CN116275050B - Preparation method of high-strength molybdenum - Google Patents
Preparation method of high-strength molybdenum Download PDFInfo
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- CN116275050B CN116275050B CN202310581104.5A CN202310581104A CN116275050B CN 116275050 B CN116275050 B CN 116275050B CN 202310581104 A CN202310581104 A CN 202310581104A CN 116275050 B CN116275050 B CN 116275050B
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 97
- 239000011733 molybdenum Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 101
- 238000000034 method Methods 0.000 claims abstract description 53
- 239000012535 impurity Substances 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 21
- 238000005098 hot rolling Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 238000000462 isostatic pressing Methods 0.000 claims abstract description 16
- 238000005096 rolling process Methods 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 238000007493 shaping process Methods 0.000 claims abstract description 9
- 238000003754 machining Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims description 35
- 239000004576 sand Substances 0.000 claims description 11
- 238000004663 powder metallurgy Methods 0.000 claims description 9
- 230000007306 turnover Effects 0.000 claims description 2
- 229910052845 zircon Inorganic materials 0.000 claims description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- CBPOHXPWQZEPHI-UHFFFAOYSA-N [Mo].[La] Chemical compound [Mo].[La] CBPOHXPWQZEPHI-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000858 La alloy Inorganic materials 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000000919 ceramic Substances 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000009770 conventional sintering Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 9
- 229910052726 zirconium Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010587 phase diagram Methods 0.000 description 4
- 238000007665 sagging Methods 0.000 description 4
- 238000007514 turning Methods 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005324 grain boundary diffusion Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
-
- 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
-
- 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
- B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining 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
- 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
- B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
- B22F2003/185—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers by hot rolling, below sintering temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/247—Removing material: carving, cleaning, grinding, hobbing, honing, lapping, polishing, milling, shaving, skiving, turning the surface
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to the technical field of molybdenum preparation, and relates to a preparation method of high-strength molybdenum, which comprises the steps of raw material selection, mixing, isostatic pressing, sintering, hot rolling, warm rolling, heat treatment, machining, low-temperature shaping and the like. And a high-energy mixer is adopted, so that high-purity molybdenum powder particles are smashed, and agglomeration is avoided. The high-purity molybdenum powder is adopted and further purified in the sintering process, and the impurity gas content of C, H, O is controlled below 10 ppm. Meanwhile, the vacuum furnace and the hydrogen furnace are adopted for multiple sintering modes, and different from the conventional sintering modes, the sintering time is prolonged, the material is compact, and holes are less. The high-strength product is formed by adopting a high-temperature and low-temperature mixing treatment mode, the plate shape of the material is ensured not to be deformed, and the impurity content of the grain boundary is low. Compared with the traditional common molybdenum and molybdenum lanthanum alloy, the alloy has obviously better strength and creep resistance, and has obvious advantages as ceramic sintering supporting pieces, high-temperature furnace components, high-temperature deformation resistance bearing pieces, aviation aerospace high Wen Jian and the like.
Description
Technical Field
The invention belongs to the technical field of molybdenum preparation, and relates to a preparation method of high-strength molybdenum.
Background
Under the high temperature condition, the grain boundary sliding and the grain boundary diffusion are main microcosmic mechanisms of the deformation (creep) of the molybdenum material. The common pure molybdenum is easy to recrystallize at the temperature of more than 900 ℃ and is in a coarse structure, and oxygen is easy to react with molybdenum to form oxide at the high temperature of 1600 ℃. Oxide and impurities gather in the grain boundary, so that the strength of the grain boundary is reduced, and phenomena such as thermal fatigue, thermal creep and the like can occur when the alloy is used at high temperature, thereby generating defects such as deformation, cracks and the like.
Disclosure of Invention
The invention aims to provide a preparation method of high-strength molybdenum, which can prepare a molybdenum product with higher purity and less impurity content, and has obviously higher strength and creep resistance compared with the traditional common molybdenum and molybdenum lanthanum alloy.
