Titanium-chromium alloy target material and preparation method thereof

Abstract

The invention discloses a titanium-chromium alloy target material and a preparation method thereof, and the preparation method comprises the following steps: mixing pretreated titanium dioxide nanotubes, pretreated titanium dioxide nano powder and chromic nitrate with deionized water according to a certain proportion, adding a proper amount of hyperdispersant and chelating agent, heating and stirring to obtain a gelatinous substance; and the gelatinous substance is put into a drying oven to be dried, a mushroom cloud fluffy substance is obtained, grinding, carbon powder doping calcination, degassing and hot isostatic pressing treatment are conducted on the mushroom cloud fluffy substance, and the titanium-chromium alloy sputtering target material is obtained. The compactness of the titanium-chromium alloy target material prepared through the preparation method is 99.50% or above, a solid-liquid mixing mode is adopted in the method, the excellent mixing effect is guaranteed, the prepared target material is small in grain size and uniform and stable in component, element components can be accurately controlled according to different element proportions, the machining performance is more excellent, and the method is suitable for industrial production. After being placed in an indoor environment for a long time, the product is not easily oxidized, and the purity is ensured.

Description

Technical Field

[0001] The invention relates to the technical field of magnetron sputtering target material preparation, and in particular to a titanium-chromium alloy target material and a preparation method thereof. Background Art

[0002] Stainless steel bipolar plates currently have the problem of poor corrosion resistance, so it is necessary to modify the surface of stainless steel bipolar plates to achieve both corrosion resistance and electrical conductivity. Titanium and chromium are both similar to stainless steel in thermal expansion coefficient, so they are often used to prepare coatings. However, when a single element is subjected to magnetron sputtering, it is very easy to form island cluster crystals and then extend to the three-dimensional interface, and there are many lattice gaps between the crystals. Laves phase TiCr2 is an intermetallic compound that is easily formed in hypereutectoid titanium-chromium alloys. It has good mechanical properties, still exhibits good surface creep resistance at 1100°C, and has good oxidation resistance. Therefore, in PEMFC (proton exchange fuel cell) applications, TiCr2 alloy is used to make targets for coating preparation, and the resulting coating has excellent corrosion resistance, thereby improving the service life of the fuel cell.

[0003] At present, the preparation methods of titanium-chromium alloy targets are mainly hot pressing or vacuum melting and casting. Titanium-chromium alloy targets sintered by hot pressing have poor density, high oxygen content, and low product production efficiency; while titanium-chromium alloys prepared by vacuum melting and casting have uneven composition, pores, complex processes, and waste of raw materials, which is not conducive to industrial production.

[0004] A Chinese invention patent application with publication number CN113088900A discloses a method for preparing a titanium-chromium alloy sputtering target for magnetic recording, comprising the following steps: taking chromium powder and titanium powder in a certain proportion and mixing them in a solid-solid phase under a protective gas, loading the mixed powder into a mold for degassing, and performing hot isostatic pressing after treatment to obtain a target material of the required shape for processing. The titanium-chromium alloy target material preparation method is solid-solid phase mixing, and its mixing uniformity will be affected by the particle size of different solids and the process conditions of the powder mixer (rotation speed, time, etc.). For different batches of products, the inconsistent mixing effect easily leads to different distribution states of various metal elements inside the target material, that is, its composition uniformity, stability and controllability are poor. Summary of the invention

[0005] In view of the problems existing in the prior art, the purpose of the present invention is to provide a titanium-chromium alloy target material and a preparation method thereof in which the metal elements are more evenly distributed, and the stability and controllability are better, so as to at least provide a beneficial choice or create conditions for solving one or more technical problems existing in the prior art.

[0006] To achieve the above objectives, the present invention adopts the following technical solutions.

[0007] A method for preparing a titanium-chromium alloy sputtering target, the preparation method comprising:

[0008] Pretreated titanium dioxide nanotubes, pretreated titanium dioxide nanopowder and chromium nitrate are mixed with deionized water in a certain proportion, and appropriate amounts of hyperdispersants and chelating agents are added, heated and stirred to obtain a gel-like substance; the gel-like substance is placed in an oven for drying to obtain a mushroom cloud fluffy substance, which is ground, calcined with carbon powder, degassed, and hot isostatically pressed to obtain the titanium-chromium alloy sputtering target.

