CN112813397B - Preparation method of molybdenum-sodium alloy plate-shaped target - Google Patents
Preparation method of molybdenum-sodium alloy plate-shaped target Download PDFInfo
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- 229910000528 Na alloy Inorganic materials 0.000 title claims abstract description 118
- QMXBEONRRWKBHZ-UHFFFAOYSA-N [Na][Mo] Chemical compound [Na][Mo] QMXBEONRRWKBHZ-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 63
- 239000010439 graphite Substances 0.000 claims abstract description 63
- 238000005245 sintering Methods 0.000 claims abstract description 57
- 238000010438 heat treatment Methods 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 42
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000003825 pressing Methods 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 22
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 22
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000003754 machining Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000005498 polishing Methods 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000013077 target material Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 9
- 238000009694 cold isostatic pressing Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000004134 energy conservation Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000002490 spark plasma sintering Methods 0.000 description 42
- 229910052799 carbon Inorganic materials 0.000 description 14
- 239000010408 film Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 239000011733 molybdenum Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000007731 hot pressing Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000001513 hot isostatic pressing Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
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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
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- 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
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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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- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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Abstract
The invention discloses a preparation method of a molybdenum-sodium alloy plate-shaped target, which comprises the following steps: firstly, dissolving and uniformly mixing sodium molybdate and a binder with deionized water, then adding molybdenum powder, spraying and granulating to obtain molybdenum-sodium alloy powder, and finally decarburizing the molybdenum-sodium alloy powder; carrying out low-pressure pre-pressing on the molybdenum-sodium alloy powder obtained in the step 1 to obtain an initial pressed compact; placing the initial pressed compact into a graphite mold, then placing the graphite mold into an SPS sintering furnace for pressurizing, and vacuumizing; finally, increasing current to heat up and sinter, releasing pressure and cooling the SPS sintering furnace to obtain a molybdenum-sodium alloy blank; and (3) machining, grinding and polishing the molybdenum-sodium alloy blank to obtain a molybdenum-sodium alloy plate-shaped target finished product. The SPS technology realizes the rapid heating/cooling rate, short sintering time, energy conservation and environmental protection, simple process and low cost, and realizes the short production cycle preparation of the molybdenum-sodium alloy plate-shaped target.
Description
Technical Field
The invention belongs to the technical field of molybdenum alloy preparation methods, and relates to a preparation method of a molybdenum-sodium alloy plate-shaped target.
Background
In recent years, thin film solar cells have been increasingly becoming light due to their high production efficiency, low transportation cost, and efficient material utilizationA development trend of the photovoltaic industry. In thin film solar cells, cuInGaSe 2 (CIGS) thin film solar cells as absorber layers are one of the most promising developments. The structure of the cell is that a molybdenum film is deposited on a soda-lime glass substrate, and then CuInGaSe is deposited on the substrate 2 The absorber layer is attached to or grown on the molybdenum film. The study shows that a small amount of sodium ions in the soda-lime glass substrate penetrate through the molybdenum film to diffuse into CuInGaSe 2 And the absorption layer improves the current carrying density of the absorption layer, thereby improving the energy conversion efficiency of the battery. In industrial production, the Na element content is not controllable because the molybdenum film hinders the diffusion of sodium ions. The research shows that the Na element content can be effectively controlled by changing the molybdenum film into the molybdenum-sodium alloy film, and the Na element is uniformly doped into CuInGaSe 2 An absorbent layer. The molybdenum-sodium alloy film is formed by direct-current magnetron sputtering deposition, and the pure molybdenum target material for preparing the molybdenum back electrode layer is replaced by a molybdenum-sodium alloy plate-shaped target material, so that the molybdenum-sodium alloy film is realized, the operation is simple, and the molybdenum-sodium alloy film is suitable for industrial production.
Therefore, the molybdenum-sodium alloy plate-shaped target with excellent research performance is a precondition for preparing the molybdenum-sodium alloy film. However, in theory, the melting points of molybdenum and sodium differ greatly, the melting point of molybdenum is 2620+ -10deg.C, the melting point of sodium is 98deg.C, and sodium with low melting point is easy to volatilize during sintering, so that Na element content is uncontrollable.
