CN114075658B - Tungsten nickel alloy sputtering target material and hot pressing preparation method thereof - Google Patents
Tungsten nickel alloy sputtering target material and hot pressing preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/247—Removing material: carving, cleaning, grinding, hobbing, honing, lapping, polishing, milling, shaving, skiving, turning the surface
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Abstract
The invention provides a tungsten nickel alloy sputtering target material and a hot pressing preparation method thereof, wherein the preparation method is to sinter tungsten nickel alloy powder with the mass ratio of Ni powder being 44.1-49.5% by mixing powder and HP to obtain the tungsten nickel alloy sputtering target material, so that the tungsten nickel alloy sputtering target material with high compactness, uniform microstructure, uniform composition and excellent machining performance can be obtained, the compactness is more than or equal to 95%, more preferably more than or equal to 99%, the application requirement of the current high-performance electrochromic glass is met, and the method has the advantages of simple process, lower cost, convenience in popularization and the like.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a tungsten-nickel alloy sputtering target material and a hot pressing preparation method thereof.
Background
The magnetron sputtering is one of the main technologies for preparing film materials, ions generated by an ion source are utilized, and are accelerated and aggregated in vacuum to form high-speed ion beam current, the high-speed ion beam current bombards the surface of a solid, and the ions and atoms on the surface of the solid are subjected to kinetic energy exchange, so that the atoms on the surface of the solid leave the solid and are deposited on the surface of a substrate, and a film with the thickness of nano or micron level is formed. The bombarded solid is a raw material for preparing a magnetron sputtering deposition film, is generally called a sputtering target material, and is intensively applied to industries such as information storage, integrated circuits, displays, automobile rearview mirrors and the like.
Sputtering targets are generally obtained by a powder metallurgy sintering molding process, and because the sputtering targets prepared by the process have unique chemical compositions, mechanical properties and physical properties, porous, semi-dense or fully dense materials and products can be directly prepared. As an important powder metallurgy sintering molding process, hot Pressing (HP) is a process method for uniaxial Pressing of powder or pressed compact at high temperature, which can generate activation diffusion and creep phenomena, and is widely applied to the fields of sintering of solid materials, large-area welding among dissimilar metals, and the like, and the main principle is lattice and grain boundary diffusion and plastic flow at high temperature. The microstructure of the material after hot pressing is generally ideal, and the method is a process method with mature technology and low cost.
Electrochromic material has wide application foreground in intelligent window, antiglare reflector, light information storage, etc. The electrochromic intelligent glass has light absorption and transmission adjustability under the action of an electric field, can selectively absorb or reflect external heat radiation and internal heat diffusion, and has reversibly changed optical properties (reflectivity, transmissivity, absorptivity and the like), so that the electrochromic intelligent glass is one development direction of energy-saving building materials. Currently, electrochromic intelligent glass has been applied to some high-grade cars and airplanes, and is widely applied to the fields of intelligent windows, anti-dazzling reflectors, optical information storage and the like.
As the basis for preparing electrochromic glass films, tungsten-nickel alloy sputtering coating targets are widely used, and during coating, tungsten-nickel alloy targets generate tungsten-nickel alloy oxide layers on the surfaces of the glass, and oxidation-reduction reaction and color change occur under the action of voltage.
CN105239043a discloses an electrochromic glass tungsten-nickel alloy target and a preparation method thereof. Firstly, tungsten powder with the purity of 99.99 percent and nickel powder with the purity of 99.9 percent are put into a high-energy ball mill, and high-purity Ar is filled 2 Mixing at the speed of 200-250r/min to obtain tungsten-nickel alloy powder; then cold isostatic pressing is used for forming, and a tungsten-nickel blank is prepared by pressurization; loading the tungsten nickel blank into a vacuum sintering furnace for sintering; closing the heating system of the vacuum sintering furnace, and discharging after cooling to room temperature along with furnace to obtain total purity>99.9 percent of color-changing glass tungsten nickel alloy target material with the nickel mass ratio of 10 to 50 percent. The preparation method comprises ball milling and powder mixing, cold isostatic pressing and vacuum sintering, and has complex process and high cost.
CN110885963a discloses a preparation method of tungsten-nickel alloy target material and tungsten-nickel alloy target material prepared by the method. The preparation method of the tungsten-nickel alloy target comprises the following steps: the preparation method comprises the following steps: mixing tungsten powder and nickel powder to obtain mixed powder; and (3) a press forming step: carrying out compression molding treatment on the mixed powder to obtain a preform; and (3) sintering: sintering the preform to obtain a sintered blank; and (3) hot isostatic pressing treatment: performing hot isostatic pressing treatment on the sintered blank to obtain a hot isostatic pressing blank; and (3) heat treatment: and performing heat treatment on the hot isostatic pressing blank, and then rapidly cooling to obtain the tungsten-nickel alloy target. The preparation method comprises the steps of powder mixing, pressing (cold isostatic pressing), sintering, hot isostatic pressing and heat treatment, and has complex process and higher cost.