[0009] As a preferred technical solution of the present invention, the titanium dioxide nanotubes are selected to be 99% high purity, the titanium dioxide nanopowder is 99% pure ultrafine spherical metal nano-titanium powder, and the chromium nitrate is chromium nitrate (III) nonahydrate provided by Aladdin Reagent Company with a purity of 99.95%.

[0010] The particle size of the titanium dioxide nanotubes is 200-400 mesh, such as 200 mesh, 250 mesh, 300 mesh, 350 mesh or 400 mesh, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0011] In the present invention, if the particle size of titanium dioxide nanotubes is less than 200 meshes, on the one hand, the uniformity of the product components is affected, making it impossible to mix evenly with chromium nitrate nonahydrate; on the other hand, the quality of target material forming is affected, and the product may be non-dense or even cracked.

[0012] The titanium dioxide nanotube annealing temperature is 450-600° C., such as 450° C., 480° C., 500° C., 550° C. or 600° C., but is not limited to the listed values, and other values ​​not listed within the range are also applicable.

[0013] Preferably, the annealing time is 1-3 h, such as 1 h, 1.5 h, 2 h, 2.5 h or 3 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0014] The size of the titanium dioxide nanopowder is 3-100 nm, such as 3 nm, 5 nm, 20 nm, 50 nm or 100 nm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0015] Preferably, 99% of the crystal form of the titanium dioxide nanopowder is rutile.

[0016] Preferably, in the mixture of titanium dioxide nanotubes and titanium dioxide nanopowder, the mass proportion of titanium dioxide nanopowder is 5-20%, such as 5%, 10%, 15% or 20%, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0017] As a preferred technical solution of the present invention, the cold plasma treatment method is: firstly perform a first cold plasma treatment under an oxygen gas flow, and then perform a second cold plasma treatment under an argon gas flow.

[0018] Preferably, the oxygen gas flow rate used in the cold plasma pretreatment is 20-50 mL / min, such as 20 mL / min, 25 mL / min, 30 mL / min, 35 mL / min, 40 mL / min, 45 mL / min or 50 mL / min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also used.

[0019] Preferably, the discharge power of the oxygen cold plasma pretreatment is 30-50W, such as 30W, 33W, 37W, 42W, 45W, 47W or 50W, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0020] Preferably, the oxygen cold plasma pretreatment discharge temperature is 100-250°C, such as 100°C, 150°C, 200°C or 250°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0021] Preferably, the argon gas flow rate used in the cold plasma pretreatment is 50-120 mL / min, such as 50 mL / min, 60 mL / min, 80 mL / min, 100 mL / min or 120 mL / min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also used.

[0022] Preferably, the discharge power of the argon cold plasma pretreatment is 3-20W, such as 3W, 8W, 12W, 15W or 20W, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0023] Preferably, the argon cold plasma pretreatment discharge temperature is 50-200°C, such as 50°C, 100°C, 150°C or 200°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0024] Preferably, the pretreated titanium dioxide nanotubes, the treated titanium dioxide nanopowder and chromium nitrate nonahydrate are mixed in a molar ratio of 1:2-2:1, such as 1:2, 1:1, 2:1, etc., but are not limited to the listed values, and other unlisted values ​​within the numerical range are also used.

[0025] Preferably, the chelating agent can be sodium citrate or EDTA, and its usage is proportional to the molar number of the selected metal material, and n (chelating agent): n (metal ion) = x, x is 1-4, such as x = 1, x = 2, x = 3 or x = 4, but is not limited to the listed values, and other values ​​not listed within the numerical range can also be used.

