CN115233065B - Molybdenum-rhenium prealloy powder and preparation method thereof - Google Patents
Molybdenum-rhenium prealloy powder and preparation method thereof Download PDFInfo
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- CN115233065B CN115233065B CN202210807763.1A CN202210807763A CN115233065B CN 115233065 B CN115233065 B CN 115233065B CN 202210807763 A CN202210807763 A CN 202210807763A CN 115233065 B CN115233065 B CN 115233065B
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- 239000000843 powder Substances 0.000 title claims abstract description 107
- YUSUJSHEOICGOO-UHFFFAOYSA-N molybdenum rhenium Chemical compound [Mo].[Mo].[Re].[Re].[Re] YUSUJSHEOICGOO-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 80
- 239000001257 hydrogen Substances 0.000 claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000002270 dispersing agent Substances 0.000 claims abstract description 28
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 23
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 22
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 22
- 239000011591 potassium Substances 0.000 claims abstract description 22
- 238000007873 sieving Methods 0.000 claims abstract description 22
- 238000005303 weighing Methods 0.000 claims abstract description 22
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005507 spraying Methods 0.000 claims abstract description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000009489 vacuum treatment Methods 0.000 claims abstract description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 70
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 36
- HRLYFPKUYKFYJE-UHFFFAOYSA-N tetraoxorhenate(2-) Chemical compound [O-][Re]([O-])(=O)=O HRLYFPKUYKFYJE-UHFFFAOYSA-N 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 25
- 238000007599 discharging Methods 0.000 claims description 25
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003595 mist Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 9
- 239000011733 molybdenum Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 238000011946 reduction process Methods 0.000 abstract description 6
- XKMVDXZPCWRMJL-UHFFFAOYSA-N [Re].[Mo]=O Chemical compound [Re].[Mo]=O XKMVDXZPCWRMJL-UHFFFAOYSA-N 0.000 abstract 1
- 230000008092 positive effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 7
- 229910000691 Re alloy Inorganic materials 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 6
- 229910003449 rhenium oxide Inorganic materials 0.000 description 6
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 5
- 238000001514 detection method Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- 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
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The application discloses molybdenum-rhenium prealloy powder, which comprises 100% by mass of rhenium metal and 100% by mass of molybdenum metal, wherein the mass percentage of the rhenium metal is 5-41% and the mass percentage of the molybdenum metal is 59% -95%. The application also discloses a preparation method of the molybdenum-rhenium prealloy powder, which comprises the following steps of 1, weighing the components; step 2, configuring a dispersing agent; step 3, spraying and mixing; step 4, hydrogen reduction; and 5, vacuum treatment. By adding trace amounts of potassium molybdate and polyethylene glycol which can be decomposed and volatilized at high temperature in the preparation process of the molybdenum-rhenium oxide mixture, the reduction process matched with the potassium molybdate and polyethylene glycol is simultaneously adapted, the purity of the prepared prealloy powder is ensured, the uniformity of powder particles is improved, the agglomeration of the particles is reduced, the oxygen content in the powder is reduced, the sieving rate of 200 meshes of the prealloy powder after reduction is improved to more than 95 percent from 70 percent, the effect is obvious, and the positive effect on improving the utilization efficiency of molybdenum and rhenium resources is realized.
Description
Technical Field
The application belongs to the technical field of metallurgy, and particularly relates to molybdenum-rhenium prealloy powder and a preparation method thereof.
Background
The rhenium element is added into the metallic molybdenum, so that the prepared molybdenum-rhenium alloy can generate a rhenium effect, not only can improve the normal temperature performance and welding performance of molybdenum, but also can reduce the anisotropy of a processed material, raise the recrystallization temperature of the material and improve the room temperature brittleness, and is widely applied to the preparation of components in severe environments such as an ultra-high temperature thermal field, a nuclear reactor and the like. The powder metallurgy method is the main method for preparing molybdenum-rhenium alloy at present, and is generally to prepare molybdenum-rhenium alloy block materials by mechanically mixing molybdenum powder and rhenium powder, and then isostatic pressing, sintering and pressure processing. The uniformity of mixing of molybdenum and rhenium elements in the powder stage plays a critical role in the performance of the material.
