CN111041319A - Tough high-temperature-resistant molybdenum oxide alloy and preparation method thereof - Google Patents
Tough high-temperature-resistant molybdenum oxide alloy and preparation method thereof Download PDFInfo
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Abstract
The invention provides a tough high-temperature-resistant molybdenum oxide alloy and a preparation method thereof, wherein the molybdenum alloy consists of molybdenum, silicon, boron and zirconium, and the preparation method comprises the following steps: the weight percentage range of silicon is 2.2-4%, the weight percentage range of boron is 0.8-1%, the weight percentage range of zirconium is 0.8-1%, and the rest is molybdenum. The invention adopts a solid-solid mixing mode to mix materials, utilizes mechanical ball milling or high-energy ball milling to prepare pre-alloyed powder with uniform particles, sinters the alloyed ball-milled powder to obtain a molybdenum alloy material, and then carries out embedding siliconizing treatment to obtain the tough and antioxidant molybdenum alloy. The molybdenum alloy prepared by the method has good compactness, strong toughness and high-temperature oxidation resistance, thereby having wide application prospect and popularization value.
Description
Technical Field
The invention relates to the field of powder metallurgy, and relates to a tough high-temperature-resistant molybdenum oxide alloy and a preparation method thereof.
Background
The molybdenum-silicon-boron alloy is a refractory material, has the characteristics of high melting point, high temperature strength, high hardness and the like, and has very important application prospect. However, the influence of different component systems, forming processes and doping elements on the relevant bonds of the metallographic structure of the alloy, and the balance of good fracture toughness and high-temperature oxidation resistance are key problems, which limit the development and application of the molybdenum alloy. Therefore, research and development of molybdenum alloys with excellent properties and improvement of the forming process and the quality of products are important directions of the researchers' efforts.
Disclosure of Invention
The invention provides a tough high-temperature-resistant molybdenum oxide alloy and a preparation method thereof, and aims to solve the problems in the prior art.
The technical scheme of the invention is as follows:
the tough high-temperature-resistant molybdenum oxide alloy is characterized in that: the tough high-temperature-resistant molybdenum oxide alloy consists of the following chemical elements in percentage by mass: 2.2 to 4 percent of Si; b, 0.8% -1%; 0.8 to 1 percent of Zr; the balance of Mo and inevitable impurities; the sum of the mass percentages of the chemical elements is 100 percent.
The preparation method of the tough high-temperature-resistant molybdenum oxide alloy is characterized by comprising the following steps: the method comprises the following steps:
step 1: taking Si powder, B powder, Zr powder and Mo powder without impurities on the surface, and mixing the Si powder: 1.4% -3%, powder B: 0.8% -1%, Zr powder: 0.8-1 percent of Mo powder, and the balance of Mo powder, weighing each elementary substance powder, mixing by using a mixer, and carrying out solid-solid ball milling on the obtained mixture in a planetary ball mill to ensure that the mixture is uniformly ball-milled to obtain pre-alloyed powder;
step 2: putting the prealloy powder obtained in the step 1 into a mold after isolated packaging, putting the mold into a cold isostatic pressing device after packaging, and setting pressure intensity and pressure maintaining time for pressing to obtain a blank;
and step 3: sintering the blank obtained in the step 2 in a sintering furnace under a vacuum condition, and cooling along with the furnace after sintering to obtain a molybdenum alloy material with the bending strength of more than 420 Mpa;
and 4, step 4: adopting an embedding method for siliconizing treatment, wherein the components of the siliconizing agent are as follows: si, NaF and Na2SiF6Powder; weighing 25 mass percent of Si powder, 5 mass percent of NaF powder and 70 mass percent of Na2SiF6Powder is subjected to ball milling and uniform mixing to obtain penetrating agent powder, the penetrating agent powder is filled into a small crucible, the molybdenum alloy obtained in the step 3 is integrally embedded into the penetrating agent powder, the small crucible is placed into a large crucible, the penetrating agent powder is filled around the small crucible, and the large crucible is sealed; the large crucible is put into a sintering furnace for sintering and heat preservation, and after siliconizing is finished, the tough high-temperature-resistant molybdenum oxide alloy with the silicon content of 2.2-4 percent can be obtained.