[0026] As a preferred technical solution of the present invention, the heating is water bath or oil bath heating, and the heating temperature is 60-80°C, such as 60°C, 65°C, 70°C, 75°C or 80°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0027] As a preferred technical solution of the present invention, the stirring rate is 400-1000rpm, such as 400rpm, 500rpm, 600rpm, 700rpm, 800rpm, 900rpm or 1000rpm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0028] Preferably, the mixing time is 4-6 hours, such as 4 hours, 5 hours or 6 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0029] As a preferred technical solution of the present invention, the heating temperature of the oven is 110-130°C, such as 110°C, 120°C or 130°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0030] As a preferred technical solution of the present invention, the carbon powder-doped calcination is to add carbon powder with an equivalent molar amount of metal elements for calcination, and the calcination temperature is 1000-1500°C, such as 1000°C, 1100°C, 1200°C, 1300°C, 1400°C or 1500°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0031] Preferably, the calcination time is 3-7 h, such as 3 h, 4 h, 5 h, 6 h or 7 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0032] As a preferred technical solution of the present invention, the degassing temperature is 300-600°C, such as 300°C, 350°C, 400°C, 450°C, 500°C, 550°C or 600°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0033] Preferably, the degassing time is 4-8 h, such as 4 h, 5 h, 6 h, 7 h or 8 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0034] As a preferred technical solution of the present invention, the vacuum degree in the mold after degassing is less than 5.0×10 -3 Pa, such as 4×10 -3 Pa, 3×10 -3 Pa, 2×10 -3 Pa, 1×10 -3 Pa, 0.5×10 -3 Pa or 0.2×10 -3 Pa, etc., but are not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0035] As a preferred technical solution of the present invention, the temperature of the hot isostatic pressing treatment is 600-1200°C, such as 600°C, 700°C, 800°C, 900°C, 1000°C, 1100°C or 1200°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0036] Preferably, the pressure of the hot isostatic pressing treatment is 90-170 MPa, such as 90 MPa, 100 MPa, 110 MPa, 120 MPa, 130 MPa, 140 MPa, 150 MPa, 160 MPa or 170 MPa, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0037] Preferably, the hot isostatic pressing treatment time is 3-6 h, such as 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h or 6 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0038] As a preferred technical solution of the present invention, the titanium-chromium alloy sputtering target obtained after the hot isostatic pressing treatment is subjected to mechanical processing, testing, cleaning and packaging.

[0039] In the present invention, the mechanical processing, testing, cleaning and packaging are all conventional operations in the art and will not be described in detail here.

[0040] As a preferred technical solution of the preparation method provided by the present invention, the preparation method of the titanium-chromium alloy target comprises: the purchased titanium dioxide nanotubes are 200-400 mesh in size, first put them into a crucible and calcine them at 450-600°C in a muffle furnace for 1-3h. Mix 5-20% of 3-100nm titanium dioxide nanopowder by mass into the annealed titanium dioxide nanotubes, pour the mixture into a HNO3 solution with a pH value of 3 and ultrasonically clean it twice, each for 30 minutes, and pour it into deionized water and ultrasonically clean it twice, each for 30 minutes. Then, under 20-50mL / min of oxygen, first complete the cold plasma treatment with a discharge power of 30-50W and a discharge temperature of 100-250°C, and then perform cold plasma treatment with 50-120mL / min of oxygen under the conditions of a discharge power of 3-20W and a discharge temperature of 50-200°C.

[0041] The titanium dioxide nanotubes and titanium dioxide nanopowder mixture obtained by pretreatment are mixed with chromium nitrate nonahydrate in a molar ratio of 1:2-2:1, sulfonate anionic aqueous hyperdispersant accounting for 2% of the mass of the titanium dioxide nanotubes and nanopowder mixture and deionized water are added and the pH value is adjusted to 7-8 with ammonia water, and then x (x=1-4) amount of sodium citrate or EDTA is added, and the pH value of the mixed solution is maintained at about 7 with ammonia water. The beaker is placed in a water bath or oil bath pot with a heating temperature of 60-80°C, and stirred at a speed of 400-1000rpm for 4- 6h to obtain a gel-like substance; the gel-like substance is placed in an oven at 110-130°C and dried until it becomes a mushroom cloud-like fluffy substance; after the mushroom cloud-like fluffy substance is ground into fine powder, carbon powder and a certain amount of organic binder in an amount equivalent to the molar amount of the metal element are added, mixed evenly and made into small balls with a diameter of 1 cm, which are placed in a crucible, and calcined for 3-7h in an atmosphere furnace at 1000-1500°C and 20mL / min of argon gas; the powder obtained after cooling to room temperature is placed in a mold and degassed at 300-600°C for 4-8h, and the vacuum degree in the mold after degassing is less than 5.0×10 -3 Pa, and after degassing, hot isostatic pressing is performed at 600-1200° C. and 90-170 MPa for 3-6 hours to obtain the titanium-chromium alloy sputtering target.

[0042] Under the action of the hyperdispersant, the mixture formed by the pretreated titanium dioxide nanotubes and titanium dioxide nanopowder is not easy to coagulate in the aqueous solution containing chromium nitrate.

[0043] Compared with the prior art, the present invention has at least the following beneficial effects.