The technical scheme adopted by the invention is a preparation method of high-strength molybdenum, which is implemented according to the following steps:
s1, selecting raw materials: selecting high-purity molybdenum powder, wherein the purity of the high-purity molybdenum powder is ensured to be more than 99.99%, and the impurity content of the high-purity molybdenum powder is ensured to be less than 0.01%;
s2, mixing: fully crushing and mixing high-purity molybdenum powder;
s3, isostatic pressing: isostatic pressing is carried out on the crushed high-purity molybdenum powder;
s4, sintering: high-temperature sintering is carried out on the high-purity molybdenum powder subjected to isostatic pressing treatment, and the sintering time is 4-10 h when the temperature is 800-1000 ℃; sintering time is 8-16 h at 1700-2100 ℃; sintering for 8-16 h at 2100-2300 ℃ to finally obtain a plate blank;
s5, hot rolling: carrying out hot rolling treatment on the plate blank, wherein the cogging temperature is 1000-1300 ℃;
s6, warm rolling: preserving heat at the temperature of 350-450 ℃ for 20-40 min, and rolling the plate blank after hot rolling treatment into a plate;
s7, heat treatment: carrying out heat treatment on the plate subjected to warm rolling treatment at 1900-2100 ℃ for 9-10 hours to obtain a molybdenum product;
s8, machining: grinding the molybdenum product, wherein the thickness dimension of the molybdenum product is controlled to be +/-0.05 mm, the length and width dimensions of the molybdenum product are controlled to be +/-0.2 mm, and the flatness of the molybdenum product is controlled to be less than 0.1 mm;
s9, low-temperature shaping: and (3) carrying out low-temperature treatment on the molybdenum product subjected to grinding treatment at 600-800 ℃ for 2-4 hours to finally obtain high-strength molybdenum.
The invention is also characterized in that:
the impurities of the high-purity molybdenum powder in S1 comprise Ca, fe and K.
The specific process of S2 is as follows: and crushing and fully mixing large-particle agglomerated molybdenum powder particles in the high-purity molybdenum powder by adopting a high-energy mixer, wherein the rotating speed of the high-energy mixer is 3500r/min-4500r/min, and the mixing time is 2h-4h.
The high-energy mixer is a 1000L high-energy mixer.
S4 is divided into three stages for sintering, wherein the first stage is carried out by adopting a mode comprising presintering and vacuum sintering, and the vacuum degree of the furnace is required to be 1.0x10 -3 Pa, pre-sintering temperature is 800-1000 ℃, and sintering time is 4-10 h; the second stage is vacuum furnace sintering, gradient slow heating is adopted, and sintering time is 8-16 h when sintering temperature is 1700-2100 ℃; in the third stage, sintering is carried out by adopting a hydrogen furnace, wherein the hydrogen flow is 0.2m 3 /h-0.4m 3 And/h, sintering at 2100-2300 ℃ for 8-16 h to obtain a sintered plate blank.
The thickness of the slab in S5 is 35mm.
The thickness of the sheet rolled in S6 was 2mm.
And S7, separating the plates subjected to heat treatment by adopting zircon sand.
And S8, controlling the frequency of the grinding treatment below 17Hz, controlling the feed rate of the grinding treatment below 0.02mm, and performing multiple turn-over grinding.
And S9, performing low-temperature treatment in a vacuum furnace.
According to the scheme, a mixing treatment procedure is increased, and a high-energy mixer is adopted, so that high-purity molybdenum powder particles are smashed, and agglomeration is avoided. In the powder selection, high-purity molybdenum powder is adopted, and further purification is carried out in the sintering process, so that the impurity gas content of C, H, O is controlled below 10 ppm. Meanwhile, the vacuum furnace and the hydrogen furnace are adopted for multiple sintering modes, and different from the conventional sintering modes, the sintering time is prolonged, the material is compact, and holes are less. In addition, a high-temperature and low-temperature mixed treatment mode is adopted for the rolled plate, so that a molybdenum product is formed, the impurity content at the grain boundary is low, the plate shape of the material is ensured, the deformation and coarsening are avoided. Compared with the traditional common molybdenum and molybdenum lanthanum alloy, the alloy has obviously better strength and creep resistance, and has obvious advantages as ceramic sintering supporting pieces, high-temperature furnace components, high-temperature deformation resistance bearing pieces, aviation aerospace high Wen Jian and the like.
