this invention is particularly suitable for... 10 Repair of B-enriched zirconium boride targets; the repaired targets were prepared by DC sputtering. 10 A zirconium boride-enriched coating was applied to the integral combustible poison of the AP1000 nuclear reactor, improving the utilization rate of waste targets.

[0016] Furthermore, this invention also provides another method for repairing zirconium boride targets. The method includes: precision machining and ultrasonic cleaning of the waste zirconium boride target material remaining after sputtering to obtain sheet-like zirconium boride targets that meet dimensional specifications; sandblasting the surfaces of the sheet-like zirconium boride targets that require bonding or repair to provide fresh bonding and repair surfaces; loading the sheet-like zirconium boride targets and highly active zirconium boride powder into a graphite mold, compacting it to ensure a tight bond between the highly active zirconium boride powder and the bonding and repair surfaces of the sheet-like zirconium boride targets, and then placing it under vacuum at 1900-2000 °C. Under conditions of ℃ and 50-100 MPa, the highly active zirconium boride powder is densified and hot-pressed together with the sheet-like zirconium boride target to form a monolithic zirconium boride target without obvious interface. The monolithic zirconium boride target is then precision-machined to ensure its dimensions meet usage requirements, thus completing the repair. This repair method utilizes a deep densification combined with hot-press bonding repair process, offering advantages of speed and efficiency for repairing complex-shaped or small-sized, thin-thick waste targets. The repaired target exhibits a uniform and highly consistent microstructure with no obvious microstructure interfaces. The repair method provided by this invention is applicable to any... 10 Remediation of waste zirconium boride targets with B abundance, including natural abundance and 10 B enrichment abundance; when applicable 10 When repairing zirconium boride targets enriched with B, the difference in abundance between the waste targets being repaired and the highly active powders used should be + / - 0.5 at%, and the abundance technical requirements of the corresponding products should be met. This method can be applied to the repair of integral combustible toxic zirconium boride waste targets in the nuclear industry, as well as to other ultra-high temperature ceramic fields. It can also be extended to the repair of other ultra-high temperature ceramics. Attached Figure Description

[0017] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 A flowchart of the repair method for zirconium boride target provided in an embodiment of the present invention is shown; Figure 2 A flowchart of a repair method for another zirconium boride target provided in an embodiment of the present invention is shown; Figure 3 The microstructure morphology at the interface of the zirconium boride target provided in the embodiment of the present invention is shown. Figure 4 The distribution of crystal elements at the interface of the zirconium boride target provided in this embodiment of the invention is shown. Figure 5 The grain distribution at the interface of the zirconium boride target provided in this embodiment of the invention is shown. Figure 6 This invention illustrates the microstructure at the interface of another zirconium boride target provided in an embodiment of the invention. Figure 7 This illustrates another zirconium boride target interface distribution provided in an embodiment of the present invention; Figure 8 This illustration shows another zirconium boride target interface grain distribution provided in an embodiment of the present invention. Detailed Implementation

[0019] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention or its application or use. Based on the embodiments of the present invention, any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention. Furthermore, all other embodiments obtained by those skilled in the art without inventive effort are within the protection scope of the present invention.

[0020] Specific experimental steps or conditions are not specified in the embodiments; they can be performed according to the conventional experimental steps or conditions described in the prior art. Reagents and other instruments used, unless otherwise specified, are all commercially available conventional reagent products. Furthermore, the accompanying drawings are merely illustrative diagrams of the embodiments of the present invention and are not necessarily drawn to scale. The same reference numerals in the drawings denote the same or similar parts, and therefore, repeated descriptions of them will be omitted. Some block diagrams shown in the drawings are functional entities and do not necessarily correspond to physically or logically independent entities.

[0021] Techniques, methods, and devices known to those skilled in the art may not be discussed in detail, but where appropriate, such techniques, methods, and devices should be considered part of this specification.

[0022] In the description of this invention, it should be understood that the use of terms such as "first" and "second" to define components is merely for the purpose of distinguishing the corresponding components. Unless otherwise stated, the above terms have no special meaning and therefore should not be construed as limiting the scope of protection of this invention.