[0044] The invention provides a method for preparing a titanium-chromium alloy sputtering target material, which is a method for preparing a titanium-chromium alloy sputtering target material based on a sol-gel method. The titanium-chromium alloy target material prepared by the preparation method has a density of more than 99.50% and a purity of more than 99.999%. In addition, the method adopts a solid-liquid mixing form to ensure an excellent mixing effect, and the metal elements are more uniform. The grain size of the prepared target material is fine, and the uniform and stable composition is ensured. The element composition can be accurately controlled according to different element ratios, and the controllability is good, the mechanical processing performance is excellent, and the target material is not easily oxidized when placed in an indoor environment for a long time, thereby ensuring purity. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 Shown is a schematic flow chart of a method for preparing a titanium-chromium alloy sputtering target provided by the present invention. DETAILED DESCRIPTION

[0046] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0047] The specific implementation of the present invention is further described below in conjunction with the accompanying drawings. Example 1.

[0048] A method for preparing a titanium-chromium alloy target material, the preparation steps of which are as follows: 1) purchasing titanium dioxide nanotubes with a size of 200 mesh, first placing the titanium dioxide nanotubes in a crucible and calcining them at 600°C for 1h in a muffle furnace and then annealing them. Mixing 10% by mass of 30nm titanium dioxide nanopowder into the annealed titanium dioxide nanotubes, the mixture is first subjected to cold plasma treatment with a discharge power of 50W and a discharge temperature of 150°C under the condition of 30mL / min of oxygen, and then subjected to cold plasma treatment with a discharge power of 10W and a discharge temperature of 100°C under the condition of 70mL / min of argon, to obtain a pretreated mixture of titanium dioxide nanotubes and titanium dioxide nanopowders.

[0049] 2) The pretreated titanium dioxide nanotube and titanium dioxide nanopowder mixture obtained in step 1) is mixed with chromium nitrate nonahydrate at a titanium-chromium molar ratio of 1:2, and then an anionic aqueous hyperdispersant and deionized water are added to obtain a mixed solution; the anionic aqueous hyperdispersant is a sulfonate dispersant, and the amount of the anionic aqueous hyperdispersant added is 2% of the mass of the titanium dioxide nanotube and nanopowder mixture.

[0050] 3) The pH value of the mixed solution in step 2) is adjusted to 7-8 with aqueous ammonia, and then EDTA with x=4 is added and the pH value of the mixed solution is maintained at about 7 with aqueous ammonia. x represents the molar ratio of the chelating agent EDTA to the metal ion.

[0051] 4) The mixed solution obtained in step 3) is heated in a water bath at 80° C. and stirred at a speed of 600 rpm for 4 hours to obtain a gel-like substance; the gel-like substance is placed in an oven at 120° C. and dried until it becomes fluffy like a mushroom cloud; the fluffy mushroom cloud-like substance is ground into fine powder, and carbon powder and a certain amount of organic binder having an equivalent molar amount of the metal element are added, the mixture is mixed evenly, and formed into small balls with a diameter of 1 cm.

[0052] 5) The small balls obtained in step 4) were placed in a crucible and calcined in an atmosphere furnace with argon gas flowing at 20 mL / min at a temperature of 1100° C. for 6 h; after calcination, the mixture was cooled to room temperature to obtain a powder.

[0053] 6) The powder obtained in step 5) was loaded into a mold and degassed at 300°C for 8 h; the vacuum degree in the mold after degassing was 2.0×10 -3 Pa; after degassing, hot isostatic pressing was carried out at 600°C and 90MPa for 6h to obtain a titanium-chromium alloy sputtering target.

[0054] 7) The titanium-chromium alloy sputtering target obtained in step 6) is mechanically processed, inspected, cleaned and packaged to obtain product 1. Example 2.

[0055] A method for preparing a titanium-chromium alloy target material, the preparation steps of which are as follows: 1) purchasing titanium dioxide nanotubes with a size of 250 meshes, firstly placing the titanium dioxide nanotubes in a crucible, calcining them in a muffle furnace for 3 hours, and then annealing, the calcination temperature being 450°C; mixing 90nm titanium dioxide nanopowder accounting for 5% by mass into the annealed titanium dioxide nanotubes, and performing two cold plasma treatments to obtain a pretreated titanium dioxide nanotube and titanium dioxide nanopowder mixture; the first cold plasma treatment is performed under 40mL / min of oxygen, the discharge power of the first cold plasma treatment is 30W, and the discharge temperature is 250°C; the second cold plasma treatment is performed under 100mL / min of argon, the discharge power of the second cold plasma treatment is 20W, and the discharge temperature is 150°C.