CN113549881a discloses a preparation method of a tungsten-nickel alloy target, which comprises selecting tungsten powder and nickel powder or multi-component alloy powder formed by the tungsten powder and other metal elements, and sequentially passing through a powder sieving treatment step, a cold isostatic pressing step, a sintering step, a straightening processing step, an annealing treatment step, a machining step and a cleaning treatment step to prepare the high tungsten-nickel alloy target. The preparation method has complex flow and higher cost, and the tungsten-nickel alloy target contains other metal elements and has lower purity.
In addition, the currently applied tungsten-nickel alloy targets are mostly manufactured by adopting a thermal spraying process, the density of the sputtering target is only about 90%, the nickel element in the targets is unevenly distributed, the sputtering performance of the product is affected, and therefore the quality of the electrochromic layer is affected.
Therefore, development of a tungsten-nickel alloy sputtering target material and a hot pressing preparation method thereof are needed at present, and the hot pressing preparation method not only can obtain the tungsten-nickel alloy sputtering target material with high density, uniform microstructure, uniform composition and excellent machining performance, meets the application requirements of the current high-performance electrochromic glass, but also has the advantages of simple process, lower cost, convenience in popularization and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides the tungsten-nickel alloy sputtering target material and the hot pressing preparation method thereof, wherein the preparation method is to sinter tungsten-nickel alloy powder with the mass ratio of Ni powder of 44.1-49.5% by powder mixing-HP to obtain the tungsten-nickel alloy sputtering target material, so that the tungsten-nickel alloy sputtering target material with high compactness, uniform microstructure, uniform components, excellent machining performance can be obtained, the compactness is more than or equal to 95%, more preferably more than or equal to 99%, the application requirements of the current high-performance electrochromic glass are met, and the method has the advantages of simple process, lower cost, convenience in popularization and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a hot pressing preparation method of a tungsten-nickel alloy sputtering target, which comprises the following steps:
(1) Preparing tungsten nickel alloy powder with the mass ratio of 44.1-49.5% of Ni powder, filling the tungsten nickel alloy powder into a mould and sealing;
(2) Carrying out hot-pressing sintering treatment on the die after the sealing in the step (1) to obtain a tungsten-nickel alloy sintered body;
(3) And (3) machining the tungsten-nickel alloy sintered body obtained in the step (2) to obtain the tungsten-nickel alloy sputtering target material.
It is worth to say that the mass ratio of Ni powder in the tungsten nickel alloy powder is 44.1-49.5%, the balance is unavoidable impurities, and the tungsten nickel alloy powder does not contain regulator powder such as tungsten trioxide, so that the purity of the final tungsten nickel alloy sputtering target material is ensured, the effective alloying of W-Ni is ensured, the compactness of the tungsten nickel alloy sputtering target material is more than or equal to 95%, and more preferably more than or equal to 99%.
According to the preparation method, the tungsten nickel alloy powder with the mass ratio of Ni powder being 44.1-49.5% is sintered by powder mixing-HP to obtain the tungsten nickel alloy sputtering target material, so that the tungsten nickel alloy sputtering target material with high density, uniform microstructure, uniform components, excellent machining performance can be obtained, the density is more than or equal to 95%, more preferably more than or equal to 99%, the application requirements of the current high-performance electrochromic glass are met, and the preparation method has the advantages of simple process, low cost, convenience in popularization and the like.
The mass ratio of the Ni powder in the tungsten nickel alloy powder is 44.1-49.5%, such as 44.1%, 44.5%, 45.0%, 45.5%, 46.0%, 46.5%, 47.0%, 47.5%, 48.0%, 48.5%, 49.0% or 49.5%, etc., but the tungsten nickel alloy powder is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
As a preferable technical scheme of the invention, the tungsten-nickel alloy powder is obtained by mixing W powder and Ni powder according to the mass ratio of 44.1-49.5% of Ni powder.
Preferably, the purity of the W powder is 99.95-99.999 wt%.
Preferably, the average particle size of the W powder is < 45 μm.
Preferably, the purity of the Ni powder is 99.95-99.99 wt%.
Preferably, the Ni powder has an average particle size of < 45 μm.
As a preferred technical scheme of the invention, the mixing is performed in a powder mixer.
Preferably, the mixing is performed by adding zirconium balls for dry blending.
Preferably, the mass ratio of the zirconium balls to the tungsten nickel alloy powder is (1-3): 10, such as 1:10, 1.5:10, 2:10, 2.5:10 or 3:10, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the mixing is performed under an argon atmosphere.
Preferably, the mixing time is 24 to 36 hours, such as 26 hours, 28 hours, 30 hours, 32 hours, 34 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferable technical scheme of the invention, the die in the step (1) is a graphite die.