[0023] Furthermore, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0024] Before providing a detailed description of the zirconium boride target, repair method, and application provided by this invention, it is necessary to explain the relevant technologies as follows: Existing methods for recycling target materials typically involve complex processes to extract valuable raw materials from the target. These processes are quite complex, and even after extracting the raw materials, a complicated process is still required to prepare a usable new target, which cannot significantly reduce recycling costs. There are also various techniques for repairing existing target materials, each with its own characteristics and applicable to different damage conditions and types of ceramic targets. For example, laser repair technology can locally heat and melt the target surface, allowing the material around cracks and pores to re-fuse and repair the damage, but it is only suitable for localized repair of flawed targets. Thermal spraying repair technology involves spraying repair materials onto the target surface at high temperatures to form a high-density repair layer, suitable for repairing oxide targets. For zirconium boride targets, which are more sensitive to oxygen content, low-pressure plasma spraying technology can achieve repair, but the powder utilization rate is low, and there are problems with boron ablation and zirconium oxidation during high-temperature spraying. Furthermore, the microstructure of the sprayed coating is a stacked layer, which differs greatly from the microstructure of the hot-pressed coating, potentially affecting sputtering performance. Other target material repair methods, such as nano-ion coating technology, utilize nanomaterials to fill microcracks and pores, forming a dense repair layer to improve the wear resistance and corrosion resistance of the target material. This method is suitable for high-precision target material repair that requires maintaining a smooth surface and low roughness, and is also suitable for localized target material repair. Ceramic adhesive or filler repair is suitable for cases with minor damage, but its effectiveness is limited for repairing large-area damage. For sputtered waste targets, the above-mentioned repair methods are not feasible due to the large amount of sputtering loss. There is an urgent need to develop a simple process method suitable for large-area target recycling and repair.

[0025] Based on this, this invention conducts in-depth research on the repair of ZrB2 sputtered waste targets. It was discovered that in the crystal structure of zirconium boride, boron and zirconium atoms are arranged in a specific lattice pattern. This structure gives zirconium boride not only covalent bonds but also ionic and metallic bonds, enhancing its electrical and thermal conductivity. Therefore, during hot-pressing sintering, the high temperature provides sufficient energy for the atoms to overcome lattice resistance and diffuse. At the contact surface of two zirconium boride ceramic blocks, atoms diffuse into each other, gradually causing the atomic arrangement at the interface to become more uniform, ultimately eliminating the interface and achieving a tight bond between the blocks. Simultaneously, the pressure generated by hot pressing induces plastic deformation in the ceramic blocks. Under pressure, microscopic protrusions and unevenness on the contact surface of the blocks are gradually flattened, increasing the actual contact area between the blocks and making the two zirconium boride targets fit more tightly, creating better conditions for atomic diffusion and bonding.

[0026] Therefore, this invention designs a method to repair sputtered ZrB2 waste targets through hot-pressing sintering, combining them to form new zirconium boride targets. The repaired ZrB2 targets have a uniform microstructure, high purity, simple phase structure, high density, and good conductivity, making them suitable for DC magnetron sputtering to prepare ZrB2 thin films. Specific implementation details are as follows: In a first aspect, the present invention provides a method for repairing zirconium boride targets, specifically for waste zirconium boride targets with a certain thickness and regular shape remaining after sputtering. Figure 1 A flowchart of the repair method for zirconium boride target provided in an embodiment of the present invention is shown, as follows: Figure 1 As shown, the repair method includes: S11. The remaining zirconium boride waste target material after sputtering is precision machined and ultrasonically cleaned to obtain sheet-shaped zirconium boride target material that meets the size specifications. In this step, the equipment used for precision machining can be a surface grinder or wire cutting machine, etc. Precision machining is used to obtain sheet-shaped zirconium boride targets with specific dimensions, and ultrasonic cleaning can remove stains and impurities from the surface of the sheet-shaped zirconium boride targets.

[0027] S12. Sandblast the surface of the sheet-like zirconium boride target that needs to be bonded or repaired to provide a fresh bonding and repair surface. In this step, the sheet-like zirconium boride targets are sandblasted to give the surfaces of the sheet-like zirconium boride targets that come into contact with each other a certain roughness, which increases the actual contact area between the blocks during hot pressing, and facilitates atomic diffusion and bonding of the zirconium boride targets.