At present, three main methods for preparing molybdenum-sodium alloy plate-shaped targets are as follows: the first is a conventional sintering method, which is not practically feasible, and the Na element content is extremely volatile at the high temperature stage of the sintering process. The second is a vacuum hot-pressing sintering method, and the molybdenum-sodium alloy plate-shaped target prepared by the method has lower relative density. The third is a hot isostatic pressing sintering method, which is a method commonly adopted at home and abroad, and the method can prepare the molybdenum-sodium alloy plate-shaped target material meeting the requirements, but the hot isostatic pressing process is longer, the time period is uncontrollable, and the sintering cost is very high.
Disclosure of Invention
The invention aims to provide a preparation method of a molybdenum-sodium alloy plate-shaped target, which solves the problems of long sintering time and low relative density in the prior art.
The technical scheme adopted by the invention is that the preparation method of the molybdenum-sodium alloy plate-shaped target material comprises the following steps:
firstly, dissolving and uniformly mixing sodium molybdate and a binder with deionized water, then adding molybdenum powder, spraying and granulating to obtain molybdenum-sodium alloy powder, and finally decarburizing the molybdenum-sodium alloy powder, wherein the mass content of sodium molybdate in the molybdenum-sodium alloy powder is 4.21-42.09%, and the balance is molybdenum powder;
step 2, performing low-pressure pre-pressing on the molybdenum-sodium alloy powder obtained in the step 1 to obtain an initial pressed compact;
step 3, placing the initial pressed compact into a graphite mold, then placing the graphite mold into a discharge plasma (SPS) sintering furnace for pressurizing, and vacuumizing; finally, increasing current to heat up and sinter, releasing pressure and cooling the SPS sintering furnace to obtain a molybdenum-sodium alloy blank;
and 4, machining, grinding and polishing the molybdenum-sodium alloy blank to obtain a molybdenum-sodium alloy plate-shaped target finished product.
The invention is also characterized in that:
in the step 3, the SPS sintering furnace is subjected to current increasing, temperature rising, sintering, pressure relief and cooling processes are specifically as follows:
the SPS sintering furnace is firstly heated to 300 ℃ from room temperature at a heating rate of 30-100 ℃/min, then heated to 600 ℃ at a heating rate of 100-200 ℃/min, finally heated to 1000-1200 ℃ at a heating rate of 30-100 ℃/min, and then heat-preserved for 5-20 min; after the heat preservation is finished, the temperature is firstly reduced to 800 ℃ at the cooling rate of 50-200 ℃/min, then reduced to 600 ℃ at the cooling rate of 50-200 ℃/min, and then slowly released, and the furnace is cooled.
In the step 2, the low-pressure pre-pressing adopts a cold isostatic pressing method, and the specific parameters are as follows: pressure of
100MPa-150MPa, and dwell time is 5min-10min.
In the step 4, the molybdenum-sodium alloy plate-shaped target finished product consists of the following components in parts by mass: na element 0.8-8.0%, and Mo element in balance, the mass percentage of the components is 100%.
The mass purity of the molybdenum powder is more than or equal to 99.95 percent, the Fisher particle size of the molybdenum powder is 3.0-4.0 mu m, and the mass purity of the sodium molybdate is more than or equal to 99.0 percent.
The beneficial effects of the invention are as follows:
the preparation method of the molybdenum-sodium alloy plate-shaped target material realizes the rapid heating/cooling rate, short sintering time, energy conservation and environmental protection, simple process and low cost by adopting the SPS technology, and realizes the short production cycle preparation of the molybdenum-sodium alloy plate-shaped target material; the molybdenum-sodium alloy plate-shaped target material obtained by sintering through SPS technology has high density, fine crystal grains and controllable Na element content and structure.
