CN112813397A - Preparation method of molybdenum-sodium alloy plate-shaped target material - Google Patents
Preparation method of molybdenum-sodium alloy plate-shaped target material 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
- 239000013077 target material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 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
- 238000010438 heat treatment Methods 0.000 claims abstract description 60
- 238000005245 sintering Methods 0.000 claims abstract description 59
- 239000000843 powder Substances 0.000 claims abstract description 42
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000001816 cooling Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 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
- 238000003825 pressing Methods 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 238000005261 decarburization Methods 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
- 238000005469 granulation Methods 0.000 claims abstract description 10
- 230000003179 granulation Effects 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
- 239000007921 spray Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 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 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000002490 spark plasma sintering Methods 0.000 description 36
- 229910052799 carbon Inorganic materials 0.000 description 14
- 239000013078 crystal Substances 0.000 description 14
- 229910052750 molybdenum Inorganic materials 0.000 description 9
- 239000011733 molybdenum Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 239000010408 film Substances 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
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001513 hot isostatic pressing Methods 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000010409 thin film Substances 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
- 238000011160 research Methods 0.000 description 3
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 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
- 239000000758 substrate Substances 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 239000006096 absorbing agent 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
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Classifications
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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
-
- 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
-
- 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
Abstract
The invention discloses a preparation method of a molybdenum-sodium alloy plate-shaped target material, which comprises the following steps: dissolving sodium molybdate and a binder in deionized water, mixing uniformly, adding molybdenum powder, performing spray granulation to obtain molybdenum-sodium alloy powder, and finally performing decarburization treatment on the molybdenum-sodium alloy powder; performing low-pressure pre-pressing on the molybdenum-sodium alloy powder obtained in the step 1 to obtain an initial pressed blank; placing the initial pressed compact in a graphite mold, then placing the graphite mold in an SPS sintering furnace for pressurization, and vacuumizing; finally, increasing current to the SPS sintering furnace, heating up, sintering, releasing pressure and cooling to obtain a molybdenum-sodium alloy blank; and machining, grinding and polishing the molybdenum-sodium alloy blank to obtain a molybdenum-sodium alloy plate-shaped target finished product. The method has the advantages of high heating/cooling rate, short sintering time, energy conservation, environmental protection, simple process and low cost by the SPS technology, and realizes the short production period preparation of the molybdenum-sodium alloy plate-shaped target material.
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 material.
Background
In recent years, thin film solar cells are gradually becoming a development trend of the photovoltaic industry due to higher production efficiency, low transportation cost and high material utilization rate. In thin film solar cells, CuInGaSe2(CIGS) thin film solar cells as absorber layers are one of the most promising developments. The structure of the battery is that a layer of molybdenum film is deposited on a soda-lime glass substrate, and then CuInGaSe is added2The absorption layer is attached to or grown on the molybdenum film. Research shows that a small amount of sodium ions in the soda-lime glass substrate penetrate through the molybdenum film and diffuse to CuInGaSe2And 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 thin film hinders the diffusion of sodium ions. Researches show that the content of Na element can be effectively controlled by replacing the molybdenum film with the molybdenum-sodium alloy film, and the Na element is uniformly doped into CuInGaSe2An absorption layer. The molybdenum-sodium alloy film is formed by direct-current magnetron sputtering deposition, and the preparation method can be realized by replacing the pure molybdenum target material for preparing the molybdenum back electrode layer with the molybdenum-sodium alloy plate-shaped target material, is simple to operate and is suitable for industrial production.
Therefore, the research on the molybdenum-sodium alloy plate-shaped target material with excellent performance is a precondition for preparing the molybdenum-sodium alloy film. However, theoretically, the melting points of molybdenum and sodium are greatly different, the melting point of molybdenum is 2620 +/-10 ℃, the melting point of sodium is 98 ℃, and sodium with a low melting point is easy to volatilize in the sintering process, so that the content of Na element is uncontrollable.