[0028] It should be noted that if more than two sheet zirconium boride targets are used for hot pressing repair during the repair process, one surface of two of the sheet zirconium boride targets can be sandblasted, while the remaining sheet zirconium boride targets need to be sandblasted on both surfaces. This ensures that when the sheet zirconium boride targets are installed in the graphite mold, the contact surfaces of adjacent sheet zirconium boride targets are fresh bonding repair surfaces after sandblasting.

[0029] In some embodiments, the roughness Ra of the bonded repair surface obtained after sandblasting is 1~3 μm.

[0030] S13. Multiple sheet-like zirconium boride targets are loaded into a graphite mold and placed in a vacuum environment at 1900-2000 ℃ and 50-100 MPa. The bonding and repair surfaces of the sheet-like zirconium boride targets that are in contact with each other are thermally pressed together to form a whole zirconium boride target. In this step, the sheet-like zirconium boride target is inserted into a graphite mold. Under high temperature and pressure, atoms diffuse into each other at the interface of the two contacting zirconium boride ceramic blocks, gradually causing the atomic arrangement at the interface to become more uniform, ultimately eliminating the interface and achieving a tight bond between the blocks. Simultaneously, the pressure generated by hot pressing induces plastic deformation in the ceramic blocks. Under pressure, microscopic protrusions and unevenness on the contact surface of the blocks are gradually flattened, increasing the actual contact area between the blocks and making the two zirconium boride targets adhere more tightly, creating better conditions for atomic diffusion and bonding.

[0031] In practice, the zirconium boride target material is loaded into a graphite mold and placed in a vacuum induction hot press furnace. A vacuum is then drawn, and when the vacuum level reaches 10... -2 After Pa, the temperature is increased. When the temperature reaches 1000 ℃, the vacuum system is closed, the gas filling valve is opened, and high-purity argon gas is introduced until the pressure inside the furnace reaches equilibrium with the external pressure. The gas filling valve is then closed, and the temperature is increased again. When the temperature reaches 1900℃-2000 ℃, the temperature is held for 1-2 hours. Then, bidirectional pressurization is started until the pressure reaches 50 MPa-100 MPa. The temperature and pressure are then maintained for a total of 3-5 hours. After cooling, the target material is removed, and the zirconium boride target material is obtained as a whole.

[0032] In some embodiments, the preferred pressure for thermo-compression bonding is 50-70 MPa, the preferred temperature is 1950-1980 °C, and the preferred time is 3-5 h.

[0033] It should be noted that the graphite mold can be a round graphite mold, a square graphite mold, or a ring-shaped cylindrical graphite mold. Different mold sizes can be designed to adapt to the repair of target materials of different shapes and specifications. The size of the graphite mold is matched with the size of the sheet-shaped zirconium boride target material with specific dimensions obtained through precision machining.

[0034] S14. The zirconium boride target material that forms a whole is precision machined so that the dimensions of the zirconium boride target material meet the usage requirements, and the repair is completed.

[0035] In the specific implementation of this step, the equipment used for precision machining can be a surface grinder or wire cutting machine, etc., to obtain a zirconium boride target material with dimensions that meet the requirements of use through precision machining.

[0036] It should be noted that, in this embodiment, the difference in relative density between the remaining zirconium boride waste targets after sputtering is no greater than 5%, in order to ensure that the microstructure of the repaired zirconium boride target is uniform and highly consistent.

[0037] Furthermore, for the repair of waste targets with uneven shapes or thin thickness, the present invention also provides another method for repairing zirconium boride targets. Figure 2 A flowchart of the repair method for zirconium boride target provided in an embodiment of the present invention is shown, as follows: Figure 2 As shown, the repair method includes: S21. The remaining zirconium boride waste target material after sputtering is precision machined and ultrasonically cleaned to obtain sheet-shaped zirconium boride target material that meets the size specifications. Step S21 is the same as step S11.

[0038] S22. Sandblast the surface of the sheet-like zirconium boride target that needs to be bonded or repaired to provide a fresh bonding and repair surface. Unlike step S12, this embodiment only involves a sheet-like zirconium boride target. Therefore, only the surface of the sheet-like zirconium boride target that needs to be bonded or repaired needs to be sandblasted to provide a fresh bonding and repair surface that comes into contact with the highly active zirconium boride powder.