In order to improve the uniformity of Mo and Re elements, rhenium-containing oxide (ammonium rhenate) and molybdenum oxide are generally mixed in the industry at present, then molybdenum-rhenium pre-alloy powder is prepared by adopting a hydrogen co-reduction mode, and the diffusion between the Mo and Re elements is accelerated by utilizing the activity and the thermal effect in the powder reduction process, so that the solid solution of the Mo and Re elements is realized in the powder stage, and the purpose of improving the uniformity of the distribution of the Mo and Re elements in the alloy is further achieved. However, when the reduction is carried out in the mode, the diffusion speed is high, the reaction is severe and uncontrollable, so that the prepared prealloyed powder is serious in agglomeration, the oxygen content of the alloy powder is high, and the sizes of the alloy powder are different. Particularly in the industrialized batch production process, the sieving rate of the product in front of the furnace is low (-200 meshes < 70%), and a large amount of prealloy powder forms unusable oversize products, so that the waste of Mo and Re rare metal materials is caused.
To solve this problem, the industry generally adopts two modes of physical crushing (air flow grinding, rolling and ball milling) and adjustment reduction technology to reduce the caking and agglomeration problems of molybdenum-rhenium prealloy powder. However, the crushing method generally needs to increase the process cost, gas and metal impurities are easy to introduce into the powder, the uniformity and the uniformity of the morphology of crushed powder particles are poor, and the reduction of the oxygen content in the powder has no substantial effect, so that the performance of the molybdenum-rhenium alloy product is finally affected; by adjusting the reduction process and mode, the agglomeration control of the Mo-Re prealloyed powder is limited, although the method is beneficial to improving the consistency and dispersibility of the pure molybdenum powder after reduction (as described in patent number 200910087582.0). Therefore, a preparation method of Mo-Re prealloy powder with good dispersibility, low agglomeration and low oxygen content is developed, and the preparation method has great significance in reducing the manufacturing cost of the Mo-Re prealloy powder and Mo-Re alloy, fully improving the resource utilization efficiency and improving the performance of the molybdenum-rhenium alloy.
Disclosure of Invention
The application aims to provide molybdenum-rhenium prealloy powder, which can ensure the dispersibility and uniformity of powder particles, improve the sieving rate of the prealloy powder and improve the yield while realizing full prealloying of molybdenum-rhenium element powder.
Another object of the present application is to provide a method for preparing the molybdenum-rhenium prealloyed powder described above,
the first technical scheme adopted by the application is as follows: the molybdenum-rhenium prealloy powder comprises 100% by mass of rhenium metal and molybdenum metal, wherein the mass percentage of the rhenium metal is 5% -41% and the mass percentage of the molybdenum metal is 59% -95%.