Preferably, after the tungsten nickel alloy powder is loaded into the die in the step (1), the compacting treatment is further included before the sealing.
Preferably, the compacting treatment comprises a manual column pressing mode to ensure flatness < 1mm.
The compaction treatment is carried out by adopting a manual column pressing mode, so that the compaction treatment can be flexibly and timely adjusted according to actual conditions, and the initial density requirement required by hot-pressed sintering treatment can be met, and further, the tungsten nickel alloy sputtering target material with the density more than or equal to 95% can be obtained by the subsequent hot-pressed sintering treatment.
In a preferred embodiment of the present invention, the target temperature of the hot press sintering treatment in the step (2) is 1270 to 1350 ℃, for example 1270 ℃, 1280 ℃, 1290 ℃, 1300 ℃, 1310 ℃, 1320 ℃, 1330 ℃, 1340 ℃, 1350 ℃, or 1350 ℃, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value ranges are equally applicable.
Preferably, the target pressure of the hot press sintering treatment in the step (2) is 25 to 35MPa, for example, 26MPa, 27MPa, 28MPa, 29MPa, 30MPa, 31MPa, 32MPa, 33MPa or 34MPa, etc., but the target pressure is not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the heat-pressing sintering treatment in the step (2) has a holding time of 60 to 180min, for example, 60min, 80min, 100min, 120min, 140min, 150min, 170min or 180min, at the target temperature and the target pressure, but the heat-pressing sintering treatment is not limited to the listed values, and other non-listed values within the range of values are equally applicable.
As a preferable technical scheme of the invention, the hot press sintering treatment in the step (2) comprises the following steps:
(i) Placing the die after the sealing in the step (1) into a hot-pressing sintering furnace, vacuumizing to below 100Pa, heating to 1000-1050 ℃ and preserving heat for 60-90 min, wherein the internal pressure of the die after the sealing is controlled to be less than 1MPa;
(ii) Heating to 1270-1350 ℃ after the heat preservation in the step (i) is finished, and preserving the heat for 50-70 min, wherein the internal pressure of the sealed die is controlled to be less than 1MPa;
(iii) After the heat preservation in the step (ii) is finished, pressurizing to 25-35 MPa, always keeping 1270-1350 ℃, and controlling the heat preservation and pressure maintaining time to be 60-180 min;
(iv) And (3) after the heat preservation and pressure maintaining in the step (iii) are finished, closing the hot-pressed sintering furnace, cooling, and then filling argon until the vacuum representation number is-0.06 to-0.08 MPa.
It should be noted that, in both step (i) and step (ii), the internal pressure of the sealed mold is controlled to be less than 1MPa, because: in the heating process, the tungsten nickel alloy powder can increase the pressure in the die due to thermal expansion, and the internal pressure is controlled to be less than 1MPa to prevent the target blank from being formed and compact in advance under the condition of insufficient temperature due to overlarge local pressure, so that the problem of nonuniform density of the target material is avoided.
It is worth noting that, aiming at tungsten nickel alloy powder with the mass ratio of Ni powder being 44.1-49.5%, the inventor can ensure W-Ni alloying only by adopting the preparation method of heating step by step and pressurizing step by step, and the tungsten nickel alloy sputtering target material with the density being more than or equal to 95%, and more preferably with the density being more than or equal to 99% after multiple experiments.
The temperature is raised to 1000 to 1050 ℃, for example 1000 ℃, 1010 ℃, 1020 ℃, 1030 ℃, 1040 ℃, 1050 ℃ or the like in the hot press sintering treatment step (i) of the present invention, but the present invention is not limited to the values listed, and other values not listed in the range are equally applicable.
The heat-pressing sintering treatment step (i) of the present invention is performed for 60 to 90 minutes, for example, 60 minutes, 65 minutes, 70 minutes, 75 minutes, 80 minutes, 85 minutes, or 90 minutes, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are applicable.
The heat-pressing sintering treatment step (ii) of the present invention is performed for 50 to 70 minutes, for example, 50 minutes, 55 minutes, 60 minutes, 65 minutes, 70 minutes, or the like, but is not limited to the values listed, and other values not listed in the range are applicable.
In the hot press sintering treatment step (iv), the vacuum representation number is-0.06 to-0.08 MPa, for example-0.06 MPa, -0.065MPa, -0.07MPa, -0.075MPa or-0.08 MPa, etc., but the present invention is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In a preferred embodiment of the present invention, the temperature rising rate of the temperature rising in the step (i) is 8 to 12℃per minute, for example, 8.5℃per minute, 9℃per minute, 9.5℃per minute, 10℃per minute, 10.5℃per minute, 11℃per minute, 11.5℃per minute, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are applicable.