Further preferred is characterized in that: in the step 1, the median particle size of the selected molybdenum powder particles is 1-3 mu m, and the purity is not lower than 99.95%; the median particle size of the silicon powder particles is 2-4 mu m, and the purity is not lower than 99.90%; the median particle size of the boron powder particles is 2-4 mu m, and the purity is not lower than 99.50%; the median particle diameter of the zirconium powder particles is 20-40 mu m, and the purity is not lower than 99.90%.
Further preferred is characterized in that: in the step 1, weighing each simple substance powder required by the alloy, and then carrying out mixing and ball milling treatment by using a mixer, wherein the ball-to-material ratio is 5:1, the duration is 15-20 hours, the obtained mixed material is subjected to solid-solid ball milling in a planetary ball mill, the ball milling duration is 20 hours, and the ball mill changes the rotation direction once per hour to ensure that the ball milling is uniform.
Further preferred is characterized in that: step 2, putting the pre-alloyed powder into a graphite die, and isolating the powder from the die in the graphite die by using graphite paper; and (5) placing the sheathed tube into a cold isostatic pressing device, wherein the pressing pressure is 200 Mpa.
Further preferred is characterized in that: and 3, sintering the sintering furnace in a vacuum environment with the sintering atmosphere within 0.01Pa and the sintering temperature of 1550-1710 ℃, so as to obtain the molybdenum alloy material with the bending strength of more than 420 MPa.
Further preferred is characterized in that: in the step 4, Ar gas is used as protective gas, the siliconizing temperature is 1000 ℃, the heat preservation time is 4-6 hours, and the sample is taken out and then subjected to ultrasonic cleaning. Removing the residual reagent on the surface, and finally drying to obtain the tough high-temperature-resistant molybdenum oxide alloy with the silicon content of 2.2-4%.
Further preferred is characterized in that: step 4, after the molybdenum alloy is wholly embedded into the infiltrant powder in the small alumina crucible, the small crucible is filled and compacted with the infiltrant powder, and the small crucible is covered with a cover, and a vent hole is covered; and then the small crucible after being covered is placed in a large alumina crucible.
Advantageous effects
The invention provides a tough high-temperature oxidation resistance molybdenum alloy and a preparation method thereof. The combination of the preparation is Moss、Mo3Si and Mo5SiB2Continuously distributed MossThe matrix can provide good room temperature fracture toughness, is a tough phase, and the surface of the matrix can be formed by Mo in a high-temperature environment3Si and Mo5SiB2The borosilicate source provided forms a glass that is protected from the substrate.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic view of a siliconizing treatment apparatus according to the present invention. The inside is a 50mL crucible, the upper end is provided with a vent for discharging vaporized infiltration agent, a sample is put into the mixed infiltration agent and then is completely filled, the opening cover is sealed, the outside is a 100mL crucible which is filled with a certain amount of the same infiltration agent, and the opening cover is sealed.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and not to be construed as limiting the invention.
The molybdenum particles used in the embodiment of the invention are purchased from Shaanxi gold Toucheng molybdenum industry group Co. Silicon, boron, zirconium, and NaF and Na2SiF6 powders were purchased from Ron reagent.
Example 1
Weighing 2520g of Mo powder, 75.6g of Si powder, 25.2g of B powder and 20.16g of Zr powder, putting the materials into a mixer for mixing for 15 hours, putting the mixed materials into a planetary ball mill (QM-3SP4) for ball milling for 20 hours, wherein the ball-material ratio is 5:1, the rotating speed is 300r/min, and the ball mill is changed once per hour in the rotating direction to uniformly ball mill the materials to obtain prealloy powder. Wherein the median particle size of the selected molybdenum powder particles is 1-3 mu m, and the purity is not lower than 99.95%; the median particle size of the silicon powder particles is 2-4 mu m, and the purity is not lower than 99.90%; the median particle size of the boron powder particles is 2-4 mu m, and the purity is not lower than 99.50%; the median particle diameter of the zirconium powder particles is 20-40 mu m, and the purity is not lower than 99.90%.