The second technical scheme adopted by the application is as follows: the preparation method of the molybdenum-rhenium pre-alloy powder comprises the following steps:
step 1, weighing the components
Weighing the following components in proportion: 0.03 to 0.05 weight percent of potassium molybdate, 0.1 to 0.5 weight percent of polyethylene glycol, 10 to 20 weight percent of water, 79.45 to 89.87 weight percent of molybdenum trioxide and ammonium rhenate mixture, and the proportion of the molybdenum trioxide and the ammonium rhenate is according to the Mo in the prepared molybdenum-rhenium pre-alloy powder: weighing Re mass ratio, wherein the total mass percentage of each component is 100%;
the total mass percent of rhenium metal and molybdenum metal in the molybdenum-rhenium prealloy powder is 100 percent, wherein the mass percent of rhenium metal is 5-41 percent, and the mass percent of molybdenum metal is 59-95 percent;
step 2, dispersant configuration
Dissolving the weighed potassium molybdate and polyethylene glycol in water according to corresponding proportion to prepare a component solution;
step 3, spray mixing
Placing the weighed molybdenum trioxide and ammonium rhenate in a closed container, spraying the dispersant solution prepared in the step 2 into the mixture of molybdenum trioxide and ammonium rhenate in the form of mist, and then spraying the mixture into the mixture of molybdenum trioxide and ammonium rhenate in the form of mist at the temperature of 1X 10 -1 ～2×10 -1 Mixing and drying under pa vacuum conditionObtaining a mixture;
step 4, hydrogen reduction
Carrying out three-stage hydrogen reduction on the mixture in the step 3 to prepare crude molybdenum-rhenium prealloy powder;
step 5, vacuum treatment
And (3) sieving the crude molybdenum-rhenium pre-alloy powder prepared in the step (4), and then carrying out vacuum heat treatment in a vacuum furnace again to finally prepare the finished molybdenum-rhenium pre-alloy powder.
The second technical proposal adopted by the application is also characterized in that,
the purity of the potassium molybdate in the step 2 is not less than 99.9 percent.
The polyethylene glycol in step 2 has a molecular weight of 400.
In the step 3, the prefabricated dispersing agent solution is sprayed into the mixture of molybdenum trioxide and ammonium rhenate by using vacuum spray drying equipment, and the mixture is rotationally mixed while vacuum is pumped.
And in the step 3, controlling the total duration of the vacuum spraying and mixing material to be 6-8 hours.
The hydrogen reduction in step 4 is performed in three stages, wherein the first stage is a zonal reduction, namely: the temperature range is 300-650 ℃,4 temperature points are taken as heat preservation points, the temperature difference between the heat preservation points is 90-100 ℃, each temperature point is preserved for 1-2 hours, and the hydrogen flow is 8-10 m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; the second stage is to reduce for 2-4 h at 700-750 ℃ with the hydrogen flow rate of 6-8 m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; the third stage is 900-950 deg.c, reduction for 2-4 hr and hydrogen flow rate of 4-6 m 3 And (h) discharging from the furnace after reduction, and cooling to room temperature to obtain crude molybdenum-rhenium prealloy powder.
In the step 5, the number of the sieving meshes is 200 meshes, and the vacuum degree is 10 during vacuum treatment -4 ～10 -5 Pa, the temperature is 1000-1050 ℃, and the heat preservation time is 0.5-1 h.
The beneficial effects of the application are as follows: by adding two substances with volatility and decomposability at high temperature, namely polyethylene glycol and potassium molybdate, into the mixture of molybdenum oxide and rhenium oxide, the volatilization-deposition effect of the oxide at different stages in the reduction process is promoted, and the effects of reducing fine particles in powder and improving the uniformity of the powder particles are achieved. The added substances are matched with unique three-stage reduction and vacuum impurity removal, so that impurities can be discharged at a high temperature stage, the dispersibility among powder particles is improved, and the removal of oxygen in the reduction process is facilitated. The method is simple to operate, is environment-friendly, can improve the sieving rate of-200 meshes of the molybdenum-rhenium prealloy powder stokehold material from 70% to more than 95%, has obvious economic effect and is suitable for industrial production.
Drawings
FIG. 1 is a morphology of Mo-41Re prealloyed powder prepared in example 1 of this application;
FIG. 2 is a morphology of Mo-14Re prealloyed powder prepared in example 3 of this application;
FIG. 3 is a prior art Mo-14Re prealloyed powder morphology.
Detailed Description
The application is described in further detail below with reference to the drawings and the detailed description, but these examples are not intended to limit the scope of the application, and those skilled in the art can make some insubstantial improvements and adaptations in light of the foregoing. The present application is not limited to these embodiments:
the molybdenum-rhenium prealloy powder provided by the application has the advantages that the total mass percentage of rhenium metal and molybdenum metal is 100%, wherein the mass percentage of rhenium metal is 5-41%, and the mass percentage of molybdenum metal is 59% -95%.