Drawings
FIG. 1 is a schematic flow chart of a method of preparing high strength molybdenum according to the present invention;
FIG. 2 is a gold phase diagram of the molybdenum prepared according to the present invention at 500 x under a metallographic microscope;
FIG. 3 is a 500 times gold phase diagram of a prior molybdenum product under a metallographic microscope;
FIG. 4 is a schematic illustration of a designed anti-sagging protocol;
FIG. 5 is a schematic representation of a designed anti-deformation protocol.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
As shown in fig. 1, the preparation method of the high-strength molybdenum sequentially comprises the steps of raw material selection, mixing, isostatic pressing, sintering, hot rolling, warm rolling, heat treatment, machining and low-temperature shaping treatment. The method comprises the following steps:
s1, selecting raw materials:
the raw material powder is high-purity molybdenum powder with purity of more than 99.99 percent, and the content of Ca, fe, K and other impurities is controlled below 0.01 percent.
S2, mixing:
before pressing, the high-purity molybdenum powder is fully mixed and smashed by a 1000L high-energy mixer, the rotating speed is 3500-4500, the mixing time is 2-4 h, and the original large-particle agglomerated molybdenum powder particles are kept smashed. The purpose is to ensure that the high-purity molybdenum powder has certain fluidity in the subsequent sintering process, and the sintered slab structure is more uniform and compact.
S3, isostatic pressing:
the isostatic pressing technology can lead the molybdenum powder to form microscopic particles under the action of pressure, improves the specific surface area and the activity of the molybdenum powder, and further leads the density of the high-purity molybdenum powder to be higher and uniform, thereby providing a good foundation for the subsequent sintering and hot rolling treatment;
s4, sintering:
in the prior art, electron beam furnace equipment is generally adopted for purification, and the invention is prepared by a powder metallurgy method. Compared with an electron beam furnace, the powder metallurgy method has potential advantages; firstly, the equipment cost is lower than that of an electron beam furnace by 10 times; meanwhile, the powder metallurgy method has simple process, and can further purify and remove impurities in the sintering process, thereby improving the purity of the powder metallurgy method.
In the powder metallurgy sintering process, the invention adopts three stages to sinter.
The first stage is performed by adopting a plurality of modes such as presintering, vacuum sintering and the like, and the vacuum degree of the furnace is required to be 1.0x10 -3 Pa, the presintering temperature is 800-1000 ℃, the presintering temperature is kept for 4-10 h, the gas and the moisture of the sintered slab are removed and volatilized, and the residual stress during pressing is eliminated.
The second stage is vacuum furnace sintering, the sintering temperature is 1700-2100 ℃, and the sintering time is kept for 8-16 h. In the heating process of the vacuum furnace, a gradient slow heating process is adopted, so that the high-purity molybdenum powder is ensured to be completely diffused at high temperature, gas impurities such as C, O, H are further volatilized, the content of the gas impurities is ensured to be reduced to below 10ppm, and the sintering density can be increased. In the working procedure, the sintering temperature is not lower than 1700 ℃, and the heat preservation time is not lower than 8 hours; the temperature is too low, the driving energy in the sintering process is insufficient, the shrinkage of the pores of the material is not obvious, the heat preservation time is too short, powder particles cannot be completely diffused, the sintering neck cannot be completely grown, and the density of the material cannot be improved; the sintering temperature is not more than 2100 ℃, the temperature is not more than 16 hours, and the cost of the sintering furnace is 250 yuan/hour mainly from the production cost. With the increase of time, the manufacturing cost is increased, and the method is uneconomical, so that the sintering temperature and the heat preservation time are in a proper range.
In the third stage, sintering is carried out by adopting a hydrogen furnace, wherein the hydrogen flow is set to be 0.2m 3 /h-0.4m 3 And/h, setting the sintering temperature between 2100-2300 ℃ and maintaining for 8-16 h, during which the reduction of pore size and pore number is ensured, and the sintering density is further increased. The temperature is too high, the molybdenum powder is recrystallized in the crystallization process, so that the structure grows up, the subsequent rolling performance is influenced, and the material is reducedToughness and elongation of (3); at the same time, the temperature is not too low and the time is not too low. This is because at this stage the number of sintered pores and the size will decrease further and the density will reach the highest value; if the temperature is too low, insufficient sintering and more pores are caused, and the material is not compact. By adopting the method, the density of the prepared sintered plate blank is more than 9.5g/cm < 3 >.