At present, the preparation methods of the molybdenum-sodium alloy plate-shaped target mainly include three methods: the first is conventional sintering, which is not practical and the Na content is very volatile at the high temperature stage of the sintering process. The second method is a vacuum hot-pressing sintering method, and the molybdenum-sodium alloy plate-shaped target material prepared by the method has lower relative density. The third method is a hot isostatic pressing sintering method, which is a method commonly adopted at home and abroad, and can prepare the molybdenum-sodium alloy plate-shaped target material meeting the requirements, but the hot isostatic pressing process is long, 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 material, 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:
step 1, dissolving sodium molybdate and a binder with deionized water, uniformly mixing, adding molybdenum powder, performing spray granulation to obtain molybdenum-sodium alloy powder, and finally performing decarburization treatment on 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 blank;
step 3, placing the initial pressed compact in a graphite mold, then placing the graphite mold in a discharge plasma (SPS) sintering furnace for pressurization, and vacuumizing; finally, increasing current to the SPS sintering furnace, heating up, sintering, releasing pressure and cooling to obtain a molybdenum-sodium alloy blank;
and 4, machining the molybdenum-sodium alloy blank, and grinding and polishing to obtain a molybdenum-sodium alloy plate-shaped target finished product.
The invention is also characterized in that:
in the step 3, the processes of increasing the current, heating up, sintering, releasing the pressure and cooling the SPS sintering furnace are specifically as follows:
raising the temperature of an SPS sintering furnace from room temperature to 300 ℃ at the temperature raising rate of 30-100 ℃/min, raising the temperature to 600 ℃ at the temperature raising rate of 100-200 ℃/min, raising the temperature to 1000-1200 ℃ at the temperature raising rate of 30-100 ℃/min, and then preserving the temperature for 5-20 min; after the heat preservation is finished, the temperature is reduced to 800 ℃ at the cooling rate of 50-200 ℃/min, then is reduced to 600 ℃ at the cooling rate of 50-200 ℃/min, and then is slowly released and is cooled along with the furnace.
And 2, cold isostatic pressing is adopted for low-pressure pre-pressing, and the specific parameters are as follows: pressure of
100MPa-150MPa, and the pressure maintaining time is 5min-10 min.
The finished product of the molybdenum-sodium alloy plate-shaped target material in the step 4 comprises the following components in parts by mass: 0.8 to 8.0 percent of Na element and the balance of Mo element, wherein the mass percentage of the components is 100 percent.
The mass purity of the molybdenum powder is more than or equal to 99.95 percent, the Fisher-Tropsch 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 invention has the beneficial effects that:
according to the preparation method of the molybdenum-sodium alloy plate-shaped target material, the heating/cooling rate is high, the sintering time is short, the energy is saved, the environment is protected, the process is simple, the cost is low, and the preparation of the molybdenum-sodium alloy plate-shaped target material in a short production period is realized through the SPS technology; the molybdenum-sodium alloy plate-shaped target material obtained by sintering through the 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 target obtained by the preparation method of the molybdenum-sodium alloy plate target of the invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
A preparation method of a molybdenum-sodium alloy plate-shaped target material comprises the following steps:
step 1, dissolving sodium molybdate and a binder with deionized water, uniformly mixing, adding molybdenum powder, uniformly stirring, performing spray granulation to obtain molybdenum-sodium alloy powder, and finally performing decarburization treatment on the molybdenum-sodium alloy powder by using 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 molybdenum powder has the mass purity of more than or equal to 99.95 percent, the Fisher-Tropsch particle size of 3.0-4.0 mu m, and the sodium molybdate has the mass purity of 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 blank; the specific parameters are as follows: the pressure is 100MPa-150MPa, and the pressure maintaining time is 5min-10 min;
step 3, placing the initial pressed compact in a high-strength and high-purity graphite mold for Spark Plasma Sintering (SPS), filling graphite paper in the graphite mold, wrapping the graphite mold by using a carbon felt, and fixing the periphery of the carbon felt by using a graphite rope; then placing the graphite mold in an SPS sintering furnace for pressurization, wherein the pressure is 20MPa-80 MPa; then, vacuumizing the SPS sintering furnace, wherein the vacuum environment can prevent the molybdenum-sodium alloy initial compact from being oxidized in the sintering process; when the vacuum degree is lower than 5Pa, increasing current to the SPS sintering furnace, heating up, sintering, releasing pressure and cooling to obtain a molybdenum-sodium alloy blank; specifically, the temperature is increased from room temperature to 300 ℃ at the heating rate of 30-100 ℃/min, then increased to 600 ℃ at the heating rate of 100-200 ℃/min, finally increased to 1000-1200 ℃ at the heating rate of 30-100 ℃/min, and then the temperature is maintained for 5-20 min; after the heat preservation is finished, the temperature is reduced to 800 ℃ at the cooling rate of 50-200 ℃/min, then is reduced to 600 ℃ at the cooling rate of 50-200 ℃/min, and then is slowly released and is cooled along with the furnace. The graphite mold comprises an upper pressure head, a lower pressure head and a graphite female mold.