Drawings
FIG. 1 is a scanning electron microscope image of a fracture of a molybdenum-sodium alloy plate-shaped target material obtained by the preparation method of the molybdenum-sodium alloy plate-shaped target material;
fig. 2 is a metallographic structure diagram of a molybdenum-sodium alloy plate-shaped target material obtained by the preparation method of the molybdenum-sodium alloy plate-shaped target material.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
A preparation method of a molybdenum-sodium alloy plate-shaped target material comprises the following steps:
firstly, dissolving and uniformly mixing sodium molybdate and a binder with deionized water, then adding molybdenum powder, uniformly stirring, spraying and granulating to obtain molybdenum-sodium alloy powder, and finally decarburizing the molybdenum-sodium alloy powder by a hydrogen furnace, wherein the mass content of sodium molybdate in the molybdenum-sodium alloy powder is 4.21-42.09%, and the balance is molybdenum powder; the mass purity of the molybdenum powder is more than or equal to 99.95 percent, the Fisher particle size of the molybdenum powder is 3.0-4.0 mu m, and the mass purity of the sodium molybdate is more than or equal to 99.0 percent;
step 2, performing low-pressure pre-pressing on the molybdenum-sodium alloy powder obtained in the step 1 to obtain an initial pressed compact; the specific parameters are as follows: the pressure is 100MPa-150MPa, and the dwell time is 5min-10min;
step 3, placing the initial pressed compact into a high-strength and high-purity graphite mold for Spark Plasma Sintering (SPS), padding graphite paper on the inner ring of the graphite mold, wrapping the graphite mold by adopting a carbon felt, and fixing the periphery of the carbon felt by virtue of a graphite rope; then placing the graphite mold in an SPS sintering furnace for pressurizing, wherein the pressure is 20MPa-80MPa; then vacuumizing the SPS sintering furnace, wherein the vacuum environment can prevent the initial pressed compact of the molybdenum-sodium alloy from being oxidized in the sintering process; when the vacuum degree is lower than 5Pa, starting to increase the current to heat up and sinter, relieve pressure and cool the SPS sintering furnace to obtain a molybdenum-sodium alloy blank; specifically, firstly, the temperature is increased to 300 ℃ from room temperature at a heating rate of 30-100 ℃/min, then the temperature is increased to 600 ℃ at a heating rate of 100-200 ℃/min, finally the temperature is increased to 1000-1200 ℃ at a heating rate of 30-100 ℃/min, and then the temperature is kept for 5-20 min; after the heat preservation is finished, the temperature is firstly reduced to 800 ℃ at the cooling rate of 50-200 ℃/min, then reduced to 600 ℃ at the cooling rate of 50-200 ℃/min, and then slowly released, and the furnace is cooled. The graphite die comprises an upper pressing head, a lower pressing head and a graphite female die.
And 4, machining, grinding and polishing the molybdenum-sodium alloy blank to obtain a molybdenum-sodium alloy plate-shaped target finished product, wherein the molybdenum-sodium alloy plate-shaped target finished product comprises the following components in parts by mass: na element 0.8-8.0%, and Mo element in balance, the mass percentage of the components is 100%.
Through the mode, the preparation method of the molybdenum-sodium alloy plate-shaped target material realizes the rapid heating/cooling rate, short sintering time, energy conservation and environmental protection, simple process and low cost through SPS technology, and realizes the short production cycle preparation of the molybdenum-sodium alloy plate-shaped target material; the molybdenum-sodium alloy plate-shaped target material obtained by SPS technology has high density, fine crystal grains and controllable Na element content and structure. The SPS technology adopted by the invention is carried out simultaneously with the pressurization and the heating of the existing vacuum hot-pressing sintering method, but the heating modes of the SPS technology and the existing vacuum hot-pressing sintering method are completely different; the vacuum hot-pressing sintering method adopts a resistance radiation heating mode to realize sintering, and the temperatures of a graphite die, a sample to be sintered and a vacuum hot-pressing sintering furnace cavity are basically consistent in the whole sintering process, so that the energy consumption is larger in the sintering process. The SPS technology realizes heating by using direct current pulse current, and the main function of the direct current pulse current is to generate high-temperature plasma; therefore, the heat of SPS sintering mainly comes from high-temperature plasma and the Joule heat generated by the mold and the powder, so that the temperature of the sintering cavity is far lower than that of the mold, the temperature rise and heat transfer speed are extremely high, the cooling speed is also high, the production time is greatly shortened, and the production cost is reduced. Compared with hot isostatic pressing, the SPS technology adopted by the invention has the advantages that the sintering temperature is lower, the sintering temperature can be reduced by 100-200 ℃ compared with the hot isostatic pressing, the SPS technology has a unique purifying and activating effect, the gas adsorbed on the surfaces of the molybdenum-sodium alloy powder particles can be eliminated, the surfaces of the powder particles are cleaned, and the sintering capacity of the particles is improved.