[0039] S23. The flake-shaped zirconium boride target and the highly active zirconium boride powder are loaded into a graphite mold and compacted to ensure that the highly active zirconium boride powder and the bonding and repair surface of the flake-shaped zirconium boride target are tightly bonded. Then, the mold is placed in a vacuum environment at 1900-2000 ℃ and 50-100 MPa. The highly active zirconium boride powder is densified and undergoes hot-press bonding with the flake-shaped zirconium boride target to form a whole zirconium boride target without obvious connection interface. In this step, the flake-shaped zirconium boride target and the highly active zirconium boride powder are loaded together into a graphite mold. Under high temperature and high pressure, the highly active zirconium boride powder is densified and hot-pressed together with the flake-shaped zirconium boride target. At the interface between the two, atoms diffuse into each other, causing the atomic arrangement at the interface to gradually become consistent, eventually eliminating the interface and achieving a tight bond. Through the high-temperature hot-press bonding process, the target is repaired to the required thickness. No additives are needed during the target repair process, achieving a clean repair of the target throughout the entire process.

[0040] In practice, the bonding and repair surface of the sheet-like zirconium boride target is first placed into a graphite mold with the latter facing upwards. Then, the weighed high-activity zirconium boride powder is added into the mold and compacted using a jack to ensure full and tight contact between the powder and the surface of the target to be repaired. The mold is then placed in a vacuum induction hot press furnace, and a vacuum is drawn. When the vacuum degree reaches 10... -2 After Pa, the temperature is increased. When the temperature reaches 1000 ℃, the vacuum system is closed, the gas filling valve is opened, and high-purity argon gas is introduced until the pressure inside the furnace reaches equilibrium with the external pressure. The gas filling valve is then closed, and the temperature is increased again. When the temperature reaches 1900 ℃-2000 ℃, it is held for 1 h-2 h. Then, bidirectional pressurization is started until the pressure reaches 50 MPa-100 MPa. The temperature and pressure are then maintained for a total of 3-5 h. After cooling, the target material is removed, and the entire zirconium boride target material is obtained.

[0041] In some embodiments, the preferred pressure for thermo-compression bonding is 50-70 MPa, the preferred temperature is 1950-1980 °C, and the preferred time is 3-5 h.

[0042] S24. Perform precision machining on the integral zirconium boride target to ensure that the dimensions of the zirconium boride target meet the usage requirements, and complete the repair.

[0043] Step S24 is the same as step S14.

[0044] Unlike the repair method provided in the first aspect above, the repair method provided in this embodiment utilizes a deep densification combined with hot-press bonding repair process to combine the waste zirconium boride target material remaining after sputtering with highly active zirconium boride powder. The highly active zirconium boride powder fills the insufficient parts of the waste zirconium boride target material. Through deep densification combined with high-temperature hot-press bonding process, the target material is repaired to the required thickness. This repair method has high repair efficiency for waste target materials with uneven shapes or thinner thicknesses. The repaired target material has a uniform and consistent microstructure with no obvious microstructure interfaces, thus improving the performance of the repaired target material.

[0045] In some embodiments, highly active zirconium boride powder is prepared by a self-propagating method, a sol-gel method, or a carbothermal reduction method.

[0046] The defect density of the highly active zirconium boride powder is not less than 10. 14 The difference between the particle size D50 of the highly active zirconium boride powder and the grain size of the waste zirconium boride target is no greater than 30 micrometers.

[0047] Thirdly, the present invention provides a zirconium boride target material, which is obtained by the repair method described in the first aspect above, or by the repair method described in the second aspect above.

[0048] Fourthly, the present invention provides an application of a zirconium boride target, wherein the zirconium boride target is obtained by the repair method described in the first aspect above, or by the repair method described in the second aspect above; the zirconium boride target is used to prepare ZrB2 thin films by DC magnetron sputtering.

[0049] The repair method provided by this invention is applicable to any 10 Remediation of waste zirconium boride targets with B abundance, including natural abundance and 10 B enrichment abundance, when applicable 10 When repairing zirconium boride targets enriched with B, the difference in abundance between the waste targets being repaired and the highly active powders used should be + / - 0.5 at%, and the abundance technical requirements of the corresponding products should be met. This method can be applied to the repair of integral combustible toxic zirconium boride waste targets in the nuclear industry, as well as to other ultra-high temperature ceramic fields. It can also be extended to the repair of other ultra-high temperature ceramics.