Placing the pre-alloyed powder into a graphite mold, and isolating the powder from the mold in the graphite mold by using graphite paper; placing the coated blank into a cold isostatic pressing device, setting the pressing pressure to be 200Mpa, keeping the pressure for 30s, and pressing to obtain a blank;
and (3) putting the pressed blank into a sintering furnace, wherein the sintering atmosphere of the sintering furnace is a vacuum environment within 0.01Pa, the sintering temperature is 1550 ℃, the heat preservation time is 6min, cooling along with the furnace after sintering is finished, and performing vacuum sintering to obtain the molybdenum alloy material with the bending strength of more than 420 Mpa.
Weighing 250g of Si powder, 50g of NaF powder and Na according to the proportion2SiF6Putting 700g of the powder into a planetary ball mill for ball milling for 20 hours, wherein the ball-material ratio is 8: 1, the rotating speed is 300 r/min. Obtaining the penetrant powder. Putting the penetrant powder into a 50mL alumina crucible, embedding the obtained molybdenum alloy into the penetrant powder, filling the 50mL crucible with the penetrant powder, compacting, and covering; and then putting the covered 50mL crucible into a 100mL crucible, filling infiltration agent powder around the 50mL crucible, then sealing the 100mL crucible, putting the 100mL crucible into a resistance furnace, adopting Ar gas as protective gas, keeping the siliconizing temperature at 1000 ℃, keeping the temperature for 4 hours, cooling along with the furnace, taking out a sample, then carrying out ultrasonic cleaning, removing the reagent remained on the surface, and finally carrying out drying treatment to obtain the tough high-temperature-resistant molybdenum oxide alloy.
Example 2
2548g of Mo powder, 39.6g of Si powder, 26.4g of B powder and 25.8g of Zr powder are weighed and put into a mixer for mixing for 20 hours, then the mixed materials are put into a planetary ball mill (QM-3SP4) for ball milling for 20 hours, the ball-material ratio is 5:1, the rotating speed is 300r/min, the ball mill changes the rotating direction once per hour, and the ball milling is uniform, so that the pre-alloy powder is obtained. Wherein the median particle size of the selected molybdenum powder particles is 1-3 mu m, and the purity is not lower than 99.95%; the median particle size of the silicon powder particles is 2-4 mu m, and the purity is not lower than 99.90%; the median particle size of the boron powder particles is 2-4 mu m, and the purity is not lower than 99.50%; the median particle diameter of the zirconium powder particles is 20-40 mu m, and the purity is not lower than 99.90%.
Placing the pre-alloyed powder into a graphite mold, and isolating the powder from the mold in the graphite mold by using graphite paper; placing the coated blank into a cold isostatic pressing device, setting the pressing pressure to be 200Mpa, keeping the pressure for 30s, and pressing to obtain a blank;
and (3) putting the pressed blank into a sintering furnace, wherein the sintering atmosphere of the sintering furnace is a vacuum environment within 0.01Pa, the sintering temperature is 1700 ℃, the heat preservation time is 6min, the blank is cooled along with the furnace after sintering, and the molybdenum alloy material with the bending strength of more than 420Mpa is obtained by vacuum sintering.
Weighing 250g of Si powder, 50g of NaF powder and Na according to the proportion2SiF6Putting 700g of the powder into a planetary ball mill for ball milling for 20 hours, wherein the ball-material ratio is 8: 1, the rotating speed is 300 r/min. Obtaining the penetrant powder. Will be provided withPutting the penetrant powder into a 50mL alumina crucible, embedding the obtained molybdenum alloy into the penetrant powder, filling the 50mL crucible with the penetrant powder, compacting, and covering; and then putting the covered 50mL crucible into a 100mL crucible, filling infiltration agent powder around the 50mL crucible, then sealing the 100mL crucible, putting the 100mL crucible into a resistance furnace, adopting Ar gas as protective gas, keeping the siliconizing temperature at 1000 ℃, keeping the temperature for 6 hours, cooling along with the furnace, taking out a sample, then carrying out ultrasonic cleaning, removing the reagent remained on the surface, and finally carrying out drying treatment to obtain the tough high-temperature-resistant molybdenum oxide alloy.