Example 1
Step 1, firstly, dissolving and uniformly mixing sodium molybdate and a binder with deionized water, and then adding molybdenum powder, and uniformly stirring, wherein the Fisher particle size of the molybdenum powder is 3.0 mu m; spraying and granulating to obtain molybdenum-sodium alloy powder, decarburizing the molybdenum-sodium alloy powder by a hydrogen furnace, wherein the mass content of sodium molybdate in the molybdenum-sodium alloy powder is 15.78%, and the balance is molybdenum powder;
step 2, performing low-pressure pre-pressing on the molybdenum-sodium alloy powder obtained in the step 1 to obtain an initial pressed compact; the low-pressure pre-pressing pressure is 100MPa, and the pressure maintaining time is 5min;
step 3, placing the initial pressed compact into a high-strength and high-purity graphite mold for Spark Plasma Sintering (SPS), padding graphite paper on the inner ring of the graphite mold, wrapping the graphite mold by adopting a carbon felt, and fixing the periphery of the carbon felt by virtue of a graphite rope; then placing the graphite mold in an SPS sintering furnace to be pressurized to 80MPa; then vacuumizing the SPS sintering furnace, when the vacuum degree is lower than 5Pa, starting to increase the current to heat up and sinter the SPS sintering furnace, firstly heating up to 300 ℃ from room temperature at the heating rate of 80 ℃/min, heating up to 600 ℃ at the heating rate of 100 ℃/min, heating up to 1100 ℃ at the heating rate of 50 ℃/min, and then preserving heat for 10min; after the heat preservation is finished, the temperature is firstly reduced to 800 ℃ at the cooling rate of 50 ℃/min, then reduced to 600 ℃ at the cooling rate of 50 ℃/min, and then slowly released, and the furnace is cooled. The graphite die comprises an upper pressing head, a lower pressing head and a graphite female die.
And 4, machining, grinding and polishing the molybdenum-sodium alloy blank to obtain a molybdenum-sodium alloy plate-shaped target finished product. Fig. 1 is a scanning electron microscope image of a cross section of a finished molybdenum-sodium alloy plate-shaped target prepared in this embodiment, and it can be seen that the molybdenum-sodium alloy plate-shaped target has uniform particles, compact arrangement and fewer hole defects. The detection shows that the relative density of the finished product of the molybdenum-sodium alloy plate-shaped target material prepared in the embodiment is 99.20%, and the grain size is about 30 mu m. Fig. 2 is a metallographic structure diagram of a molybdenum-sodium alloy plate-shaped target product prepared in this embodiment, and it can be seen that the crystal grains are fine, the structure distribution is uniform, and the crystal grains are equiaxed.
Example 2
Step 1, firstly, dissolving and uniformly mixing sodium molybdate and a binder with deionized water, and then adding molybdenum powder, and uniformly stirring, wherein the Fisher particle size of the molybdenum powder is 3.0 mu m; spraying and granulating to obtain molybdenum-sodium alloy powder, decarburizing the molybdenum-sodium alloy powder by a hydrogen furnace, wherein the mass content of sodium molybdate in the molybdenum-sodium alloy powder is 15.78%, and the balance is molybdenum powder;
step 2, performing low-pressure pre-pressing on the molybdenum-sodium alloy powder obtained in the step 1 to obtain an initial pressed compact; the low-pressure pre-pressing pressure is 130MPa, and the pressure maintaining time is 8min;
step 3, placing the initial pressed compact into a high-strength and high-purity graphite mold for Spark Plasma Sintering (SPS), padding graphite paper on the inner ring of the graphite mold, wrapping the graphite mold by adopting a carbon felt, and fixing the periphery of the carbon felt by virtue of a graphite rope; then placing the graphite mold in an SPS sintering furnace to be pressurized to 50MPa; then vacuumizing the SPS sintering furnace, when the vacuum degree is lower than 5Pa, starting to increase the current to heat up and sinter the SPS sintering furnace, firstly heating up to 300 ℃ from room temperature at a heating rate of 30 ℃/min, heating up to 600 ℃ at a heating rate of 120 ℃/min, heating up to 1000 ℃ at a heating rate of 30 ℃/min, and then preserving heat for 10min; after the heat preservation is finished, the temperature is firstly reduced to 800 ℃ at the cooling rate of 50 ℃/min, then reduced to 600 ℃ at the cooling rate of 50 ℃/min, and then slowly released, and the furnace is cooled. The graphite die comprises an upper pressing head, a lower pressing head and a graphite female die.