The application discloses a preparation method of molybdenum-rhenium prealloy powder, which comprises the following steps:
step 1, weighing the components
Weighing the following components in proportion: 0.03 to 0.05 weight percent of potassium molybdate, 0.1 to 0.5 weight percent of polyethylene glycol, 10 to 20 weight percent of water, 79.45 to 89.87 weight percent of molybdenum trioxide and ammonium rhenate mixture, and the proportion of the molybdenum trioxide and the ammonium rhenate is according to the Mo in the prepared molybdenum-rhenium pre-alloy powder: weighing Re mass ratio, wherein the total mass percentage of each component is 100%;
the total mass percent of rhenium metal and molybdenum metal in the molybdenum-rhenium prealloy powder is 100 percent, wherein the mass percent of rhenium metal is 5-41 percent, and the mass percent of molybdenum metal is 59-95 percent;
step 2, dispersant configuration
Dissolving the weighed potassium molybdate and polyethylene glycol in water according to corresponding proportion to prepare a component solution; the purity of the potassium molybdate is more than 99.9 percent; the molecular weight of the polyethylene glycol is 400;
step 3, spray mixing
Placing the weighed molybdenum trioxide and ammonium rhenate in a closed container, spraying the prepared dispersing agent solution in the step 2 into a mixture of molybdenum trioxide and ammonium rhenate in a mist form by utilizing vacuum spray drying equipment, rotationally mixing while spraying, simultaneously extracting vacuum, controlling the total duration of vacuum spray mixing to be 6-8 h, and then controlling the total duration of vacuum spray mixing to be 1 multiplied by 10 -1 ～2×10 -1 Heating, mixing and drying under pa vacuum condition to obtain a mixture;
step 4, hydrogen reduction
Carrying out three-stage hydrogen reduction on the mixture in the step 3, wherein the hydrogen reduction is carried out in three stages, and the first stage is temperature zone reduction, namely: the temperature range is 300-650 ℃,4 temperature points are taken as heat preservation points, the temperature difference between the heat preservation points is 90-100 ℃, each temperature point is preserved for 1-2 hours, and the hydrogen flow is 8-10 m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; the second stage is to reduce for 2-4 h at 700-750 ℃ with the hydrogen flow rate of 6-8 m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; the third stage is 900-950 deg.c, reduction for 2-4 hr and hydrogen flow rate of 4-6 m 3 And (h) discharging the powder after reduction and cooling to room temperature to prepare crude molybdenum-rhenium prealloy powder;
step 5, vacuum treatment
Sieving the crude molybdenum-rhenium prealloy powder prepared in the step 4, wherein the sieving number is 200 meshes, and performing vacuum heat treatment in a vacuum furnace again, wherein the vacuum degree is 10 during the vacuum treatment -4 ～10 -5 Pa, the temperature is 1000-1050 ℃, the heat preservation time is 0.5-1 h, and finally the finished molybdenum-rhenium prealloy powder is prepared.
The preparation of the molybdenum-rhenium prealloyed powder of the present application and its properties are further illustrated by the following examples.