Preferably, the temperature rising rate of the temperature rising in the step (ii) is 3 to 6 ℃ per minute, for example, 3.5 ℃ per minute, 4 ℃ per minute, 4.5 ℃ per minute, 5 ℃ per minute, 5.5 ℃ per minute, or 5.5 ℃ per minute, etc., but the temperature rising rate is not limited to the recited values, and other values not recited in the range of the values are equally applicable.
Preferably, the time of the pressurization in step (iii) is 50 to 70min, for example 52min, 55min, 58min, 60min, 62min, 64min, 65min or 68min, etc., but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, in the step (iv), after the temperature in the hot press sintering furnace is reduced to 200 ℃, the blank in the die is taken out, and the tungsten-nickel alloy sintered body is obtained.
As a preferred technical solution of the present invention, the machining in the step (3) includes wire cutting and/or grinding;
preferably, after the machining in the step (3), welding the tungsten-nickel alloy sputtering target material with a copper back plate or an aluminum back plate, machining to a target size, and then sequentially detecting, cleaning, drying and packaging to obtain the tungsten-nickel alloy target material assembly.
As a preferable technical scheme of the invention, the hot pressing preparation method comprises the following steps:
(1) Preparing tungsten nickel alloy powder with the mass ratio of 44.1-49.5% of Ni powder, filling the tungsten nickel alloy powder into a graphite mold, compacting the tungsten nickel alloy powder in the graphite mold by adopting a manual column pressing mode to ensure that the flatness is less than 1mm, and sealing;
wherein the tungsten nickel alloy powder is obtained by mixing W powder and Ni powder according to the mass ratio of the Ni powder of 44.1-49.5%, the purity of the W powder is 99.95-99.999 wt%, the average grain diameter is less than 45 mu m, the purity of the Ni powder is 99.95-99.99 wt%, and the average grain diameter is less than 45 mu m; the mixing is carried out in a powder mixer, a mode of adding zirconium balls for dry mixing is adopted, the ball material mass ratio of the zirconium balls to the tungsten-nickel alloy powder is controlled to be (1-3): 10, and the zirconium balls and the tungsten-nickel alloy powder are uniformly mixed for 24-36 hours under the protection of argon;
(2) Hot pressing and sintering:
(i) Placing the sealed die in the step (1) into a hot-pressing sintering furnace, vacuumizing to below 100Pa, heating to 1000-1050 ℃ at a heating rate of 8-12 ℃/min, and preserving heat for 60-90 min, wherein the internal pressure of the sealed die is controlled to be less than 1MPa;
(ii) After the heat preservation in the step (i) is finished, heating to 1270-1350 ℃ at a heating rate of 3-6 ℃/min, and preserving the heat for 50-70 min, wherein the internal pressure of the sealed die is controlled to be less than 1MPa;
(iii) After the heat preservation in the step (ii) is finished, pressurizing to 25-35 MPa for 50-70 min, always keeping 1270-1350 ℃, and controlling the heat preservation and pressure maintaining time to be 60-180 min;
(iv) After the heat preservation and pressure maintaining in the step (iii) are finished, closing the hot-pressed sintering furnace, cooling, then filling argon until the vacuum representation number is-0.06 to-0.08 MPa, and taking out the blank in the die after the temperature in the hot-pressed sintering furnace is reduced to 200 ℃ to obtain a tungsten-nickel alloy sintered body;
(3) And (3) performing wire cutting and/or grinding on the tungsten-nickel alloy sintered body obtained in the step (2) to obtain the tungsten-nickel alloy sputtering target material.