And 4, machining, grinding and polishing the molybdenum-sodium alloy blank to obtain a molybdenum-sodium alloy plate-shaped target finished product. The molybdenum-sodium alloy plate-shaped target finished product prepared by the embodiment has uniform particles, compact arrangement and fewer hole defects. The relative density of the finished molybdenum-sodium alloy plate-shaped target product prepared in the embodiment is 98.90 percent through detection, and the grain size is about 30 mu m. The molybdenum-sodium alloy plate-shaped target finished product prepared by the embodiment has fine grains, uniform tissue distribution and equiaxial grains.
Example 3
Step 1, firstly, dissolving and uniformly mixing sodium molybdate and a binder with deionized water, and then adding molybdenum powder, and uniformly stirring, wherein the Fisher particle size of the molybdenum powder is 3.2 mu m; spraying and granulating to obtain molybdenum-sodium alloy powder, decarburizing the molybdenum-sodium alloy powder by a hydrogen furnace, wherein the mass content of sodium molybdate in the molybdenum-sodium alloy powder is 4.21%, and the balance is molybdenum powder;
step 2, performing low-pressure pre-pressing on the molybdenum-sodium alloy powder obtained in the step 1 to obtain an initial pressed compact; the low-pressure pre-pressing pressure is 130MPa, and the pressure maintaining time is 8min;
step 3, placing the initial pressed compact into a high-strength and high-purity graphite mold for Spark Plasma Sintering (SPS), padding graphite paper on the inner ring of the graphite mold, wrapping the graphite mold by adopting a carbon felt, and fixing the periphery of the carbon felt by virtue of a graphite rope; then placing the graphite mold in an SPS sintering furnace to be pressurized to 30MPa; then vacuumizing the SPS sintering furnace, when the vacuum degree is lower than 5Pa, starting to increase the current to heat up and sinter the SPS sintering furnace, firstly heating up to 300 ℃ from room temperature at a heating rate of 60 ℃/min, heating up to 600 ℃ at a heating rate of 120 ℃/min, heating up to 1000 ℃ at a heating rate of 60 ℃/min, and then preserving heat for 5min; after the heat preservation is finished, the temperature is firstly reduced to 800 ℃ at the cooling rate of 100 ℃/min, then reduced to 600 ℃ at the cooling rate of 100 ℃/min, and then slowly released, and the furnace is cooled. The graphite die comprises an upper pressing head, a lower pressing head and a graphite female die.
And 4, machining, grinding and polishing the molybdenum-sodium alloy blank to obtain a molybdenum-sodium alloy plate-shaped target finished product. The molybdenum-sodium alloy plate-shaped target finished product prepared by the embodiment has uniform particles, compact arrangement and fewer hole defects. The detection shows that the relative density of the finished product of the molybdenum-sodium alloy plate-shaped target material prepared in the embodiment is 98.60%, and the grain size is about 30 mu m. The molybdenum-sodium alloy plate-shaped target finished product prepared by the embodiment has fine grains, uniform tissue distribution and equiaxial grains.
Example 4
Step 1, firstly, dissolving and uniformly mixing sodium molybdate and a binder with deionized water, and then adding molybdenum powder, and uniformly stirring, wherein the Fisher particle size of the molybdenum powder is 3.5 mu m; spraying and granulating to obtain molybdenum-sodium alloy powder, decarburizing the molybdenum-sodium alloy powder by a hydrogen furnace, wherein the mass content of sodium molybdate in the molybdenum-sodium alloy powder is 10.52%, and the balance is molybdenum powder;
step 2, performing low-pressure pre-pressing on the molybdenum-sodium alloy powder obtained in the step 1 to obtain an initial pressed compact; the low-pressure pre-pressing pressure is 140MPa, and the pressure maintaining time is 6min;
step 3, placing the initial pressed compact into a high-strength and high-purity graphite mold for Spark Plasma Sintering (SPS), padding graphite paper on the inner ring of the graphite mold, wrapping the graphite mold by adopting a carbon felt, and fixing the periphery of the carbon felt by virtue of a graphite rope; then placing the graphite mold in an SPS sintering furnace to be pressurized to 60MPa; then vacuumizing the SPS sintering furnace, when the vacuum degree is lower than 5Pa, starting to increase the current to heat up and sinter the SPS sintering furnace, firstly heating up to 300 ℃ from room temperature at the heating rate of 80 ℃/min, heating up to 600 ℃ at the heating rate of 140 ℃/min, finally heating up to 1100 ℃ at the heating rate of 50 ℃/min, and then preserving heat for 8min; after the heat preservation is finished, the temperature is firstly reduced to 800 ℃ at the cooling rate of 100 ℃/min, then reduced to 600 ℃ at the cooling rate of 100 ℃/min, and then slowly released, and the furnace is cooled. The graphite die comprises an upper pressing head, a lower pressing head and a graphite female die.