Example 3
2551g of Mo powder, 44.9g of Si powder, 21.6g of B powder and 22.3g of Zr powder are weighed and put into a mixer for mixing for 15 hours, then the mixed materials are put into a planetary ball mill (QM-3SP4) for ball milling for 20 hours, the ball-material ratio is 5:1, the rotating speed is 300r/min, the ball mill changes the rotating direction once per hour, and the ball milling is uniform, so that the pre-alloy powder is obtained. Wherein the median particle size of the selected molybdenum powder particles is 1-3 mu m, and the purity is not lower than 99.95%; the median particle size of the silicon powder particles is 2-4 mu m, and the purity is not lower than 99.90%; the median particle size of the boron powder particles is 2-4 mu m, and the purity is not lower than 99.50%; the median particle diameter of the zirconium powder particles is 20-40 mu m, and the purity is not lower than 99.90%.
Placing the pre-alloyed powder into a graphite mold, and isolating the powder from the mold in the graphite mold by using graphite paper; placing the coated blank into a cold isostatic pressing device, setting the pressing pressure to be 200Mpa, keeping the pressure for 30s, and pressing to obtain a blank;
and (3) putting the pressed blank into a sintering furnace, wherein the sintering atmosphere of the sintering furnace is a vacuum environment within 0.01Pa, the sintering temperature is 1600 ℃, the heat preservation time is 6min, the blank is cooled along with the furnace after sintering, and the molybdenum alloy material with the bending strength of more than 420MPa is obtained by vacuum sintering.
Weighing 250g of Si powder, 50g of NaF powder and Na according to the proportion2SiF6Putting 700g of the powder into a planetary ball mill for ball milling for 20 hours, wherein the ball-material ratio is 8: 1, the rotating speed is 300 r/min. Obtaining the penetrant powder. Putting the penetrant powder into a 50mL alumina crucible, embedding the obtained molybdenum alloy into the penetrant powder, filling the 50mL crucible with the penetrant powder, compacting, and covering; then the 50mL crucible after being covered is put into 100mL crucibleIn the crucible, 50mL of crucible is filled with infiltrant powder, then 100mL of crucible is sealed, 100mL of crucible is put into a resistance furnace, Ar gas is used as protective gas, the siliconizing temperature is 1000 ℃, the heat preservation time is 5 hours, after cooling along with the furnace, a sample is taken out and then is subjected to ultrasonic cleaning, the reagent remained on the surface is removed, and finally drying treatment is carried out, so that the tough high-temperature resistant molybdenum oxide alloy is obtained.
Example 4
2508g of Mo powder, 79.2g of Si powder, 26.4g of B powder and 26.4g of Zr powder are weighed and put into a mixer for mixing for 18 hours, then the mixed materials are put into a planetary ball mill (QM-3SP4) for ball milling for 20 hours, the ball-material ratio is 5:1, the rotating speed is 300r/min, the ball mill changes the rotating direction once per hour, and the ball milling is uniform, so that the pre-alloy powder is obtained. Wherein the median particle size of the selected molybdenum powder particles is 1-3 mu m, and the purity is not lower than 99.95%; the median particle size of the silicon powder particles is 2-4 mu m, and the purity is not lower than 99.90%; the median particle size of the boron powder particles is 2-4 mu m, and the purity is not lower than 99.50%; the median particle diameter of the zirconium powder particles is 20-40 mu m, and the purity is not lower than 99.90%.
Placing the pre-alloyed powder into a graphite mold, and isolating the powder from the mold in the graphite mold by using graphite paper; placing the coated blank into a cold isostatic pressing device, setting the pressing pressure to be 200Mpa, keeping the pressure for 30s, and pressing to obtain a blank;
and (3) putting the pressed blank into a sintering furnace, wherein the sintering atmosphere of the sintering furnace is a vacuum environment within 0.01Pa, the sintering temperature is 1700 ℃, the heat preservation time is 6min, the blank is cooled along with the furnace after sintering, and the molybdenum alloy material with the bending strength of more than 420Mpa is obtained by vacuum sintering.