The second purpose of the invention is to provide a tungsten-nickel alloy sputtering target material, which is obtained by the hot pressing preparation method.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the preparation method, the tungsten nickel alloy powder with the mass ratio of Ni powder being 44.1-49.5% is sintered by powder mixing-HP to obtain the tungsten nickel alloy sputtering target material, so that the tungsten nickel alloy sputtering target material with high density, uniform microstructure, uniform components, excellent machining performance can be obtained, the density is more than or equal to 95%, more preferably more than or equal to 99%, the application requirements of the current high-performance electrochromic glass are met, and the preparation method has the advantages of simple process, low cost, convenience in popularization and the like.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a hot pressing preparation method of a tungsten nickel alloy sputtering target, which comprises the following steps:
(1) Preparing tungsten-nickel alloy powder with the mass ratio of Ni powder being 45.5%, filling the tungsten-nickel alloy powder into a graphite mold, compacting the tungsten-nickel alloy powder in the graphite mold by adopting a manual column pressing mode, ensuring the flatness to be less than 1mm, and sealing;
the tungsten nickel alloy powder is obtained by mixing W powder and Ni powder according to the mass ratio of the Ni powder being 45.5%, wherein the purity of the W powder is 99.999wt%, the average grain diameter is less than 45 mu m, the purity of the Ni powder is 99.99wt%, and the average grain diameter is less than 45 mu m; the mixing is carried out in a powder mixer, a mode of adding zirconium balls for dry mixing is adopted, the ball material mass ratio of the zirconium balls to the tungsten-nickel alloy powder is controlled to be 3:10, and the zirconium balls and the tungsten-nickel alloy powder are uniformly mixed for 32 hours under the protection of argon;
(2) Hot pressing and sintering:
(i) Placing the die after the sealing in the step (1) into a hot-pressing sintering furnace, vacuumizing to below 100Pa, heating to 1000 ℃ at a heating rate of 10 ℃/min, and preserving heat for 70min, wherein the internal pressure of the die after the sealing is controlled to be less than 1MPa;
(ii) After the heat preservation in the step (i) is finished, heating to 1300 ℃ at a heating rate of 5 ℃/min and preserving the heat for 60min, wherein the internal pressure of the sealed die is controlled to be less than 1MPa;
(iii) After the heat preservation in the step (ii) is finished, pressurizing to 30MPa for 60min, and always keeping the temperature at 1300 ℃, wherein the heat preservation and pressure keeping time is controlled to be 120min;
(iv) After the heat preservation and pressure maintaining in the step (iii) are finished, closing the hot-pressing sintering furnace, cooling, then filling argon until the vacuum representation number is-0.07 MPa, and taking out the blank in the die after the temperature in the hot-pressing sintering furnace is reduced to 200 ℃ to obtain a tungsten nickel alloy sintered body;
(3) And (3) performing wire cutting and/or grinding on the tungsten-nickel alloy sintered body obtained in the step (2) to obtain the tungsten-nickel alloy sputtering target material.
Example 2
The embodiment provides a hot pressing preparation method of a tungsten nickel alloy sputtering target, which comprises the following steps:
(1) Preparing tungsten-nickel alloy powder with the mass ratio of Ni powder being 44.1%, filling the tungsten-nickel alloy powder into a graphite mold, compacting the tungsten-nickel alloy powder in the graphite mold by adopting a manual column pressing mode, ensuring the flatness to be less than 1mm, and sealing;
the tungsten nickel alloy powder is obtained by mixing W powder and Ni powder according to the mass ratio of the Ni powder being 44.1%, wherein the purity of the W powder is 99.999wt%, the average grain diameter is less than 45 mu m, the purity of the Ni powder is 99.99wt%, and the average grain diameter is less than 45 mu m; the mixing is carried out in a powder mixer, a mode of adding zirconium balls for dry mixing is adopted, the ball material mass ratio of the zirconium balls to the tungsten-nickel alloy powder is controlled to be 3:10, and the zirconium balls and the tungsten-nickel alloy powder are uniformly mixed for 24 hours under the protection of argon;
(2) Hot pressing and sintering:
(i) Placing the die after the sealing in the step (1) into a hot-pressing sintering furnace, vacuumizing to below 100Pa, heating to 1000 ℃ at a heating rate of 8 ℃/min, and preserving heat for 60min, wherein the internal pressure of the die after the sealing is controlled to be less than 1MPa;
(ii) After the heat preservation in the step (i) is finished, heating to 1270 ℃ at a heating rate of 3 ℃/min and preserving the heat for 50min, wherein the internal pressure of the sealed die is controlled to be less than 1MPa;
(iii) After the heat preservation in the step (ii) is finished, pressurizing to 25MPa for 50min, and always keeping 1270 ℃, wherein the heat preservation and pressure keeping time is controlled to be 60min;
(iv) After the heat preservation and pressure maintaining in the step (iii) are finished, closing the hot-pressing sintering furnace, cooling, then filling argon until the vacuum representation number is-0.06 MPa, and taking out the blank in the die after the temperature in the hot-pressing sintering furnace is reduced to 200 ℃ to obtain a tungsten nickel alloy sintered body;
(3) And (3) performing wire cutting and/or grinding on the tungsten-nickel alloy sintered body obtained in the step (2) to obtain the tungsten-nickel alloy sputtering target material.