And 4, machining, grinding and polishing the molybdenum-sodium alloy blank to obtain a molybdenum-sodium alloy plate-shaped target finished product. The molybdenum-sodium alloy plate-shaped target finished product prepared by the embodiment has uniform particles, compact arrangement and fewer hole defects. The detection shows that the relative density of the finished product of the molybdenum-sodium alloy plate-shaped target material prepared in the embodiment is 99.00%, and the grain size is about 30 mu m. The molybdenum-sodium alloy plate-shaped target finished product prepared by the embodiment has fine grains, uniform tissue distribution and equiaxial grains.
Example 5
Step 1, firstly, dissolving and uniformly mixing sodium molybdate and a binder with deionized water, and then adding molybdenum powder, and uniformly stirring, wherein the Fisher particle size of the molybdenum powder is 4 mu m; spraying and granulating to obtain molybdenum-sodium alloy powder, decarburizing the molybdenum-sodium alloy powder by a hydrogen furnace, wherein the mass content of sodium molybdate in the molybdenum-sodium alloy powder is 42.09%, and the balance is molybdenum powder;
step 2, performing low-pressure pre-pressing on the molybdenum-sodium alloy powder obtained in the step 1 to obtain an initial pressed compact; the low-pressure pre-pressing pressure is 140MPa, and the pressure maintaining time is 8min;
step 3, placing the initial pressed compact into a high-strength and high-purity graphite mold for Spark Plasma Sintering (SPS), padding graphite paper on the inner ring of the graphite mold, wrapping the graphite mold by adopting a carbon felt, and fixing the periphery of the carbon felt by virtue of a graphite rope; then placing the graphite mold in an SPS sintering furnace to be pressurized to 20MPa; then vacuumizing the SPS sintering furnace, when the vacuum degree is lower than 5Pa, starting to increase the current to heat up and sinter the SPS sintering furnace, firstly heating up to 300 ℃ from room temperature at a heating rate of 100 ℃/min, heating up to 600 ℃ at a heating rate of 160 ℃/min, heating up to 1200 ℃ at a heating rate of 100 ℃/min, and then preserving heat for 20min; after the heat preservation is finished, the temperature is firstly reduced to 800 ℃ at the cooling rate of 200 ℃/min, then reduced to 600 ℃ at the cooling rate of 200 ℃/min, and then slowly released, and the furnace is cooled. The graphite die comprises an upper pressing head, a lower pressing head and a graphite female die.
And 4, machining, grinding and polishing the molybdenum-sodium alloy blank to obtain a molybdenum-sodium alloy plate-shaped target finished product. The molybdenum-sodium alloy plate-shaped target finished product prepared by the embodiment has uniform particles, compact arrangement and fewer hole defects. The relative density of the finished molybdenum-sodium alloy plate-shaped target product prepared in the embodiment is 98.2 percent through detection, and the grain size is about 30 mu m. The molybdenum-sodium alloy plate-shaped target finished product prepared by the embodiment has fine grains, uniform tissue distribution and equiaxial grains.