Example 1
Step 1, weighing the components
Weighing the following components in proportion: 0.3g of potassium molybdate, 1g of polyethylene glycol 400, 100g of water, and 898.7g of the total mass of the molybdenum trioxide and ammonium rhenate mixture, wherein the proportion of the molybdenum trioxide to the ammonium rhenate is according to Mo in the prepared molybdenum-rhenium pre-alloy powder: re mass ratio 59:41, 537.8g and 360.9g of molybdenum trioxide and ammonium rhenate respectively, and the total weight is 1kg;
step 2, dispersant configuration
Dissolving the weighed potassium molybdate and polyethylene glycol in water to prepare a dispersing agent solution;
step 3, spray mixing
Placing the weighed molybdenum trioxide and ammonium rhenate in a closed container, spraying a prefabricated dispersing agent solution into a molybdenum and rhenium oxide mixture in a mist form, adding the prepared dispersing agent into the mixture in a mist form, and controlling the total duration of vacuum spraying and mixing to be 6 hours; then at 1X 10 -1 Heating, mixing and drying for 8 hours under pa vacuum condition to obtain a mixture;
step 4, hydrogen reduction
The mixture is reduced by hydrogen, the first stage is reduced to 300 ℃,400 ℃,500 ℃ and 600 ℃ and is respectively kept at the temperature for 1h, the total reduction is carried out for 4h, and the hydrogen flow is 8m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; the second stage of reduction is carried out at 700 ℃ for 2h, and the hydrogen flow is 6m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; in the third stage, the temperature is reduced to 900 ℃ and the hydrogen flow is 4m after 2h of reduction 3 And (h) discharging from the furnace after reduction, and cooling to room temperature to obtain crude molybdenum-rhenium prealloy powder.
Step 5, vacuum treatment
Sieving the powder after three-stage hydrogen reduction with 200 mesh sieve, and vacuum degree of 10 -4 Pa, the temperature is 1000 ℃, and the temperature is kept for 0.5h, so as to prepare Mo-Re composite powder;
the appearance of the prepared powder is shown in figure 1, the 200-mesh sieving rate of the powder is 96.3%, and the oxygen content of the powder is 0.057wt%.
Example 2
The preparation method of the Mo-30Re composite powder comprises the following specific steps:
step 1, weighing the components
Weighing the following components in proportion: 0.4g of potassium molybdate, 3g of polyethylene glycol 400, 150g of water, 846.6g of the total mass of the molybdenum trioxide and ammonium rhenate mixture, and the proportion of the molybdenum trioxide to the ammonium rhenate is according to Mo in the prepared molybdenum-rhenium pre-alloy powder: re mass ratio 70:30, 598.7g and 247.9g respectively;
step 2, dispersant configuration
Dissolving the weighed potassium molybdate and polyethylene glycol in water to prepare a dispersing agent solution;
step 3, spray mixing
Placing the weighed molybdenum trioxide and ammonium rhenate in a closed container, spraying a prefabricated dispersing agent solution into a molybdenum and rhenium oxide mixture in a mist form, adding the prepared dispersing agent into the mixture in a mist form, and controlling the total duration of vacuum spraying and mixing at 7h; then at 1.5X10 -1 Heating, mixing and drying for 7 hours under pa vacuum condition to obtain a mixture;
step 4, hydrogen reduction
Reducing the mixed materials by hydrogen, wherein the first stage of reduction is carried out at 350 ℃,450 ℃,550 ℃ and 650 ℃ for 1.5 hours, the total reduction is carried out for 6 hours, and the hydrogen flow is 10m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; the second stage of reduction is carried out at 750 ℃ for 4 hours, and the hydrogen flow is 8m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; in the third stage, the temperature is reduced to 950 ℃ and the hydrogen flow is 6m after 4h of reduction 3 And (h) discharging from the furnace after reduction, and cooling to room temperature to obtain crude molybdenum-rhenium prealloy powder.
Step 5, vacuum treatment
Sieving the powder after three-stage hydrogen reduction with 200 mesh sieve, and vacuum degree of 10 -5 Pa,1000 ℃, and preserving heat for 1h. Mo-Re prealloyed powder is prepared.