[0056] 2) The pretreated titanium dioxide nanotubes and titanium dioxide nanopowder obtained in step 1) are mixed with chromium nitrate nonahydrate at a titanium-chromium molar ratio of 3:4, and then an anionic aqueous hyperdispersant and deionized water are added to obtain a mixed solution; the anionic aqueous hyperdispersant is a sulfonate dispersant, and the amount of the anionic aqueous hyperdispersant added is 2% of the mass of the mixture of the titanium dioxide nanotubes and nanopowder.

[0057] 3) The pH value of the mixed solution in step 2) is adjusted to 7-8 with aqueous ammonia, and then sodium citrate with x=3 is added and the pH value of the mixed solution is maintained at about 7 with aqueous ammonia. x represents the molar ratio of the chelating agent sodium citrate to the metal ion.

[0058] 4) The mixed solution obtained in step 3) is stirred at a speed of 800 rpm in an oil bath at 70° C. for 5 hours to obtain a gel-like substance; the gel-like substance is placed in an oven at 110° C. and dried until it becomes fluffy like a mushroom cloud; the fluffy mushroom cloud-like substance is ground into fine powder, and carbon powder and a certain amount of organic binder having an equivalent molar amount of the metal element are added, the mixture is mixed evenly, and formed into small balls with a diameter of 1 cm.

[0059] 5) The small balls obtained in step 4) were placed in a crucible and calcined in an atmosphere furnace with argon gas flowing at 20 mL / min at a temperature of 1200° C. for 5 h; after calcination, the powder was obtained after cooling to room temperature.

[0060] 6) The powder obtained in step 5) was placed into a mold and degassed at 500°C for 5 h; the vacuum degree in the mold after degassing was 0.5×10 -3 Pa; after degassing, hot isostatic pressing was carried out at 900°C and 150MPa for 4h to obtain a titanium-chromium alloy sputtering target.

[0061] 7) The titanium-chromium alloy sputtering target obtained in step 6) is mechanically processed, inspected, cleaned and packaged to obtain product 2. Example 3.

[0062] A method for preparing a titanium-chromium alloy target material, the preparation steps of which are as follows: 1) purchasing titanium dioxide nanotubes with a size of 230 meshes, first putting the titanium dioxide nanotubes into a crucible, calcining them in a muffle furnace for 1.5 hours, and then annealing, the calcination temperature being 520°C; mixing 80nm titanium dioxide nanopowder accounting for 12% by mass into the annealed titanium dioxide nanotubes, and performing two cold plasma treatments to obtain a pretreated titanium dioxide nanotube and titanium dioxide nanopowder mixture; the first cold plasma treatment is performed under 30mL / min of oxygen, the discharge power of the first cold plasma treatment is 40W, and the discharge temperature is 125°C; the second cold plasma treatment is performed under 80mL / min of argon, the discharge power of the second cold plasma treatment is 10W, and the discharge temperature is 130°C.

[0063] 2) The pretreated titanium dioxide nanotubes and titanium dioxide nanopowder obtained in step 1) are mixed with chromium nitrate nonahydrate at a titanium-chromium molar ratio of 4:7, and then an anionic aqueous hyperdispersant and deionized water are added to obtain a mixed solution; the anionic aqueous hyperdispersant is a sulfonate dispersant, and the amount of the anionic aqueous hyperdispersant added is 2% of the mass of the mixture of the titanium dioxide nanotubes and nanopowder.

[0064] 3) The pH value of the mixed solution in step 2) is adjusted to 7-8 with aqueous ammonia, and then the pH value of the mixed solution is maintained at about 7 with aqueous ammonia after adding a mixture of EDTA and sodium citrate with x=2. x represents the molar ratio of the chelating agent EDTA and sodium citrate to the metal ion, and the molar amount of EDTA in the mixture of EDTA and sodium citrate: the molar amount of sodium citrate is 1:1.

[0065] 4) The mixed solution obtained in step 3) is stirred at a speed of 1000 rpm in a water bath at 60° C. for 5 hours to obtain a gel-like substance; the gel-like substance is placed in an oven at 130° C. and dried until it becomes fluffy like a mushroom cloud; the fluffy mushroom cloud-like substance is ground into fine powder, and carbon powder and a certain amount of organic binder having an equivalent molar amount of the metal element are added, the mixture is mixed evenly, and formed into small balls with a diameter of 1 cm.