[0050] To enable those skilled in the art to more clearly understand the present invention, the following embodiments are provided to illustrate in detail a zirconium boride target, its repair method, and its application.

[0051] Example 1 Two targets to be repaired were processed into 65mm circular targets with a thickness of 5mm. The relative densities of the two targets were 95.6% and 94.8%, respectively. After ultrasonic cleaning, the surfaces to be bonded were pre-treated by sandblasting to a roughness of 1.2μm. A 65mm graphite mold was selected, and one target was placed in the mold with the bonding surface facing up, while the second target was placed in the mold with the bonding surface facing down. The mold was placed in a vacuum induction hot press furnace, and a vacuum was drawn. When the vacuum degree reached 10... -2 After Pa, the temperature is raised. When the temperature reaches 1000℃, the vacuum system is shut off, the gas filling valve is opened, and high-purity argon gas is introduced until the pressure inside the furnace reaches equilibrium with the external pressure. The gas filling valve is then closed. When the temperature reaches 1980℃, the temperature is held for 1 hour. After that, bidirectional pressurization is started until the pressure reaches 23 tons. Then, the temperature and pressure are held for a total of 5 hours. After cooling, the repaired zirconium boride target material is taken out.

[0052] The relative density of the prepared target material was measured to be 95% after surface grinding with a diamond wheel; the microstructure morphology of the target material interface was analyzed. Figure 3 The microstructure morphology at the interface of the zirconium boride target provided in the embodiment of the present invention is shown. Figure 4 The distribution of crystal elements at the interface of the zirconium boride target provided in this embodiment of the invention is shown, such as... Figure 3 , 4 As shown, SEM analysis revealed a uniform microstructure, with uniform distribution of zirconium and boron elements and no obvious interface effects.

[0053] Figure 5 The grain distribution at the interface of the zirconium boride target provided in the embodiment of the present invention is shown, such as... Figure 5 As shown, EBSD analysis reveals that the grain growth at the interface tends to be uniform (the interface is located in the vertical direction on the right side of the image), with an average grain size of 12-15 μm.

[0054] Example 2 The target material to be repaired was processed into a 65mm circular target with a thickness of 5mm. The relative density of the target material to be repaired was 95.6%. After ultrasonic cleaning, the surface to be bonded was pre-treated by sandblasting to control the roughness to 1.3μm. ZrO2 powder, natural abundance H3BO3 powder, and C powder were weighed and mixed evenly according to the ratio. Highly active zirconium boride powder (the particle size D50 of the highly active zirconium boride powder is 27μm) was synthesized by carbothermal reduction. The synthesis time was 3-5 hours. The defect density of the synthesized powder was calculated to be 5×10. 14 (Obtained using X-ray diffraction combined with multiple convolution contour fitting); Select a 65mm graphite mold, place a target material with the bonding surface facing up into the mold, then add the weighed powder into the mold and compact it with a jack to ensure full and tight contact between the powder and the target material to be repaired; Place the mold in a vacuum induction hot press furnace, evacuate the vacuum, and when the vacuum degree reaches 10... -2 After Pa, the temperature is raised. When the temperature reaches 1000℃, the vacuum system is shut off, the gas filling valve is opened, and high-purity argon gas is introduced until the pressure inside the furnace reaches equilibrium with the external pressure. The gas filling valve is then closed. When the temperature reaches 1980℃, the temperature is held for 1 hour. After that, bidirectional pressurization is started until the pressure reaches 23 tons. Then, the temperature and pressure are held for a total of 5 hours. After cooling, the repaired zirconium boride target material is taken out.

[0055] The relative density of the prepared target material, measured after surface grinding with a diamond wheel, was 95.2%. Microstructure analysis was performed at the target material interface. Figure 6 This illustrates another microstructure morphology at the interface of a zirconium boride target provided in an embodiment of the present invention. Figure 7 This illustrates another zirconium boride target interface distribution provided in an embodiment of the present invention, such as... Figure 6 , 7 As shown, SEM analysis revealed a uniform microstructure, with uniform distribution of zirconium and boron elements and no obvious interface effects.

[0056] Figure 8 This illustrates another zirconium boride target interface grain distribution provided in an embodiment of the present invention, such as... Figure 8As shown, EBSD analysis reveals that the grain growth at the interface tends to be uniform (at the interface, the left side is the repair target end, and the right side is the powder densification target end), with the grain size at the repair target end being slightly larger than that at the powder densification end.