And 4, machining the molybdenum-sodium alloy blank, grinding and polishing 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: 0.8 to 8.0 percent of Na element and the balance of Mo element, wherein the mass percentage of the components is 100 percent.
Through the way, the preparation method of the molybdenum-sodium alloy plate-shaped target material realizes high heating/cooling rate, short sintering time, energy conservation and environmental protection, simple process and low cost through the SPS technology, and realizes the preparation of the molybdenum-sodium alloy plate-shaped target material in a short production period; the molybdenum-sodium alloy plate-shaped target material obtained by the SPS technology has high density, fine crystal grains and controllable Na element content and structure. The SPS technology adopted by the invention and the existing vacuum hot pressing sintering method are carried out simultaneously by pressurizing and heating, but the heating modes of the SPS technology and the heating method are completely different; the vacuum hot-pressing sintering method is to realize sintering by adopting a resistance radiation heating mode, and the temperature of the graphite mold, a sample to be sintered and a vacuum hot-pressing sintering furnace cavity is basically consistent in the whole sintering process, so that the energy consumption is larger in the sintering process. The SPS technology utilizes direct current pulse current to realize heating, and the direct current pulse current mainly has the function of generating high-temperature plasma; therefore, the heat of SPS sintering mainly comes from high-temperature plasma and Joule heat generated by the die and the powder, so that the temperature of the sintering cavity is far lower than that of the die, the heating and heat transfer speeds are extremely high, the cooling speed is 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, meanwhile, the SPS technology has unique purifying and activating effects, can eliminate gas adsorbed on the surfaces of molybdenum-sodium alloy powder particles, cleans the surfaces of the powder particles and improves the sintering capacity of the particles.
Example 1
Step 1, dissolving sodium molybdate and a binder by deionized water, mixing uniformly, adding molybdenum powder, and stirring uniformly, wherein the Fisher particle size of the molybdenum powder is 3.0 mu m; carrying out spray granulation to obtain molybdenum-sodium alloy powder, and finally carrying out decarburization treatment on the molybdenum-sodium alloy powder by using 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 blank; pre-pressing at low pressure of 100MPa for 5 min;
step 3, placing the initial pressed compact in a high-strength and high-purity graphite mold for Spark Plasma Sintering (SPS), filling graphite paper in the graphite mold, wrapping the graphite mold by using a carbon felt, and fixing the periphery of the carbon felt by using a graphite rope; then placing the graphite mold in an SPS sintering furnace, and pressurizing to 80 MPa; then vacuumizing the SPS sintering furnace, starting to increase current for heating and sintering when the vacuum degree is lower than 5Pa, heating from room temperature to 300 ℃ at the heating rate of 80 ℃/min, then heating to 600 ℃ at the heating rate of 100 ℃/min, finally heating to 1100 ℃ at the heating rate of 50 ℃/min, and then preserving heat for 10 min; after the heat preservation is finished, the temperature is reduced to 800 ℃ at the cooling rate of 50 ℃/min, then the temperature is reduced to 600 ℃ at the cooling rate of 50 ℃/min, and then the pressure is slowly released, and the furnace is cooled. The graphite mold comprises an upper pressure head, a lower pressure head and a graphite female mold.
And 4, machining the molybdenum-sodium alloy blank, and grinding and polishing 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 product of the molybdenum-sodium alloy plate-shaped target material prepared in this embodiment, and it can be seen that particles of the molybdenum-sodium alloy plate-shaped target material are uniform and closely arranged, and the defects of holes are few. Through detection, 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 μm. Fig. 2 is a metallographic structure diagram of a finished product of the molybdenum-sodium alloy plate-shaped target material prepared in this embodiment, and it can be seen that crystal grains are fine, the structure distribution is uniform, and the crystal grains are equiaxial.