[0066] 5) The small balls obtained in step 4) were placed in a crucible and calcined in an atmosphere furnace with argon gas flowing at 20 mL / min at a temperature of 1300° C. for 4 h; after calcination, the powder was obtained after cooling to room temperature.

[0067] 6) The powder obtained in step 5) was placed into a mold and degassed at 600°C for 4 h; the vacuum degree in the mold after degassing was 1.0×10 -3 Pa; after degassing, hot isostatic pressing was carried out at 1100°C and 150MPa for 3.5h to obtain a titanium-chromium alloy sputtering target.

[0068] 7) The titanium-chromium alloy sputtering target obtained in step 6) is mechanically processed, inspected, cleaned and packaged to obtain product 3. Example 4.

[0069] A method for preparing a titanium-chromium alloy target material, the preparation steps of which are as follows: 1) purchasing titanium dioxide nanotubes with a size of 330 meshes, firstly placing the titanium dioxide nanotubes in a crucible, calcining them in a muffle furnace for 2 hours, and then annealing, the calcination temperature being 480°C; mixing 75nm titanium dioxide nanopowder accounting for 9% by mass into the annealed titanium dioxide nanotubes, and performing two cold plasma treatments to obtain a pretreated titanium dioxide nanotube and titanium dioxide nanopowder mixture; the first cold plasma treatment is performed under 35mL / min of oxygen, the discharge power of the first cold plasma treatment is 42W, and the discharge temperature is 160°C; the second cold plasma treatment is performed under 70mL / min of argon, the discharge power of the second cold plasma treatment is 14W, and the discharge temperature is 180°C.

[0070] 2) The pretreated titanium dioxide nanotubes and titanium dioxide nanopowder obtained in step 1) are mixed with chromium nitrate nonahydrate at a titanium-chromium molar ratio of 1:1, and then an anionic aqueous hyperdispersant and deionized water are added to obtain a mixed solution; the anionic aqueous hyperdispersant is a sulfonate dispersant, and the amount of the anionic aqueous hyperdispersant added is 2% of the mass of the mixture of the titanium dioxide nanotubes and nanopowder.

[0071] 3) The pH value of the mixed solution in step 2) is adjusted to 7-8 with aqueous ammonia, and then EDTA (x=1) is added and the pH value of the mixed solution is maintained at about 7 with aqueous ammonia. x represents the molar ratio of the chelating agent EDTA to the metal ion.

[0072] 4) The mixed solution obtained in step 3) is stirred at a speed of 700 rpm in a water bath at 75° C. for 4 hours to obtain a gel-like substance; the gel-like substance is placed in an oven at 120° C. and dried until it becomes fluffy like a mushroom cloud; the fluffy mushroom cloud-like substance is ground into fine powder, and carbon powder and a certain amount of organic binder having an equivalent molar amount of the metal element are added, the mixture is mixed evenly, and formed into small balls with a diameter of 1 cm.

[0073] 5) The small balls obtained in step 4) were placed in a crucible and calcined in an atmosphere furnace with argon gas flowing at 20 mL / min at a temperature of 1500° C. for 7 h; after calcination, the powder was obtained after cooling to room temperature.

[0074] 6) The powder obtained in step 5) was placed into a mold and degassed at 600°C for 8 h; the vacuum degree in the mold after degassing was 0.1×10 -3Pa; after degassing, hot isostatic pressing was carried out at 1200°C and 170MPa for 3h to obtain a titanium-chromium alloy sputtering target.

[0075] 7) The titanium-chromium alloy sputtering target obtained in step 6) is mechanically processed, inspected, cleaned and packaged to obtain product 4. Example 5.

[0076] A method for preparing a titanium-chromium alloy target material, the preparation steps of which are as follows: 1) purchasing titanium dioxide nanotubes with a size of 380 meshes, firstly placing the titanium dioxide nanotubes in a crucible, calcining them in a muffle furnace for 1 hour, and then annealing, the calcination temperature being 580°C; mixing 55nm titanium dioxide nanopowder accounting for 17% by mass into the annealed titanium dioxide nanotubes, and performing two cold plasma treatments to obtain a pretreated titanium dioxide nanotube and titanium dioxide nanopowder mixture; the first cold plasma treatment is performed under 44mL / min of oxygen, the discharge power of the first cold plasma treatment is 38W, and the discharge temperature is 220°C; the second cold plasma treatment is performed under 90mL / min of argon, the discharge power of the second cold plasma treatment is 10W, and the discharge temperature is 70°C.