The detection shows that the 200-mesh sieving rate of the prepared powder is 96.8%, and the oxygen content of the powder is 0.045wt%;
example 3
The preparation method of the Mo-14Re pre-alloy powder comprises the following specific steps:
step 1, weighing the components
Weighing the following components in proportion: 0.5g of potassium molybdate, 5g of polyethylene glycol 400, 200g of water, and 794.5g of the total mass of the molybdenum trioxide and ammonium rhenate mixture, wherein the proportion of the molybdenum trioxide to the ammonium rhenate is according to Mo in the prepared molybdenum-rhenium pre-alloy powder: re mass ratio 86:14, 686.4g and 108.1g respectively;
step 2, dispersant configuration
Dissolving the weighed potassium molybdate and polyethylene glycol in water to prepare a dispersing agent solution;
step 3, spray mixing
Placing the weighed molybdenum trioxide and ammonium rhenate in a closed container, spraying a prefabricated dispersing agent solution into a molybdenum and rhenium oxide mixture in a mist form, adding the prepared dispersing agent into the mixture in a mist form, and controlling the total duration of vacuum spraying and mixing to be 8 hours; then at 2X 10 -1 Heating, mixing and drying for 7 hours under pa vacuum condition to obtain a mixture;
step 4, hydrogen reduction
The mixed materials are subjected to hydrogen reduction, the first stage of reduction is carried out at 300 ℃,390 ℃,480 ℃ and 570 ℃ for 2h, the total reduction is carried out for 8h, and the hydrogen flow is 9m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; the second stage of reduction is carried out at 730 ℃ for 3h, and the hydrogen flow is 7m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; in the third stage, the temperature is reduced to 930 ℃ and the hydrogen flow is 5m after 3h of reduction 3 And (h) discharging from the furnace after reduction, and cooling to room temperature to obtain crude molybdenum-rhenium prealloy powder.
Step 4, vacuum treatment
Sieving the powder after three-stage hydrogen reduction with 200 mesh sieve, and vacuum degree of 10 -5 Pa,1050 ℃, and preserving heat for 1h. Preparing Mo-Re composite powder;
the powder morphology is shown in figure 2, the 200 mesh sieving rate of the powder is 95.6%, and the oxygen content is 0.053wt%.
Example 4
The preparation method of the Mo-5Re composite powder comprises the following specific steps:
step 1, weighing the components
Weighing the following components in proportion: 0.4g of potassium molybdate, 4g of polyethylene glycol 400, 180g of water, 815.6g of total mass of the molybdenum trioxide and ammonium rhenate mixture, and the proportion of the molybdenum trioxide to the ammonium rhenate is according to Mo in the prepared molybdenum-rhenium pre-alloy powder: re mass ratio 95:5, weighing 776.5g and 39.1g respectively;
step 2, dispersant configuration
Dissolving the weighed potassium molybdate and polyethylene glycol in water to prepare a dispersing agent solution;
step 3, spray mixing
And (3) placing the weighed molybdenum trioxide and ammonium rhenate in a closed container, spraying a prefabricated dispersing agent solution into a molybdenum and rhenium oxide mixture in a mist form, adding the prepared dispersing agent into the mixture in a mist form, and controlling the total duration of vacuum spraying and mixing at 7h. Then at 1X 10 -1 Heating, mixing and drying for 7 hours under pa vacuum condition to obtain a mixture;
step 4, hydrogen reduction
Reducing the mixed materials by hydrogen, wherein the first stage of reduction is carried out at 330 ℃,430 ℃,530 ℃ and 630 ℃ for 1.3 hours, the total reduction is carried out for 5.2 hours, and the hydrogen flow is 9m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; the second stage of reduction is carried out at 730 ℃ for 3h, and the hydrogen flow is 7m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; in the third stage, the temperature is reduced to 930 ℃ and the hydrogen flow is 5m after 3h of reduction 3 And (h) discharging from the furnace after reduction, and cooling to room temperature to obtain crude molybdenum-rhenium prealloy powder.
Step 4, vacuum treatment
Sieving the powder after three-stage hydrogen reduction with 200 mesh sieve, and vacuum-treating at 10 -4 Pa,1050 ℃, and preserving heat for 0.7h. And preparing Mo-Re composite powder.