S5, hot rolling:
and (3) carrying out hot rolling procedure treatment on the sintered plate blank, wherein the sintering thickness is 35mm, and the cogging temperature is 1000-1300 ℃. In the process, if the cogging temperature is lower than 1000 ℃, the deformation of the material is difficult, and the rolling is easy to crack; above 1300 ℃, the structure coarsens, which has an adverse effect on the subsequent properties.
In this step, the total working ratio is ensured to be more than 90%, and a hot-rolled slab with a thickness of 3.5mm is finally obtained, the density of which is close to the theoretical density of 10.2g/cm 3 . In the actual production process, the invention has the advantage that reversing rolling is needed when the pass processing rate is 30 percent so as to ensure that the grains in the length direction and the width direction are basically consistent.
S6, warm rolling:
preserving heat for 20-40 min at the temperature of 350-450 ℃, and the thickness of the rolled plate is 2.0mm.
S7, heat treatment:
the rolled plate is subjected to high-temperature heat treatment in a sintering furnace, the process is a key process of the whole product, a plurality of plates can be treated each time, the middle is separated by zirconium sand, the treatment temperature is 1900-2100 ℃, and the heat preservation time is kept for 9-10 h.
This step is critical and determines whether molybdenum is capable of being formed without deformation at high temperatures, so that the temperature and time must be controlled strictly to obtain a molybdenum product.
S8, machining:
and (3) carrying out grinding process treatment on the molybdenum product, wherein the thickness dimension is controlled to be +/-0.05 mm, the length and width dimensions are controlled to be +/-0.2 mm, and the flatness is controlled to be less than 0.1 mm. Because the zirconium sand adhered on the surface after molybdenum is treated at high temperature can bring away grains in the length direction under the action of shearing force when a large surface is ground, and macroscopic phenomenon is shown as slag falling phenomenon, the zirconium sand at the edge needs to be polished away firstly when grinding is carried out, so that slag falling is prevented. In addition, the grinding speed is not too high, otherwise deformation is caused, so the grinding frequency is controlled below 17Hz, the grinding feed is controlled below 0.02mm, and the grinding is performed by turning over for multiple times.
S9, low-temperature shaping:
and (3) carrying out low-temperature treatment on the polished plate in a vacuum furnace at 600-800 ℃ for 2-4 hours to eliminate the stress after grinding and ensure the flatness of the material, and finally obtaining the high-strength molybdenum.
In order to further illustrate the technical scheme of the invention, the following specific examples are provided for the purpose of illustration.
Example 1
S1, selecting raw materials:
the raw material powder is high-purity molybdenum powder with purity of more than 99.99 percent, and the content of Ca, fe, K and other impurities is controlled below 0.01 percent.
S2, mixing:
before pressing, the high-purity molybdenum powder is fully mixed by a 1000L high-energy mixer, smashed, and mixed for 2 hours at the rotating speed of 3500 r/min.
S3, isostatic pressing:
and carrying out an isostatic pressing treatment procedure to ensure that the density of the high-purity molybdenum powder is higher and uniform.
S4, sintering:
in the powder metallurgy sintering process, the invention adopts three stages to sinter.
The first stage is performed by adopting a plurality of modes such as presintering, vacuum sintering and the like, and the vacuum degree of the furnace is required to be 1.0x10 -3 Pa, the pre-sintering temperature is 800 ℃, and the pre-sintering time is kept for 4 hours.
The second stage is vacuum furnace sintering, the sintering temperature is 1700 ℃, and the sintering time is kept for 8 hours. In the heating process of the vacuum furnace, a gradient slow heating process is adopted, gas impurities such as C, O, H are further volatilized, and the content of the gas impurities is guaranteed to be reduced to below 10 ppm.
In the third stage, sintering is carried out by adopting a hydrogen furnace, wherein the hydrogen flow is set to be 0.2m 3 And/h, the sintering temperature was set between 2100℃and maintained for 8h. By adopting the method, the density of the prepared sintered plate blank is more than 9.5g/cm < 3 >.