[0057] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. In addition, those skilled in the art can combine and integrate the different embodiments or examples described in this specification.

[0058] For the sake of simplicity, the method embodiments are described as a series of actions. However, those skilled in the art should understand that the present invention is not limited to the described order of actions, as some steps can be performed in other orders or simultaneously according to the present invention. Furthermore, those skilled in the art should also understand that the embodiments described in the specification are preferred embodiments, and the actions and components involved are not necessarily essential to the present invention.

[0059] The foregoing has provided a detailed description of the zirconium boride target, repair method, and application provided by the present invention. Specific examples have been used to illustrate the principles and implementation methods of the present invention. The descriptions of the above embodiments are only for the purpose of helping to understand the method and core ideas of the present invention. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of the present invention. Therefore, the content of this specification should not be construed as a limitation of the present invention.

Claims

1. A method of repairing a zirconium boride target material, characterized by, The repairing method comprises: The boron zirconium waste target material remaining after sputtering is precisely machined and ultrasonically cleaned to obtain a sheet-shaped boron zirconium target material meeting the size specification; The surface of the sheet-shaped boron zirconium target material that needs to be bonded or repaired is sandblasted to provide a fresh bonding and repairing surface; A plurality of the sheet-shaped boron zirconium target materials are loaded into a graphite mold and placed in a vacuum, 1900-2000 ℃ and 50-100 Mpa environment, the bonding and repairing surfaces of the sheet-shaped boron zirconium target materials in contact with each other are hot-pressed to form a boron zirconium target material whole; The boron zirconium target material whole is precisely machined so that the size of the boron zirconium target material meets the use requirement and the repairing is completed.

2. The method for repairing a zirconium boride target according to claim 1, wherein The roughness Ra of the bonding and repairing surface is 1-3 μm.

3. The method of claim 1, wherein the zirconium boride target is repaired by, The pressure of the hot-pressing is 50-70 Mpa, the temperature is 1950-1980 ℃, and the time is 3-5 h.

4. The method of claim 1, wherein the zirconium boride target is a target for use in a plasma display panel. The difference between the relative densities of the plurality of sheet-shaped boron zirconium target materials is not more than 5%.

5. A method of repairing a zirconium boride target material, characterized by, The repairing method comprises: The surface of the sheet-shaped boron zirconium target material that needs to be bonded or repaired is sandblasted to provide a fresh bonding and repairing surface; The sheet-shaped boron zirconium target material and high-activity boron zirconium powder are loaded into a graphite mold, compacted to make the high-activity boron zirconium powder tightly combined with the bonding and repairing surface of the sheet-shaped boron zirconium target material, and then placed in a vacuum, 1900-2000 ℃ and 50-100 Mpa environment, the high-activity boron zirconium powder is densified and hot-pressed with the sheet-shaped boron zirconium target material to form a boron zirconium target material whole without obvious connecting interface; The boron zirconium target material whole is precisely machined so that the size of the boron zirconium target material meets the use requirement and the repairing is completed.

6. The method of repairing a zirconium boride target according to claim 5, wherein The roughness Ra of the bonding and repairing surface is 1-3 μm.

7. The method of repairing a zirconium boride target according to claim 5, wherein The pressure of the hot-pressing is 50-70 Mpa, the temperature is 1950-1980 ℃, and the time is 4-6 h.

8. The method of claim 5, wherein the boron-doped zirconium target is a target having a diameter of 300 mm or more. The high-activity boron zirconium powder is prepared by a self-propagating method, a sol-gel method or a carbon thermal reduction method; The high-activity zirconium boride powder has a defect density of not less than 10 14 ; The difference between the particle size D50 of the high-activity boron zirconium powder and the grain size of the boron zirconium waste target material is not more than 30 microns.

9. A zirconium boride target material, characterized by, The boron zirconium target material is obtained by the repairing method of any one of claims 1-4 or the repairing method of any one of claims 5-8.

10. Use of a zirconium boride target material, characterized in that The boron zirconium target material is obtained by the repairing method of any one of claims 1-4 or the repairing method of any one of claims 5-8; the boron zirconium target material is used for preparing a ZrB2 thin film by direct current magnetron sputtering.

Images