The powder prepared by detection has a 200-mesh sieving rate of 97.3% and an oxygen content of 0.043%.
Example 5
The preparation method of the Mo-20Re composite powder comprises the following specific steps:
step 1, weighing the components
Weighing the following components in proportion: 0.35g of potassium molybdate, 3.5g of polyethylene glycol 400, 190g of water, and 806.15g of the total mass of the molybdenum trioxide and ammonium rhenate mixture, wherein the proportion of the molybdenum trioxide to the ammonium rhenate is according to Mo in the prepared molybdenum-rhenium pre-alloy powder: re mass ratio 80:20, 649.0g and 157.15g respectively;
step 2 dispersant configuration
Dissolving the weighed potassium molybdate and polyethylene glycol in the weighed water to prepare a component solution; step 3, spray mixing
Placing the weighed molybdenum trioxide and ammonium rhenate in a closed container, spraying a prefabricated dispersing agent solution into a molybdenum and rhenium oxide mixture in a mist form, adding the prepared dispersing agent into the mixture in a mist form, and controlling the total duration of vacuum spraying and mixing to be 6 hours; then at 1X 10 -1 Heating, mixing and drying for 6 hours under pa vacuum condition to obtain a mixture;
step 3, hydrogen reduction
The mixed materials are subjected to hydrogen reduction, the first stage of reduction is carried out at 300 ℃,400 ℃,500 ℃ and 600 ℃ for 1.5 hours, the total reduction is carried out for 6 hours, and the hydrogen flow is 10m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; the second stage of reduction is carried out at 710 ℃ for 4 hours, and the hydrogen flow is 7m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; in the third stage, the temperature is reduced to 910 ℃ for 4 hours, and the hydrogen flow is 5m 3 And (h) discharging from the furnace after reduction, and cooling to room temperature to obtain crude molybdenum-rhenium prealloy powder.
Step 4, vacuum treatment
Sieving the powder after three-stage hydrogen reduction with 200 mesh sieve, and vacuum degree of 10 -4 Pa,1030 ℃, and preserving heat for 1h. Mo-Re prealloyed powder is prepared.
The powder prepared by detection has a sieving rate of 95.2% by 200 meshes and an oxygen content of 0.038wt%.
Comparative example
According to the traditional mixing process, mo-14Re prealloyed powder is prepared by the following specific steps:
step 1, weighing the components
Mo in the molybdenum-rhenium prealloy powder prepared in accordance with the molybdenum trioxide to ammonium rhenate ratio: re mass ratio 86:14, for comparison, the total mass of the molybdenum trioxide and ammonium rhenate mixture was 794.5g, 686.4g and 108.1g, respectively;
step 2 of the method, in which the step 2,
molybdenum trioxide and ammonium rhenate at 1X 10 -1 Heating, mixing and drying for 7 hours under pa vacuum condition to obtain a mixture;
step 3, hydrogen reduction
The mixture is subjected to two-stage hydrogen reduction by referring to a common reduction process, wherein the first stage reduction is carried out at 500 ℃ for 6h with the hydrogen flow of 9m 3 And (h) cooling and discharging after reduction; the second stage is to reduce to 930 ℃ for 3h with the hydrogen flow of 5m 3 /h；
The powder morphology is shown in figure 3, the powder agglomeration is serious, the powder-200 mesh sieving rate is 72.6%, and the tested oxygen content is 0.134wt%.
The comparative example is a molybdenum-rhenium prealloy powder prepared by the conventional technical scheme, and compared with the example 3 of the application, the molybdenum-rhenium prealloy powder prepared by the conventional technical scheme has less uniformity of particles and less sieving rate than the molybdenum-rhenium prealloy powder prepared by the technical scheme, and the oxygen content in the powder is higher than the molybdenum-rhenium prealloy powder prepared by the technical scheme of the application, although the proportion of the raw materials is the same.