S5, hot rolling:
the sintered slab was subjected to a hot rolling process at a sintered thickness of 35mm and a cogging temperature of 1000 ℃. In this step, the total working ratio is ensured to be more than 90%, and a hot-rolled slab with a thickness of 3.5mm is finally obtained, the density of which is close to the theoretical density of 10.1g/cm 3 。
S6, warm rolling:
preserving heat for 20min at the temperature of 350 ℃, wherein the thickness of the rolled plate is 2.0mm.
S7, heat treatment:
and (3) carrying out high-temperature heat treatment on the rolled plate in a sintering furnace, wherein a plurality of plates can be treated each time, the middle is separated by zirconium sand, the treatment temperature is 1900 ℃, and the heat preservation time is kept for 9 hours.
S8, machining:
and (3) carrying out grinding process treatment on the molybdenum product, wherein the thickness dimension is controlled to be +/-0.05 mm, the length and width dimensions are controlled to be +/-0.2 mm, and the flatness is controlled to be less than 0.1 mm. During grinding, zirconium sand at the edge is firstly ground away to prevent slag from falling. In addition, the grinding speed is not too fast, the grinding frequency is controlled below 17Hz, the grinding feed is controlled below 0.02mm, and the grinding is performed by turning over for multiple times.
S9, low-temperature shaping:
and (3) carrying out low-temperature treatment on the polished plate in a vacuum furnace at 600 ℃, and preserving heat for 2 hours to finally obtain the high-strength molybdenum.
Example 2
S1, selecting raw materials:
the raw material powder is high-purity molybdenum powder with purity of more than 99.99 percent, and the content of Ca, fe, K and other impurities is controlled below 0.01 percent.
S2, mixing:
before pressing, the high-purity molybdenum powder is fully mixed by a 1000L high-energy mixer, smashed, and mixed for 3 hours at 4000 r/min.
S3, isostatic pressing:
and carrying out an isostatic pressing treatment procedure to ensure that the density of the high-purity molybdenum powder is higher and uniform.
S4, sintering:
in the powder metallurgy sintering process, the invention adopts three stages to sinter.
The first stage is performed by adopting a plurality of modes such as presintering, vacuum sintering and the like, and the vacuum degree of the furnace is required to be 1.0x10 -3 Pa, the pre-sintering temperature is 900 ℃, and the pre-sintering temperature is kept for 7h.
The second stage is vacuum furnace sintering, the sintering temperature is 1900 ℃, and the sintering time is 12 hours. In the heating process of the vacuum furnace, a gradient slow heating process is adopted, gas impurities such as C, O, H are further volatilized, and the content of the gas impurities is guaranteed to be reduced to below 10 ppm.
In the third stage, sintering is carried out by adopting a hydrogen furnace, wherein the hydrogen flow is set to be 0.3m 3 And/h, the sintering temperature is set between 2200 ℃ and maintained for 12h. By adopting the method, the density of the prepared sintered plate blank is more than 9.5g/cm < 3 >.
S5, hot rolling:
the sintered slab was subjected to a hot rolling process at a firing temperature of 1200 ℃ at a firing thickness of 35mm. In this step, the total working ratio is ensured to be more than 90%, and a hot-rolled slab with a thickness of 3.5mm is finally obtained, the density of which is close to the theoretical density of 10.2g/cm 3 。
S6, warm rolling:
preserving the temperature for 30min at the temperature of 400 ℃, wherein the thickness of the rolled plate is 2.0mm.
S7, heat treatment:
and (3) carrying out high-temperature heat treatment on the rolled plate in a sintering furnace, wherein a plurality of plates can be treated each time, the middle is separated by zirconium sand, the treatment temperature is 2000 ℃, and the heat preservation is carried out for 9.5 hours.
S8, machining:
and (3) carrying out grinding process treatment on the molybdenum product, wherein the thickness dimension is controlled to be +/-0.05 mm, the length and width dimensions are controlled to be +/-0.2 mm, and the flatness is controlled to be less than 0.1 mm. During grinding, zirconium sand at the edge is firstly ground away to prevent slag from falling. In addition, the grinding speed is not too fast, the grinding frequency is controlled below 17Hz, the grinding feed is controlled below 0.02mm, and the grinding is performed by turning over for multiple times.