Example 2
Step 1, dissolving sodium molybdate and a binder by deionized water, mixing uniformly, adding molybdenum powder, and stirring uniformly, wherein the Fisher particle size of the molybdenum powder is 3.0 mu m; carrying out spray granulation to obtain molybdenum-sodium alloy powder, and finally carrying out decarburization treatment on the molybdenum-sodium alloy powder by using 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 blank; the low-pressure pre-compression pressure is 130MPa, and the pressure maintaining time is 8 min;
step 3, placing the initial pressed compact in a high-strength and high-purity graphite mold for Spark Plasma Sintering (SPS), filling graphite paper in the graphite mold, wrapping the graphite mold by using a carbon felt, and fixing the periphery of the carbon felt by using a graphite rope; then placing the graphite mold in an SPS sintering furnace, and pressurizing to 50 MPa; then vacuumizing the SPS sintering furnace, starting to increase current for heating and sintering when the vacuum degree is lower than 5Pa, heating from room temperature to 300 ℃ at the heating rate of 30 ℃/min, then heating to 600 ℃ at the heating rate of 120 ℃/min, finally heating to 1000 ℃ at the heating rate of 30 ℃/min, and then preserving heat for 10 min; after the heat preservation is finished, the temperature is reduced to 800 ℃ at the cooling rate of 50 ℃/min, then the temperature is reduced to 600 ℃ at the cooling rate of 50 ℃/min, and then the pressure is slowly released, and the furnace is cooled. The graphite mold comprises an upper pressure head, a lower pressure head and a graphite female mold.
And 4, machining the molybdenum-sodium alloy blank, and grinding and polishing to obtain a molybdenum-sodium alloy plate-shaped target finished product. The finished product of the molybdenum-sodium alloy plate-shaped target material prepared by the embodiment has uniform particles, tight arrangement and less hole defects. Through detection, the relative density of the finished product of the molybdenum-sodium alloy plate-shaped target material prepared by the embodiment is 98.90%, and the grain size is about 30 μm. The finished product of the molybdenum-sodium alloy plate-shaped target material prepared by the embodiment has fine crystal grains, uniform tissue distribution and equiaxial crystal grains.
Example 3
Step 1, dissolving sodium molybdate and a binder by deionized water, mixing uniformly, adding molybdenum powder, and stirring uniformly, wherein the Fisher particle size of the molybdenum powder is 3.2 mu m; carrying out spray granulation to obtain molybdenum-sodium alloy powder, and finally carrying out decarburization treatment on the molybdenum-sodium alloy powder by using 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 blank; the low-pressure pre-compression pressure is 130MPa, and the pressure maintaining time is 8 min;
step 3, placing the initial pressed compact in a high-strength and high-purity graphite mold for Spark Plasma Sintering (SPS), filling graphite paper in the graphite mold, wrapping the graphite mold by using a carbon felt, and fixing the periphery of the carbon felt by using a graphite rope; then placing the graphite mold in an SPS sintering furnace, and pressurizing to 30 MPa; then vacuumizing the SPS sintering furnace, starting to increase current for heating and sintering when the vacuum degree is lower than 5Pa, heating from room temperature to 300 ℃ at the heating rate of 60 ℃/min, then heating to 600 ℃ at the heating rate of 120 ℃/min, finally heating to 1000 ℃ at the heating rate of 60 ℃/min, and then preserving heat for 5 min; after the heat preservation is finished, the temperature is reduced to 800 ℃ at the cooling rate of 100 ℃/min, then the temperature is reduced to 600 ℃ at the cooling rate of 100 ℃/min, and then the pressure is slowly released, and the furnace is cooled. The graphite mold comprises an upper pressure head, a lower pressure head and a graphite female mold.
And 4, machining the molybdenum-sodium alloy blank, and grinding and polishing to obtain a molybdenum-sodium alloy plate-shaped target finished product. The finished product of the molybdenum-sodium alloy plate-shaped target material prepared by the embodiment has uniform particles, tight arrangement and less hole defects. Through detection, 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 μm. The finished product of the molybdenum-sodium alloy plate-shaped target material prepared by the embodiment has fine crystal grains, uniform tissue distribution and equiaxial crystal grains.