Weighing 250g of Si powder, 50g of NaF powder and Na according to the proportion2SiF6Putting 700g of the powder into a planetary ball mill for ball milling for 20 hours, wherein the ball-material ratio is 8: 1, the rotating speed is 300 r/min. Obtaining the penetrant powder. Putting the penetrant powder into a 50mL alumina crucible, embedding the obtained molybdenum alloy into the penetrant powder, filling the 50mL crucible with the penetrant powder, compacting, and covering; then placing the covered 50mL crucible into a 100mL crucible, filling the penetrating agent powder around the 50mL crucible, then sealing the 100mL crucible, placing the 100mL crucible into a resistance furnace, adopting Ar gas as protective gas, the siliconizing temperature is 1000 ℃, the heat preservation time is 4 hours,and cooling the sample along with the furnace, taking out the sample, performing ultrasonic cleaning to remove the reagent remained on the surface, and finally performing drying treatment to obtain the tough high-temperature-resistant molybdenum oxide alloy.
Example 5
2561g of Mo powder, 37.0g of Si powder, 21.1g of B powder and 21.1g of Zr powder are weighed and put into a mixer for mixing for 15 hours, then the mixed materials are put into a planetary ball mill (QM-3SP4) for ball milling for 20 hours, the ball-material ratio is 5:1, the rotating speed is 300r/min, the ball mill changes the rotating direction once per hour, and the ball milling is uniform, so that the pre-alloy powder is obtained. Wherein the median particle size of the selected molybdenum powder particles is 1-3 mu m, and the purity is not lower than 99.95%; the median particle size of the silicon powder particles is 2-4 mu m, and the purity is not lower than 99.90%; the median particle size of the boron powder particles is 2-4 mu m, and the purity is not lower than 99.50%; the median particle diameter of the zirconium powder particles is 20-40 mu m, and the purity is not lower than 99.90%.
Placing the pre-alloyed powder into a graphite mold, and isolating the powder from the mold in the graphite mold by using graphite paper; placing the coated blank into a cold isostatic pressing device, setting the pressing pressure to be 200Mpa, keeping the pressure for 30s, and pressing to obtain a blank;
and (3) putting the pressed blank into a sintering furnace, wherein the sintering atmosphere of the sintering furnace is a vacuum environment within 0.01Pa, the sintering temperature is 1710 ℃, the heat preservation time is 6min, the blank is cooled along with the furnace after sintering, and the molybdenum alloy material with the bending strength of more than 420Mpa is obtained by vacuum sintering.
Weighing 250g of Si powder, 50g of NaF powder and Na according to the proportion2SiF6Putting 700g of the powder into a planetary ball mill for ball milling for 20 hours, wherein the ball-material ratio is 8: 1, the rotating speed is 300 r/min. Obtaining the penetrant powder. Putting the penetrant powder into a 50mL alumina crucible, embedding the obtained molybdenum alloy into the penetrant powder, filling the 50mL crucible with the penetrant powder, compacting, and covering; and then putting the covered 50mL crucible into a 100mL crucible, filling infiltration agent powder around the 50mL crucible, then sealing the 100mL crucible, putting the 100mL crucible into a resistance furnace, adopting Ar gas as protective gas, keeping the siliconizing temperature at 1000 ℃, keeping the temperature for 4 hours, cooling along with the furnace, taking out a sample, then carrying out ultrasonic cleaning, removing the reagent remained on the surface, and finally carrying out drying treatment to obtain the tough high-temperature-resistant molybdenum oxide alloy.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (8)
1. A tough high-temperature-resistant molybdenum oxide alloy is characterized in that: the tough high-temperature-resistant molybdenum oxide alloy consists of the following chemical elements in percentage by mass: 2.2 to 4 percent of Si; b, 0.8% -1%; 0.8 to 1 percent of Zr; the balance of Mo and inevitable impurities; the sum of the mass percentages of the chemical elements is 100 percent.