S9, low-temperature shaping:
and (3) carrying out low-temperature treatment on the polished plate in a vacuum furnace at 700 ℃, and preserving heat for 3 hours to finally obtain the high-strength molybdenum.
Example 3
S1, selecting raw materials:
the raw material powder is high-purity molybdenum powder with purity of more than 99.99 percent, and the content of Ca, fe, K and other impurities is controlled below 0.01 percent.
S2, mixing:
before pressing, the high-purity molybdenum powder is fully mixed by a 1000L high-energy mixer, smashed, and mixed for 4 hours at the rotating speed of 4500 r/min.
S3, isostatic pressing:
and carrying out an isostatic pressing treatment procedure to ensure that the density of the high-purity molybdenum powder is higher and uniform.
S4, sintering:
in the powder metallurgy sintering process, the invention adopts three stages to sinter.
The first stage is carried out by adopting a plurality of modes such as presintering, vacuum sintering and the like, wherein the vacuum degree of a furnace is 1.0x10 < -3 > Pa, the presintering temperature is 1000 ℃, and the presintering is kept for 10 hours.
And sintering in a vacuum furnace at 2100 ℃ for 16h in the second stage. In the heating process of the vacuum furnace, a gradient slow heating process is adopted, gas impurities such as C, O, H are further volatilized, and the content of the gas impurities is guaranteed to be reduced to below 10 ppm.
In the third stage, sintering is carried out by adopting a hydrogen furnace, wherein the hydrogen flow is set to be 0.4m 3 And/h, the sintering temperature is set between 2300 ℃ and maintained for 16h. By adopting the method, the density of the prepared sintered plate blank is more than 9.5g/cm < 3 >.
S5, hot rolling:
the sintered slab was subjected to a hot rolling process at a sintering thickness of 35mm and a cogging temperature of 1300 ℃. In this step, the total working ratio is ensured to be more than 90%, and a hot-rolled slab with a thickness of 3.5mm is finally obtained, the density of which is close to the theoretical density of 10.2g/cm 3 。
S6, warm rolling:
preserving heat for 40min at the temperature of 450 ℃, wherein the thickness of the rolled plate is 2.0mm.
S7, heat treatment:
and (3) carrying out high-temperature heat treatment on the rolled plate in a sintering furnace, wherein a plurality of plates can be treated each time, the middle of the plates are separated by zirconium sand, the treatment temperature is 2100 ℃, and the plates are kept for 10 hours.
S8, machining:
and (3) carrying out grinding process treatment on the molybdenum product, wherein the thickness dimension is controlled to be +/-0.05 mm, the length and width dimensions are controlled to be +/-0.2 mm, and the flatness is controlled to be less than 0.1 mm. During grinding, zirconium sand at the edge is firstly ground away to prevent slag from falling. In addition, the grinding speed is not too fast, the grinding frequency is controlled below 17Hz, the grinding feed is controlled below 0.02mm, and the grinding is performed by turning over for multiple times.
S9, low-temperature shaping:
and (3) carrying out low-temperature treatment on the polished plate in a vacuum furnace at 800 ℃, and preserving the heat for 4 hours to finally obtain the high-strength molybdenum.
The preparation method adopts high-purity molybdenum powder as raw material, ensures that the purity of the molybdenum material reaches more than 99.99 percent, thereby improving the oxidation resistance, corrosion resistance and heat resistance of molybdenum; through high-temperature sintering and hot rolling treatment, molybdenum crystals can be grown to obtain high-strength molybdenum, and the requirements of high strength and high stability of continuous use of the molybdenum are met; through low-temperature shaping treatment, the grain boundary structure of molybdenum can be optimized, so that the high-temperature characteristic of the molybdenum is improved.
As shown in table 1, the content of impurities such as Al, ca, fe, mg, ni, si, C, N, P, O in the molybdenum of the present invention is far lower than that in pure molybdenum.