Example 6
Step 1, firstly, dissolving and uniformly mixing sodium molybdate and a binder with deionized water, and then adding molybdenum powder, and uniformly stirring, wherein the Fisher particle size of the molybdenum powder is 4 mu m; spraying and granulating to obtain molybdenum-sodium alloy powder, decarburizing the molybdenum-sodium alloy powder by a hydrogen furnace, wherein the mass content of sodium molybdate in the molybdenum-sodium alloy powder is 42.09%, and the balance is molybdenum powder;
step 2, performing low-pressure pre-pressing on the molybdenum-sodium alloy powder obtained in the step 1 to obtain an initial pressed compact; the low-pressure pre-pressing pressure is 100MPa, and the pressure maintaining time is 8min;
step 3, placing the initial pressed compact into a high-strength and high-purity graphite mold for Spark Plasma Sintering (SPS), padding graphite paper on the inner ring of the graphite mold, wrapping the graphite mold by adopting a carbon felt, and fixing the periphery of the carbon felt by virtue of a graphite rope; then placing the graphite mold in an SPS sintering furnace to be pressurized to 20MPa; then vacuumizing the SPS sintering furnace, when the vacuum degree is lower than 5Pa, starting to increase the current to heat up and sinter the SPS sintering furnace, firstly heating up to 300 ℃ from room temperature at a heating rate of 100 ℃/min, heating up to 600 ℃ at a heating rate of 200 ℃/min, finally heating up to 1200 ℃ at a heating rate of 100 ℃/min, and then preserving heat for 15min; after the heat preservation is finished, the temperature is firstly reduced to 800 ℃ at the cooling rate of 100 ℃/min, then reduced to 600 ℃ at the cooling rate of 100 ℃/min, and then slowly released, and the furnace is cooled. The graphite die comprises an upper pressing head, a lower pressing head and a graphite female die.
And 4, machining, grinding and polishing the molybdenum-sodium alloy blank to obtain a molybdenum-sodium alloy plate-shaped target finished product. The molybdenum-sodium alloy plate-shaped target finished product prepared by the embodiment has uniform particles, compact arrangement and fewer hole defects. The relative density of the finished molybdenum-sodium alloy plate-shaped target product prepared in the embodiment is 98.0 percent through detection, and the grain size is about 30 mu m. The molybdenum-sodium alloy plate-shaped target finished product prepared by the embodiment has fine grains, uniform tissue distribution and equiaxial grains.
Claims (3)
1. The preparation method of the molybdenum-sodium alloy plate-shaped target material is characterized by comprising the following steps of:
firstly, dissolving and uniformly mixing sodium molybdate and a binder with deionized water, then adding molybdenum powder, spraying and granulating to obtain molybdenum-sodium alloy powder, and finally decarburizing the molybdenum-sodium alloy powder, wherein the mass content of sodium molybdate in the molybdenum-sodium alloy powder is 4.21-42.09%, and the balance is molybdenum powder;
step 2, carrying out low-pressure pre-pressing on the molybdenum-sodium alloy powder obtained in the step 1 to obtain an initial pressed compact;
step 3, placing the initial pressed compact into a graphite mold, then placing the graphite mold into an SPS sintering furnace for pressurizing, and vacuumizing; finally, increasing current, heating, sintering, releasing pressure and cooling the SPS sintering furnace to obtain a molybdenum-sodium alloy blank;
step 4, machining, grinding and polishing the molybdenum-sodium alloy blank to obtain a molybdenum-sodium alloy plate-shaped target finished product;
the low-pressure pre-pressing in the step 2 adopts a cold isostatic pressing method, and the specific parameters are as follows: the pressure is 100MPa-150MPa, and the dwell time is 5min-10min;
in the step 3, the process of increasing current, heating, sintering, releasing pressure and cooling the SPS sintering furnace comprises the following steps:
the SPS sintering furnace is firstly heated to 300 ℃ from room temperature at a heating rate of 30-100 ℃/min, then heated to 600 ℃ at a heating rate of 100-200 ℃/min, finally heated to 1000-1200 ℃ at a heating rate of 30-100 ℃/min, and then heat-preserved for 5-20 min; after the heat preservation is finished, the temperature is firstly reduced to 800 ℃ at the cooling rate of 50-200 ℃/min, then reduced to 600 ℃ at the cooling rate of 50-200 ℃/min, and then slowly released, and the furnace is cooled.
2. The method for preparing the molybdenum-sodium alloy plate-shaped target according to claim 1, wherein the molybdenum-sodium alloy plate-shaped target finished product in the step 4 comprises the following components in mass: na element 0.8-8.0%, and Mo element in balance, the mass percentage of the components is 100%.
3. The method for preparing a molybdenum-sodium alloy plate-shaped target according to claim 1, wherein the mass purity of the molybdenum powder is 99.95% or more, the fermi particle size of the molybdenum powder is 3.0 μm-4.0 μm, and the mass purity of the sodium molybdate is 99.0% or more.
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