Claims (5)
1. The preparation method of the molybdenum-rhenium prealloy powder is characterized in that the total mass percentage of rhenium metal and molybdenum metal in the molybdenum-rhenium prealloy powder is 100%, wherein the mass percentage of the rhenium metal is 5% -41%, and the mass percentage of the molybdenum metal is 59% -95%;
the preparation method comprises the following steps:
step 1, weighing the components
Weighing the following components in proportion: 0.03 to 0.05 weight percent of potassium molybdate, 0.1 to 0.5 weight percent of polyethylene glycol, 10 to 20 weight percent of water, 79.45 to 89.87 weight percent of molybdenum trioxide and ammonium rhenate mixture, and the proportion of the molybdenum trioxide and the ammonium rhenate is according to the Mo in the prepared molybdenum-rhenium pre-alloy powder: weighing Re mass ratio, wherein the total mass percentage of each component is 100%;
the total mass percentage of rhenium metal and molybdenum metal in the molybdenum-rhenium pre-alloy powder is 100%, wherein the mass percentage of rhenium metal is 5% -41%, and the mass percentage of molybdenum metal is 59% -95%;
step 2, dispersant configuration
Dissolving the weighed potassium molybdate and polyethylene glycol in water according to corresponding proportion to prepare a component solution;
step 3, spray mixing
Placing the weighed molybdenum trioxide and ammonium rhenate in a closed container, spraying the dispersant solution prepared in the step 2 into the mixture of molybdenum trioxide and ammonium rhenate in the form of mist, and then spraying the mixture into the mixture of molybdenum trioxide and ammonium rhenate in the form of mist at the temperature of 1X 10 -1 ～2×10 -1 Mixing and drying under pa vacuum condition to obtain a mixture;
step 4, hydrogen reduction
Carrying out three-stage hydrogen reduction on the mixture in the step 3 to prepare crude molybdenum-rhenium prealloy powder;
the hydrogen reduction is carried out in three stages, wherein the first stage is a zonal reduction, namely: the temperature range is 300-650 ℃,4 temperature points are taken as heat preservation points, the temperature difference between the heat preservation points is 90-100 ℃, each temperature point is preserved for 1-2 hours, and the hydrogen flow is 8-10 m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; the second stage is to reduce for 2-4 h at 700-750 ℃ with the hydrogen flow rate of 6-8 m 3 And/h, discharging from the furnace after reduction and cooling to room temperature; the third stage is 900-950 deg.c, reduction for 2-4 hr and hydrogen flow rate of 4-6 m 3 And (h) discharging from the furnace after reduction and cooling to room temperature to obtain crude molybdenum-rhenium prealloy powder;
step 5, vacuum treatment
Sieving the crude molybdenum-rhenium prealloy powder prepared in the step 4, wherein the sieving number is 200 meshes, and performing vacuum heat treatment in a vacuum furnace again, wherein the vacuum degree is 10 during the vacuum treatment -4 ～10 -5 Pa, the temperature is 1000-1050 ℃, the heat preservation time is 0.5-1 h, and finally the finished molybdenum-rhenium prealloy powder is prepared.
2. The method for producing molybdenum-rhenium prealloyed powder according to claim 1, characterized in that the purity of the potassium molybdate in the step 2 is not less than 99.9%.
3. The method for preparing molybdenum-rhenium prealloyed powder according to claim 1, wherein the polyethylene glycol in the step 2 has a molecular weight of 400.
4. The method for preparing molybdenum-rhenium prealloy powder according to claim 1, wherein the step 3 is characterized in that the pre-prepared dispersant solution is sprayed into the mixture of molybdenum trioxide and ammonium rhenate by a vacuum spray drying apparatus while rotating and mixing while drawing vacuum.
5. The method for preparing molybdenum-rhenium prealloyed powder according to claim 1, wherein the total duration of the vacuum spray-mixing in the step 3 is controlled to be 6-8 hours.
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