Example 3
The embodiment provides a hot pressing preparation method of a tungsten nickel alloy sputtering target, which comprises the following steps:
(1) Preparing tungsten-nickel alloy powder with the mass ratio of the Ni powder being 49.5%, filling the tungsten-nickel alloy powder into a graphite mold, compacting the tungsten-nickel alloy powder in the graphite mold by adopting a manual column pressing mode, ensuring the flatness to be less than 1mm, and sealing;
the tungsten nickel alloy powder is obtained by mixing W powder and Ni powder according to the mass ratio of the Ni powder of 49.5%, wherein the purity of the W powder is 99.999wt%, the average grain diameter is less than 45 mu m, the purity of the Ni powder is 99.99wt%, and the average grain diameter is less than 45 mu m; the mixing is carried out in a powder mixer, a mode of adding zirconium balls for dry mixing is adopted, the ball material mass ratio of the zirconium balls to the tungsten-nickel alloy powder is controlled to be 3:10, and the zirconium balls and the tungsten-nickel alloy powder are uniformly mixed for 36 hours under the protection of argon;
(2) Hot pressing and sintering:
(i) Placing the die after the sealing in the step (1) into a hot-pressing sintering furnace, vacuumizing to below 100Pa, heating to 1050 ℃ at a heating rate of 12 ℃/min, and preserving heat for 90min, wherein the internal pressure of the die after the sealing is controlled to be less than 1MPa;
(ii) After the heat preservation in the step (i) is finished, heating to 1350 ℃ at a heating rate of 6 ℃/min and preserving the heat for 70min, wherein the internal pressure of the sealed die is controlled to be less than 1MPa;
(iii) After the heat preservation in the step (ii) is finished, pressurizing to 35MPa for 70min, and always keeping 1350 ℃, wherein the heat preservation and pressure keeping time is controlled to be 180min;
(iv) After the heat preservation and pressure maintaining in the step (iii) are finished, closing the hot-pressing sintering furnace, cooling, then filling argon until the vacuum representation number is-0.08 MPa, and taking out the blank in the die after the temperature in the hot-pressing sintering furnace is reduced to 200 ℃ to obtain a tungsten nickel alloy sintered body;
(3) And (3) performing wire cutting and/or grinding on the tungsten-nickel alloy sintered body obtained in the step (2) to obtain the tungsten-nickel alloy sputtering target material.
Example 4
The embodiment provides a hot pressing preparation method of a tungsten nickel alloy sputtering target material, which is based on the hot pressing preparation method described in embodiment 1, and is different only in that: defining the target temperature of step (ii) and step (iii) to be 1250 ℃.
Example 5
The embodiment provides a hot pressing preparation method of a tungsten nickel alloy sputtering target material, which is based on the hot pressing preparation method described in embodiment 1, and is different only in that: defining the target temperatures of step (ii) and step (iii) to be 1370 ℃.
Example 6
The embodiment provides a hot pressing preparation method of a tungsten nickel alloy sputtering target material, which is based on the hot pressing preparation method described in embodiment 1, and is different only in that: combining the step (i) and the step (ii) of the hot-press sintering treatment in the step (2) into one-step temperature rise, and specifically comprises the following steps:
(2) Hot pressing and sintering:
(i) Placing the die after the sealing in the step (1) into a hot-pressing sintering furnace, vacuumizing to below 100Pa, heating to 1300 ℃ at a heating rate of 10 ℃/min, and preserving heat for 120min, wherein the internal pressure of the die after the sealing is controlled to be less than 1MPa;
(ii) After the heat preservation in the step (i) is finished, pressurizing to 30MPa for 60min, and always keeping the temperature at 1300 ℃, wherein the heat preservation and pressure keeping time is controlled to be 120min;
(iii) And (3) after the heat preservation and pressure maintaining in the step (ii) are finished, closing the hot-pressed sintering furnace, cooling, then filling argon until the vacuum representation number is-0.07 MPa, and taking out the blank in the die after the temperature in the hot-pressed sintering furnace is reduced to 200 ℃ to obtain the tungsten-nickel alloy sintered body.
Comparative example 1
The comparative example adopts the preparation method of the tungsten-nickel alloy target material described in the embodiment 1 in CN110885963A to prepare the tungsten-nickel alloy sputtering target material with the Ni mass ratio of 45.5%.
The tungsten-nickel alloy sputtering targets obtained in the examples and the comparative examples were subjected to the following performance tests:
(1) Density: measuring the actual density of the tungsten-nickel alloy sputtering target material according to a basket hanging method disclosed in national standard GB/T3850-2015 ' density measuring method for compact sintered metal material and hard alloy ', calculating the theoretical density of the tungsten-nickel alloy sputtering target material according to a theoretical formula, and obtaining the tungsten-nickel alloy sputtering target material according to a calculation formula of ' density=actual density/theoretical density multiplied by 100%;
(2) Uniformity of internal structure of target material: firstly, taking a visual standard sample as a standard, and then precisely processing, wherein the surface is clean, the color and luster are uniform, and no bunchy or punctiform spots appear, so that the internal structure is uniform, and no segregation phenomenon appears.
The results of the relevant tests on the tungsten nickel alloy sputtering targets obtained in the above examples and comparative examples are shown in table 1.