TABLE 1 comparison of high strength molybdenum and ordinary pure molybdenum compositions
As shown in FIG. 2, the molybdenum prepared by the invention has smooth surface and no grain boundary as can be seen from a gold phase diagram. As shown in fig. 3, the gold phase diagram of the conventional molybdenum product is equiaxed, has grain boundaries, conventional molybdenum and impurities are easy to segregate at the grain boundaries, and when the product is used at a high temperature exceeding 1600 ℃, the structure grows up, coarsens, the grain boundaries are wider, and the grain boundaries become weak areas of the whole material, so that deformation and even cracking are easy to occur to fracture.
As such, compared with the traditional common molybdenum and molybdenum lanthanum alloy, the molybdenum prepared by the method has obviously better strength and creep resistance, and has obvious advantages as ceramic sintering supporting pieces, high-temperature furnace components, high-temperature deformation-resistant supporting pieces, high Wen Jian on aviation and aerospace and the like.
The main performance parameters of high strength molybdenum are as follows:
(1) The purity of the material is more than 99.99 percent, and the content of C, O, N in impurities is less than or equal to 10ppm;
(2) The density of molybdenum is close to the theoretical density rho and is more than or equal to 10.2g/cm < 3 >;
(3) The grain boundary of the structure is narrow under the high-temperature treatment of molybdenum, and the impurity segregation is less;
(4) After high temperature treatment at 1800 ℃, the deformation resistance is strong and is improved by more than 10 times compared with pure molybdenum.
In order to further verify the properties of the molybdenum prepared by the method of the invention, sag resistance experiments and deformation experiments were specially designed.
The anti-sagging protocol was as follows:
test sample: pure molybdenum sample No. 1, pure molybdenum sample No. 2, molybdenum lanthanum sample No. 3, molybdenum lanthanum sample No. 4, high-strength molybdenum sample No. 5 and high-strength molybdenum sample No. 6;
test sample size: a sheet material with a length of 100mm and a width of 10mm and 2 mm;
test time: 10. hours;
test temperature: 1800 ℃;
the test method comprises the following steps: an anti-deformation experiment was performed using the dead weight of the work, as shown in fig. 4, where l is the deformation amount.
Experimental results: as shown in Table 2, the deformation amount of the high-strength molybdenum prepared by the method is only 0.2. 0.2mm, and the sagging resistance of the high-strength molybdenum is improved by 10 times compared with that of pure molybdenum.
TABLE 2 high strength molybdenum to pure molybdenum, molybdenum lanthanum alloy high temperature deformation resistance comparison (sag resistance experiment)
The anti-deformation protocol was as follows:
test sample: pure molybdenum sample No. 1, pure molybdenum sample No. 2, high-strength molybdenum sample No. 3 and high-strength molybdenum sample No. 4;
test sample: thickness 2mm width 130mm height 260 mm;
test time: 3 hours;
test temperature: 1600 ℃.
Load: 98g;
the test method comprises the following steps: the test panels were supported at four corners with 4 columns of 10mm height and after 3 hours of incubation at 1600℃the flatness was measured as shown in FIG. 5.
Experimental results: as shown in table 3, the flatness of the high-strength molybdenum sample No. 3 and the high-strength molybdenum sample No. 4 were less different before and after deformation, only 0.02; the flatness of the pure molybdenum sample No. 1 and the pure molybdenum sample No. 2 change greatly before and after deformation, and reach 0.13-0.14; therefore, the high-strength molybdenum prepared by the method has better deformation resistance.
TABLE 3 results of anti-deformation test of crystalline molybdenum and pure molybdenum
In conclusion, the molybdenum prepared by the method has good sagging resistance and deformation resistance, excellent high-temperature performance and oxidation resistance, and can stably operate for a long time in a high-temperature environment. Therefore, the method can be widely used for manufacturing the working environments under high-temperature, static pressure and corrosion environments such as ceramic supporting pieces, high-temperature furnaces, vacuum furnaces, nuclear reactors and the like.