Example 4
Step 1, dissolving sodium molybdate and a binder by deionized water, mixing uniformly, adding molybdenum powder, and stirring uniformly, wherein the Fisher particle size of the molybdenum powder is 3.5 mu m; carrying out spray granulation to obtain molybdenum-sodium alloy powder, and finally carrying out decarburization treatment on the molybdenum-sodium alloy powder by using a hydrogen furnace, wherein the mass content of sodium molybdate in the molybdenum-sodium alloy powder is 10.52 percent, 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 blank; the low-pressure pre-pressing pressure is 140MPa, and the pressure maintaining time is 6 min;
step 3, placing the initial pressed compact in a high-strength and high-purity graphite mold for Spark Plasma Sintering (SPS), filling graphite paper in the graphite mold, wrapping the graphite mold by using a carbon felt, and fixing the periphery of the carbon felt by using a graphite rope; then placing the graphite mold in an SPS sintering furnace, and pressurizing to 60 MPa; then vacuumizing the SPS sintering furnace, starting to increase current for heating and sintering when the vacuum degree is lower than 5Pa, heating from room temperature to 300 ℃ at the heating rate of 80 ℃/min, then heating to 600 ℃ at the heating rate of 140 ℃/min, finally heating to 1100 ℃ at the heating rate of 50 ℃/min, and then preserving heat for 8 min; after the heat preservation is finished, the temperature is reduced to 800 ℃ at the cooling rate of 100 ℃/min, then the temperature is reduced to 600 ℃ at the cooling rate of 100 ℃/min, and then the pressure is slowly released, and the furnace is cooled. The graphite mold comprises an upper pressure head, a lower pressure head and a graphite female mold.
And 4, machining the molybdenum-sodium alloy blank, and grinding and polishing to obtain a molybdenum-sodium alloy plate-shaped target finished product. The finished product of the molybdenum-sodium alloy plate-shaped target material prepared by the embodiment has uniform particles, tight arrangement and less hole defects. Through detection, the relative density of the finished product of the molybdenum-sodium alloy plate-shaped target material prepared by the embodiment is 99.00%, and the grain size is about 30 μm. The finished product of the molybdenum-sodium alloy plate-shaped target material prepared by the embodiment has fine crystal grains, uniform tissue distribution and equiaxial crystal grains.
Example 5
Step 1, dissolving sodium molybdate and a binder by deionized water, mixing uniformly, adding molybdenum powder, and stirring uniformly, wherein the Fisher particle size of the molybdenum powder is 4 mu m; carrying out spray granulation to obtain molybdenum-sodium alloy powder, and finally carrying out decarburization treatment on the molybdenum-sodium alloy powder by using 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 blank; the low-pressure pre-pressing pressure is 140MPa, and the pressure maintaining time is 8 min;
step 3, placing the initial pressed compact in a high-strength and high-purity graphite mold for Spark Plasma Sintering (SPS), filling graphite paper in the graphite mold, wrapping the graphite mold by using a carbon felt, and fixing the periphery of the carbon felt by using a graphite rope; then placing the graphite mold in an SPS sintering furnace, and pressurizing for 20 MPa; then vacuumizing the SPS sintering furnace, starting to increase current for heating and sintering when the vacuum degree is lower than 5Pa, heating from room temperature to 300 ℃ at the heating rate of 100 ℃/min, then heating to 600 ℃ at the heating rate of 160 ℃/min, finally heating to 1200 ℃ at the heating rate of 100 ℃/min, and then preserving heat for 20 min; after the heat preservation is finished, the temperature is reduced to 800 ℃ at the cooling rate of 200 ℃/min, then the temperature is reduced to 600 ℃ at the cooling rate of 200 ℃/min, and then the pressure is slowly released, and the furnace is cooled. The graphite mold comprises an upper pressure head, a lower pressure head and a graphite female mold.
And 4, machining the molybdenum-sodium alloy blank, and grinding and polishing to obtain a molybdenum-sodium alloy plate-shaped target finished product. The finished product of the molybdenum-sodium alloy plate-shaped target material prepared by the embodiment has uniform particles, tight arrangement and less hole defects. Through detection, the relative density of the finished product of the molybdenum-sodium alloy plate-shaped target material prepared by the embodiment is 98.2%, and the grain size is about 30 μm. The finished product of the molybdenum-sodium alloy plate-shaped target material prepared by the embodiment has fine crystal grains, uniform tissue distribution and equiaxial crystal grains.