[0077] 2) The pretreated titanium dioxide nanotubes and titanium dioxide nanopowder obtained in step 1) are mixed with chromium nitrate nonahydrate at a titanium-chromium molar ratio of 5:3, and then an anionic aqueous hyperdispersant and deionized water are added to obtain a mixed solution; the anionic aqueous hyperdispersant is a sulfonate dispersant, and the amount of the anionic aqueous hyperdispersant added is 2% of the mass of the mixture of the titanium dioxide nanotubes and nanopowder.

[0078] 3) The pH value of the mixed solution in step 2) is adjusted to 7-8 with aqueous ammonia, and then the pH value of the mixed solution is maintained at about 7 with aqueous ammonia after adding a mixture of EDTA and sodium citrate with x=3. x represents the molar ratio of the chelating agent EDTA and sodium citrate to the metal ion, and the molar amount of EDTA in the mixture of EDTA and sodium citrate: the molar amount of sodium citrate is 1:1.

[0079] 4) The mixed solution obtained in step 3) is stirred at a speed of 800 rpm in a water bath at 75° C. for 4.5 hours to obtain a gel-like substance; the gel-like substance is placed in an oven at 130° C. and dried until it becomes a mushroom cloud-like fluffy substance; the mushroom cloud-like fluffy substance is ground into fine powder, and carbon powder and a certain amount of organic binder having an equivalent molar amount of the metal element are added, the mixture is mixed evenly, and formed into small balls with a diameter of 1 cm.

[0080] 5) The small balls obtained in step 4) were placed in a crucible and calcined in an atmosphere furnace with argon gas flowing at 20 mL / min at a temperature of 1400° C. for 5 h; after calcination, the powder was obtained after cooling to room temperature.

[0081] 6) The powder obtained in step 5) was placed into a mold and degassed at 500°C for 5 h. The vacuum degree in the mold after degassing was 1.0×10 -3 Pa; after degassing, hot isostatic pressing was carried out at 800°C and 130MPa for 5h to obtain a titanium-chromium alloy sputtering target.

[0082] 7) The titanium-chromium alloy sputtering target obtained in step 6) is mechanically processed, inspected, cleaned and packaged to obtain product 5.

[0083] The density of the titanium-chromium alloy sputtering target prepared in Examples 1-5 was tested. The test method was based on GB / T231.1-2018. The results are shown in Table 1.

[0084] Table 1. Properties of titanium-chromium alloy sputtering targets prepared in Examples 1-5 Example Sample Ti:Cr element ratio Relative molecular weight purity / % Density / % Example 1 1：2 50.41 99.9998 99.59 Example 2 3：4 50.14 99.9999 99.83 Example 3 4：7 50.37 99.9995 99.76 Example 4 1：1 49.70 99.9997 99.53 Example 5 5：3 49.37 99.9998 99.90 .

[0085] It can be seen from Table 1 that the density of the titanium-chromium alloy target prepared by the present invention is above 99.50%, and the purity is above 99.999%; moreover, the metal elements are respectively uniform and stable, and the element composition can be accurately controlled according to different element proportions.

[0086] The technical features of the above embodiments may be combined arbitrarily. To make the description concise, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0087] The above embodiments only express several implementation methods of the present invention, and the description is relatively specific and detailed, but it cannot be understood as limiting the scope of the invention patent. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. The parts not described in the specific embodiments are all prior art or common knowledge.

[0088] It should be noted that, in the description of the present invention, the content of the present invention can be more easily understood by referring to the detailed description of the preferred implementation method of the present invention and the embodiments included. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meanings as those of ordinary skill in the art to which the present invention belongs. When there is a conflict, the definitions in this specification shall prevail.

[0089] In the present invention, the term "prepared from..." is used synonymously with "comprising". The terms "comprising", "including", "having", "containing" or any other variation thereof, as used in the present invention, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus comprising the listed elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0090] In the present invention, when an amount, concentration, or other value or parameter is expressed as a range, a preferred range, or a range limited by a series of upper preferred values ​​and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted as including a range of "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5" etc. When a numerical range is described in the present invention, unless otherwise stated, the range is intended to include its end values ​​and all integers and fractions within the range.