TABLE 1
| Group of | Density of the product | Uniformity of internal structure of target material |
| Example 1 | 99.3％ | Uniform and even color |
| Example 2 | 97.9％ | Uniform and even color |
| Example 3 | 99.5％ | Uniform and even color |
| Example 4 | 95.2％ | Uniform and even color |
| Example 5 | 99.9％ | Uniform and even color, and occasionally appearance of bunchy or punctiform flower spots |
| Example 6 | 95.8％ | Uniform and even color, and occasionally appearance of bunchy or punctiform flower spots |
| Comparative example 1 | 99.9％ | Uniform and even color |
From table 1, the following points can be seen:
(1) According to the preparation method, the tungsten nickel alloy powder with the mass ratio of Ni powder being 44.1-49.5% is sintered by powder mixing-HP to obtain the tungsten nickel alloy sputtering target material, so that the tungsten nickel alloy sputtering target material with high density, uniform microstructure, uniform components, excellent machining performance can be obtained, the density is more than or equal to 95%, more preferably more than or equal to 99%, the application requirements of the current high-performance electrochromic glass are met, and the preparation method has the advantages of simple process, low cost, convenience in popularization and the like;
(2) Comparing example 1 with example 4, the density of the tungsten nickel alloy sputtering target is reduced because the target temperature of the hot press sintering in example 4 is 1250 ℃ and is lower than 1270-1350 ℃ according to the invention;
(3) Comparing example 1 with example 5, since the target temperature of hot press sintering in example 5 is 1370 ℃ and is higher than 1270-1350 ℃ in the invention, although the density is slightly increased, the internal structure of the target occasionally has bunched or punctiform spots;
(4) Comparing example 1 with example 6, in example 6, the stepwise heating in the hot-press sintering treatment is replaced by one-step heating, so that the tungsten-nickel alloy powder in the die is extremely easy to be heated unevenly, further the compactness of the tungsten-nickel alloy sputtering target is reduced, and the internal structure of the target occasionally generates bunchy or punctiform variegates;
(5) Comparing example 1 with comparative example 1, the performance of the tungsten-nickel alloy sputtering target material obtained by the two is basically the same, but the preparation method of comparative example 1 comprises the steps of raw material preparation, cold isostatic pressing, sintering in hydrogen atmosphere, hot isostatic pressing treatment and heat treatment, and has the defects of complex process and higher production cost.
The applicant states that the detailed process equipment and process flows of the present invention are described by the above examples, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon, the above detailed process equipment and process flows. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (16)
1. The hot-pressing preparation method of the tungsten-nickel alloy sputtering target material is characterized by comprising the following steps of:
(1) Preparing tungsten nickel alloy powder with the mass ratio of 44.1-49.5% of Ni powder, filling the tungsten nickel alloy powder into a mould and sealing;
the tungsten-nickel alloy powder is obtained by mixing W powder and Ni powder according to the mass ratio of the Ni powder of 44.1-49.5%; the purity of the W powder is 99.95-99.999wt%; the average grain diameter of the W powder is less than 45 mu m; the purity of the Ni powder is 99.95-99.99wt%; the average grain diameter of the Ni powder is less than 45 mu m;
(2) Carrying out hot-pressing sintering treatment on the die after the sealing in the step (1) to obtain a tungsten-nickel alloy sintered body;
wherein, the hot press sintering treatment comprises the following steps:
(i) Placing the die after the sealing in the step (1) into a hot-pressing sintering furnace, vacuumizing to below 100Pa, heating to 1000-1050 ℃ and preserving heat for 60-90 min, wherein the internal pressure of the die after the sealing is controlled to be less than 1MPa;
(ii) Heating to 1270-1350 ℃ after the heat preservation in the step (i) is finished, and preserving the heat for 50-70 min, wherein the internal pressure of the sealed die is controlled to be less than 1MPa;
(iii) After the heat preservation in the step (ii) is finished, pressurizing to 25-35 MPa, and always keeping 1270-1350 ℃, wherein the heat preservation and pressure keeping time is controlled to be 60-180 min;
(iv) After the heat preservation and pressure maintaining in the step (iii) are finished, closing the hot-pressing sintering furnace, cooling, and then filling argon until the vacuum representation number is-0.06 to-0.08 MPa;
(3) And (3) machining the tungsten-nickel alloy sintered body obtained in the step (2) to obtain the tungsten-nickel alloy sputtering target material.
2. The hot press preparation method according to claim 1, wherein the mixing is performed in a powder mixer.
3. The hot press preparation method according to claim 1, wherein the mixing is performed by adding zirconium balls for dry mixing; the mass ratio of the zirconium balls to the tungsten nickel alloy powder is (1-3) 10.
4. The hot press manufacturing method according to claim 1, wherein the mixing is performed under an argon atmosphere.
5. The hot press preparation method according to claim 1, wherein the mixing time is 24 to 36 hours.
6. The hot press manufacturing method according to claim 1, wherein the die of step (1) is a graphite die.
7. The hot press manufacturing method according to claim 1, further comprising a compacting process after the tungsten nickel alloy powder is charged into the mold in step (1) and before the sealing.
8. The hot press manufacturing method according to claim 7, wherein the compacting treatment includes a compacting treatment by a manual press column method, ensuring flatness < 1mm.
9. The hot press preparation method according to claim 1, wherein the heating rate of the heating in the step (i) is 8-12 ℃/min.