Example 6
Step 1, dissolving sodium molybdate and a binder by deionized water, mixing uniformly, adding molybdenum powder, and stirring uniformly, wherein the Fisher particle size of the molybdenum powder is 4 mu m; carrying out spray granulation to obtain molybdenum-sodium alloy powder, and finally carrying out decarburization treatment on the molybdenum-sodium alloy powder by using 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 blank; the low-pressure pre-pressing pressure is 100MPa, and the pressure maintaining time is 8 min;
step 3, placing the initial pressed compact in a high-strength and high-purity graphite mold for Spark Plasma Sintering (SPS), filling graphite paper in the graphite mold, wrapping the graphite mold by using a carbon felt, and fixing the periphery of the carbon felt by using a graphite rope; then placing the graphite mold in an SPS sintering furnace, and pressurizing for 20 MPa; then vacuumizing the SPS sintering furnace, starting to increase current for heating and sintering when the vacuum degree is lower than 5Pa, heating from room temperature to 300 ℃ at the heating rate of 100 ℃/min, then heating to 600 ℃ at the heating rate of 200 ℃/min, finally heating to 1200 ℃ at the heating rate of 100 ℃/min, and then preserving heat for 15 min; after the heat preservation is finished, the temperature is reduced to 800 ℃ at the cooling rate of 100 ℃/min, then the temperature is reduced to 600 ℃ at the cooling rate of 100 ℃/min, and then the pressure is slowly released, and the furnace is cooled. The graphite mold comprises an upper pressure head, a lower pressure head and a graphite female mold.
And 4, machining the molybdenum-sodium alloy blank, and grinding and polishing to obtain a molybdenum-sodium alloy plate-shaped target finished product. The finished product of the molybdenum-sodium alloy plate-shaped target material prepared by the embodiment has uniform particles, tight arrangement and less hole defects. Through detection, the relative density of the finished product of the molybdenum-sodium alloy plate-shaped target material prepared by the embodiment is 98.0%, and the grain size is about 30 μm. The finished product of the molybdenum-sodium alloy plate-shaped target material prepared by the embodiment has fine crystal grains, uniform tissue distribution and equiaxial crystal grains.
Claims (5)
1. A preparation method of a molybdenum-sodium alloy plate-shaped target material is characterized by comprising the following steps:
step 1, dissolving sodium molybdate and a binder with deionized water, uniformly mixing, adding molybdenum powder, performing spray granulation to obtain molybdenum-sodium alloy powder, and finally performing decarburization treatment on 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 blank;
step 3, placing the initial pressed compact in a graphite mold, then placing the graphite mold in an SPS sintering furnace for pressurization, and vacuumizing; finally, increasing current to the SPS sintering furnace, heating up, sintering, releasing pressure and cooling to obtain a molybdenum-sodium alloy blank;
and 4, machining the molybdenum-sodium alloy blank, and grinding and polishing to obtain a molybdenum-sodium alloy plate-shaped target finished product.
2. The method for preparing the molybdenum-sodium alloy plate-shaped target material according to claim 1, wherein the steps of increasing the current, heating, sintering, releasing the pressure and cooling the SPS sintering furnace in the step 3 are specifically as follows:
raising the temperature of the SPS sintering furnace from room temperature to 300 ℃ at the temperature raising rate of 30-100 ℃/min, raising the temperature to 600 ℃ at the temperature raising rate of 100-200 ℃/min, raising the temperature to 1000-1200 ℃ at the temperature raising rate of 30-100 ℃/min, and then preserving the heat for 5-20 min; after the heat preservation is finished, the temperature is reduced to 800 ℃ at the cooling rate of 50-200 ℃/min, then is reduced to 600 ℃ at the cooling rate of 50-200 ℃/min, and then is slowly released and is cooled along with the furnace.
3. The method for preparing the molybdenum-sodium alloy plate-shaped target material according to claim 1, wherein the low-pressure pre-pressing in the step 2 is performed by a cold isostatic pressing method, and the specific parameters are as follows: the pressure is 100MPa-150MPa, and the pressure maintaining time is 5min-10 min.
4. The method for preparing the molybdenum-sodium alloy plate-shaped target material according to claim 1, wherein the finished product of the molybdenum-sodium alloy plate-shaped target material in the step 4 comprises the following components in parts by mass: 0.8 to 8.0 percent of Na element and the balance of Mo element, wherein the mass percentage of the components is 100 percent.
5. The method for preparing the molybdenum-sodium alloy plate-shaped target material according to claim 1, wherein the molybdenum powder has a mass purity of 99.95% or more, the Freund's particle size of the molybdenum powder is 3.0 μm to 4.0 μm, and the sodium molybdate has a mass purity of 99.0% or more.
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