[0091] In addition, the indefinite articles "a" and "an" before the elements or components of the present invention have no restrictions on the quantity requirements (i.e. the number of occurrences) of the elements or components. Therefore, "a" or "an" should be interpreted as including one or at least one, and the elements or components in the singular form also include the plural form, unless the number is obviously intended to be in the singular form.

Claims

1. A method for preparing a titanium-chromium alloy target, characterized in that: Here are the steps: The pretreated titanium dioxide nanotube and titanium dioxide nanopowder mixture is mixed with chromium nitrate at a titanium-chromium molar ratio of 1:2-2:1, deionized water, a hyperdispersant and a chelating agent are added to the mixture, and the pH value is maintained at 7-8 with ammonia water, and heated and stirred to obtain a gel-like substance; the gel-like substance is placed in an oven for drying to obtain a mushroom cloud fluffy substance, and the mushroom cloud fluffy substance is ground, calcined with carbon powder, degassed, and hot static pressed to obtain the titanium-chromium alloy sputtering target; The pretreatment method of the mixture of titanium dioxide nanotubes and titanium dioxide nanopowders is as follows: firstly annealing the titanium dioxide nanotubes, mixing the annealed titanium dioxide nanotubes and titanium dioxide nanopowders and performing acid washing and cold plasma treatment; In the mixture of titanium oxide nanotubes and titanium dioxide nanopowder, the mass proportion of titanium dioxide nanopowder is 5-20%.

2. The method for preparing a titanium-chromium alloy target according to claim 1, characterized in that: The size of the titanium dioxide nanotube is 200-400 meshes, the particle size of the titanium dioxide nanopowder is 3-100nm, and the main crystal form of the titanium dioxide nanopowder is rutile.

3. The method for preparing a titanium-chromium alloy target according to claim 1, characterized in that: The annealing process of the titanium dioxide nanotubes is as follows: the titanium dioxide nanotubes are placed in a crucible and annealed in a muffle furnace at 450-600° C. for 1-3 hours.

4. The method for preparing a titanium-chromium alloy target according to claim 1, characterized in that: In the mixture formed by titanium dioxide nanotubes and titanium dioxide nanopowder, the mass proportion of titanium dioxide nanopowder is 5-20%.

5. The method for preparing a titanium-chromium alloy target according to claim 1, characterized in that: The pickling method is as follows: pour the mixture into HNO3 solution and perform ultrasonic cleaning twice, each time for 30±5 minutes; then pour the mixture into deionized water and perform ultrasonic cleaning twice, each time for 30±5 minutes.

6. The method for preparing a titanium-chromium alloy target according to claim 1, characterized in that: The cold plasma treatment method is: first use oxygen with a gas flow rate of 20-50mL / min at a discharge power of 30-50W and a discharge temperature of 100-250°C for treatment, and then use argon with a gas flow rate of 50-120mL / min at a discharge power of 3-20W and a discharge temperature of 50-200°C for treatment.

7. The method for preparing a titanium-chromium alloy target according to claim 1, characterized in that: The super dispersant is a sulfonate anionic water-based super dispersant.

8. The method for preparing a titanium-chromium alloy target according to claim 1, characterized in that: The chelating agent is selected from one or more of sodium citrate and EDTA, and the dosage of the chelating agent is proportional to the molar number of the metal ion, chelating agent: metal ion=x, x=1-4.

9. The method for preparing a titanium-chromium alloy target according to claim 1, characterized in that: The heating and stirring is water bath or oil bath heating, the heating temperature is 60-80°C, the stirring rate is 400-1000rpm, and the mixing time is 4-6h; The heating temperature of the oven is 110-130°C; The carbon powder calcination is to add carbon powder in an amount equivalent to the molar amount of the metal element, mix evenly with an organic binder, prepare small balls with a diameter of 1±0.5 cm, and calcine at a calcination temperature of 1000-1500° C. for 3-7 hours in an argon atmosphere furnace; The degassing temperature is 300-600°C, the degassing time is 4-8h, and the vacuum degree in the mold after degassing is less than 5.0×10 -3 Pa; The temperature of the hot isostatic pressing treatment is 600-1200°C, the pressure is 90-170MPa, and the treatment time is 3-6h; After the hot isostatic pressing treatment, the titanium-chromium alloy sputtering target material obtained is subjected to mechanical processing, testing, cleaning and packaging.

10. A titanium-chromium alloy target, characterized in that: The target is prepared by the method for preparing a titanium-chromium alloy target as described in any one of claims 1 to 9.

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