10. The hot press preparation method according to claim 1, wherein the heating rate of the heating in the step (ii) is 3-6 ℃/min.
11. The hot press preparation method according to claim 1, wherein the pressurizing time in the step (iii) is 50-70 min.
12. The hot press manufacturing method according to claim 1, wherein in the step (iv), after the temperature in the hot press sintering furnace is lowered to 200 ℃, the blank in the mold is taken out to obtain the tungsten nickel alloy sintered body.
13. The hot press manufacturing method according to claim 1, wherein the machining of step (3) includes wire cutting and/or grinding.
14. The method according to claim 1, wherein after the machining in the step (3), the tungsten-nickel alloy sputtering target material is welded with a back plate, and then machined to a target size, and then sequentially subjected to detection, cleaning, drying and packaging to obtain a tungsten-nickel alloy target material assembly.
15. The hot press preparation method according to claim 1, characterized in that the hot press preparation method comprises the steps of:
(1) Preparing tungsten nickel alloy powder with the mass ratio of 44.1-49.5% of Ni powder, filling the tungsten nickel alloy powder into a graphite mold, compacting the tungsten nickel alloy powder in the graphite mold by adopting a manual column pressing mode to ensure that the flatness is less than 1mm, and sealing;
the tungsten nickel alloy powder is obtained by mixing W powder and Ni powder according to the mass ratio of the Ni powder of 44.1-49.5%, wherein the purity of the W powder is 99.95-99.999wt%, the average grain diameter is less than 45 mu m, the purity of the Ni powder is 99.95-99.99wt%, and the average grain diameter is less than 45 mu m; the mixing is carried out in a powder mixer, a mode of adding zirconium balls for dry mixing is adopted, the ball material mass ratio of the zirconium balls to the tungsten-nickel alloy powder is controlled to be (1-3): 10, and the zirconium balls and the tungsten-nickel alloy powder are uniformly mixed for 24-36 hours under the protection of argon;
(2) Hot pressing and sintering:
(i) Placing the sealed die in the step (1) into a hot-pressing sintering furnace, vacuumizing to below 100Pa, heating to 1000-1050 ℃ at a heating rate of 8-12 ℃/min, and preserving heat for 60-90 min, wherein the internal pressure of the sealed die is controlled to be less than 1MPa;
(ii) After the heat preservation in the step (i) is finished, heating to 1270-1350 ℃ at a heating rate of 3-6 ℃/min, and preserving the heat for 50-70 min, wherein the internal pressure of the sealed die is controlled to be less than 1MPa;
(iii) After the heat preservation in the step (ii) is finished, pressurizing to 25-35 MPa for 50-70 min, and always keeping 1270-1350 ℃, wherein the heat preservation and pressure keeping time is controlled to be 60-180 min;
(iv) After the heat preservation and pressure maintaining in the step (iii) are finished, closing the hot-pressed sintering furnace, cooling, then filling argon until the vacuum representation number is-0.06 to-0.08 MPa, and taking out the blank in the die after the temperature in the hot-pressed sintering furnace is reduced to 200 ℃ to obtain a tungsten nickel alloy sintered body;
(3) And (3) performing wire cutting and/or grinding on the tungsten-nickel alloy sintered body obtained in the step (2) to obtain the tungsten-nickel alloy sputtering target material.
16. A tungsten nickel alloy sputtering target, characterized in that it is obtained by the hot pressing method according to any one of claims 1 to 15.
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|---|---|---|---|---|
| AT14157U1 (en) * | 2013-12-20 | 2015-05-15 | Plansee Se | W-Ni-sputtering target |
| CN105239043A (en) * | 2015-10-22 | 2016-01-13 | 厦门映日新材料科技有限公司 | Electrochromic glass tungsten-nickel alloy target and preparation method thereof |
| CN113088909A (en) * | 2021-03-31 | 2021-07-09 | 宁波江丰电子材料股份有限公司 | Nickel-chromium alloy sputtering target material and hot-pressing preparation method thereof |
| CN113549881A (en) * | 2021-05-31 | 2021-10-26 | 洛阳科威钨钼有限公司 | Preparation method of tungsten-nickel alloy target material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT14157U1 (en) * | 2013-12-20 | 2015-05-15 | Plansee Se | W-Ni-sputtering target |
| CN105239043A (en) * | 2015-10-22 | 2016-01-13 | 厦门映日新材料科技有限公司 | Electrochromic glass tungsten-nickel alloy target and preparation method thereof |
| CN113088909A (en) * | 2021-03-31 | 2021-07-09 | 宁波江丰电子材料股份有限公司 | Nickel-chromium alloy sputtering target material and hot-pressing preparation method thereof |
| CN113549881A (en) * | 2021-05-31 | 2021-10-26 | 洛阳科威钨钼有限公司 | Preparation method of tungsten-nickel alloy target material |
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