Claims (10)
1. The preparation method of the high-strength molybdenum is characterized by comprising the following steps of:
s1, selecting raw materials: selecting high-purity molybdenum powder, wherein the purity of the high-purity molybdenum powder is ensured to be more than 99.99%, and the impurity content of the high-purity molybdenum powder is ensured to be less than 0.01%;
s2, mixing: fully crushing and mixing high-purity molybdenum powder;
s3, isostatic pressing: isostatic pressing is carried out on the crushed high-purity molybdenum powder;
s4, sintering: high-temperature sintering is carried out on the high-purity molybdenum powder subjected to isostatic pressing treatment, and the sintering time is 4-10 h when the temperature is 800-1000 ℃; sintering time is 8-16 h at 1700-2100 ℃; sintering for 8-16 h at 2100-2300 ℃ to finally obtain a plate blank;
s5, hot rolling: carrying out hot rolling treatment on the plate blank, wherein the cogging temperature is 1000-1300 ℃;
s6, warm rolling: preserving heat at the temperature of 350-450 ℃ for 20-40 min, and rolling the plate blank after hot rolling treatment into a plate;
s7, heat treatment: carrying out heat treatment on the plate subjected to warm rolling treatment at 1900-2100 ℃ for 9-10 hours to obtain a high-strength product;
s8, machining: grinding the molybdenum product, wherein the thickness dimension of the molybdenum product is controlled to be +/-0.05 mm, the length and width dimensions of the molybdenum product are controlled to be +/-0.2 mm, and the flatness of the molybdenum product is controlled to be less than 0.1 mm;
s9, low-temperature shaping: the molybdenum product after grinding treatment is stored for 3 hours at 600-800 ℃ for low-temperature treatment, and finally high-strength molybdenum is obtained;
in the powder metallurgy sintering process, three stages are adopted for sintering:
the first stage is carried out by adopting a plurality of modes of pre-sintering and vacuum sintering, and the vacuum degree of the furnace is required to be 1.0x10 -3 Pa, and the presintering temperature is 800-1000 ℃;
the second stage is vacuum furnace sintering, the sintering temperature is 1700-2100 ℃, and a gradient slow heating process is adopted in the heating process of the vacuum furnace, so that the high-purity molybdenum powder is ensured to be completely diffused at high temperature, gas impurities such as C, O, H are further volatilized, the content of the gas impurities is ensured to be reduced to below 10ppm, and the sintering density can be increased;
in the third stage, sintering is carried out by adopting a hydrogen furnace, wherein the hydrogen flow is set to be 0.2m 3 /h-0.4m 3 /h。
2. The method for preparing high-strength molybdenum according to claim 1, wherein the impurities of the high-purity molybdenum powder in S1 include Ca, fe, and K.
3. The method for preparing high-strength molybdenum according to claim 1, wherein the specific process of S2 is: and crushing and fully mixing large-particle agglomerated molybdenum powder particles in the high-purity molybdenum powder by adopting a high-energy mixer, wherein the rotating speed of the high-energy mixer is 3500r/min-4500r/min, and the mixing time is 2h-4h.
4. A method of producing high strength molybdenum as defined in claim 3, wherein the high energy blender is a 1000L high energy blender.
5. The method for preparing high-strength molybdenum according to claim 1, wherein the step S4 is divided into three stages for sintering;
the first stage is carried out by adopting a mode comprising presintering and vacuum sintering, wherein the vacuum degree of the furnace is required to be 1.0x10 -3 Pa, pre-sintering temperature is 800-1000 ℃, and sintering time is 4-10 h;
the second stage is vacuum furnace sintering, gradient slow heating is adopted, and sintering time is 8-16 h when sintering temperature is 1700-2100 ℃;
and in the third stage, sintering is carried out by adopting a hydrogen furnace, wherein the hydrogen flow is 0.3m < 3 >/h, and the sintering time is 8-16 h when the sintering temperature is 2100-2300 ℃ to obtain a sintered plate blank.
6. The method for preparing high-strength molybdenum according to claim 1, wherein the thickness of the slab in S5 is 35mm.
7. The method for preparing high-strength molybdenum according to claim 1, wherein the thickness of the sheet rolled in S6 is 2mm.
8. The method for preparing high-strength molybdenum according to claim 1, wherein the heat-treated plates in S7 are separated by zircon sand.
9. The method for preparing high-strength molybdenum according to claim 1, wherein the frequency of the grinding treatment in S8 is controlled below 17Hz, the feed rate of the grinding treatment is controlled below 0.02mm, and the high-strength molybdenum is subjected to multiple turn-over grinding.
10. The method for preparing high-strength molybdenum according to claim 1, wherein the low-temperature treatment is performed in a vacuum furnace in S9.
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