2. A method for preparing the tough high temperature resistant molybdenum oxide alloy of claim 1, which is characterized in that: the method comprises the following steps:
step 1: taking Si powder, B powder, Zr powder and Mo powder without impurities on the surface, and mixing the Si powder: 1.4% -3%, powder B: 0.8% -1%, Zr powder: 0.8-1 percent of Mo powder, and the balance of Mo powder, weighing each elementary substance powder, mixing by using a mixer, and carrying out solid-solid ball milling on the obtained mixture in a planetary ball mill to ensure that the mixture is uniformly ball-milled to obtain pre-alloyed powder;
step 2: putting the prealloy powder obtained in the step 1 into a mold after isolated packaging, putting the mold into a cold isostatic pressing device after packaging, and setting pressure intensity and pressure maintaining time for pressing to obtain a blank;
and step 3: sintering the blank obtained in the step 2 in a sintering furnace under a vacuum condition, and cooling along with the furnace after sintering to obtain a molybdenum alloy material with the bending strength of more than 420 Mpa;
and 4, step 4: adopting an embedding method for siliconizing treatment, wherein the components of the siliconizing agent are as follows: si, NaF and Na2SiF6Powder; weighing 25 mass percent of Si powder, 5 mass percent of NaF powder and 70 mass percent of Na2SiF6Powder is ball-milled and mixed evenly to obtain penetrating agent powder, the penetrating agent powder is filled into a small crucible, and the molybdenum alloy obtained in the step 3 is wholly embedded into the penetrating agent powderThen placing the small crucible into the large crucible, and sealing the large crucible after filling the infiltrant powder around the small crucible; the large crucible is put into a sintering furnace for sintering and heat preservation, and after siliconizing is finished, the tough high-temperature-resistant molybdenum oxide alloy with the silicon content of 2.2-4 percent can be obtained.
3. The preparation method of the tough high-temperature-resistant molybdenum oxide alloy according to claim 2, characterized by comprising the following steps: in the step 1, the median particle size of the selected molybdenum powder particles is 1-3 mu m, and the purity is not lower than 99.95%; the median particle size of the silicon powder particles is 2-4 mu m, and the purity is not lower than 99.90%; the median particle size of the boron powder particles is 2-4 mu m, and the purity is not lower than 99.50%; the median particle diameter of the zirconium powder particles is 20-40 mu m, and the purity is not lower than 99.90%.
4. The preparation method of the tough high-temperature-resistant molybdenum oxide alloy according to claim 2, characterized by comprising the following steps: in the step 1, weighing each simple substance powder required by the alloy, and then carrying out mixing and ball milling treatment by using a mixer, wherein the ball-to-material ratio is 5:1, the duration is 15-20 hours, the obtained mixed material is subjected to solid-solid ball milling in a planetary ball mill, the ball milling duration is 20 hours, and the ball mill changes the rotation direction once per hour to ensure that the ball milling is uniform.
5. The preparation method of the tough high-temperature-resistant molybdenum oxide alloy according to claim 2, characterized by comprising the following steps: step 2, putting the pre-alloyed powder into a graphite die, and isolating the powder from the die in the graphite die by using graphite paper; and (5) placing the sheathed tube into a cold isostatic pressing device, wherein the pressing pressure is 200 Mpa.
6. The preparation method of the tough high-temperature-resistant molybdenum oxide alloy according to claim 2, characterized by comprising the following steps: and 3, sintering the sintering furnace in a vacuum environment with the sintering atmosphere within 0.01Pa and the sintering temperature of 1550-1710 ℃, so as to obtain the molybdenum alloy material with the bending strength of more than 420 MPa.
7. The preparation method of the tough high-temperature-resistant molybdenum oxide alloy according to claim 2, wherein in the step 4, Ar gas is used as protective gas, the siliconizing temperature is 1000 ℃, the heat preservation time is 4-6 hours, and the sample is taken out and then subjected to ultrasonic cleaning. Removing the residual reagent on the surface, and finally drying to obtain the tough high-temperature-resistant molybdenum oxide alloy with the silicon content of 2.2-4%.
8. The method for preparing the tough high-temperature-resistant molybdenum oxide alloy according to claim 2, wherein in the step 4, after the molybdenum alloy is wholly embedded into the infiltrant powder in the small alumina crucible, the small crucible is filled and compacted with the infiltrant powder, covered and covered with the vent; and then the small crucible after being covered is placed in a large alumina crucible.
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| CN112779448A (en) * | 2020-12-27 | 2021-05-11 | 西北工业大学 | High-temperature-resistant molybdenum oxide alloy and preparation method thereof |
| CN112828298A (en) * | 2020-12-31 | 2021-05-25 | 中国人民解放军空军工程大学 | Preparation method of high-temperature molybdenum alloy spherical powder |
| CN114850473A (en) * | 2022-04-13 | 2022-08-05 | 金堆城钼业股份有限公司 | Molybdenum and molybdenum alloy material sintering method and application thereof |
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