CN108145157B - Preparation method of high-performance molybdenum-rhenium alloy bar - Google Patents
Preparation method of high-performance molybdenum-rhenium alloy bar Download PDFInfo
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- CN108145157B CN108145157B CN201711424694.1A CN201711424694A CN108145157B CN 108145157 B CN108145157 B CN 108145157B CN 201711424694 A CN201711424694 A CN 201711424694A CN 108145157 B CN108145157 B CN 108145157B
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- YUSUJSHEOICGOO-UHFFFAOYSA-N molybdenum rhenium Chemical compound [Mo].[Mo].[Re].[Re].[Re] YUSUJSHEOICGOO-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910000691 Re alloy Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 46
- 238000005096 rolling process Methods 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 238000005245 sintering Methods 0.000 claims abstract description 36
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 28
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000137 annealing Methods 0.000 claims abstract description 25
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 239000011733 molybdenum Substances 0.000 claims abstract description 15
- 238000000748 compression moulding Methods 0.000 claims abstract description 5
- 238000005303 weighing Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000011049 filling Methods 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 49
- 239000001257 hydrogen Substances 0.000 claims description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 33
- 230000009467 reduction Effects 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 19
- HRLYFPKUYKFYJE-UHFFFAOYSA-N tetraoxorhenate(2-) Chemical compound [O-][Re]([O-])(=O)=O HRLYFPKUYKFYJE-UHFFFAOYSA-N 0.000 claims description 19
- 238000003754 machining Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 238000009694 cold isostatic pressing Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- 239000000956 alloy Substances 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 description 26
- 238000012545 processing Methods 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000009864 tensile test Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000007514 turning Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 229910001182 Mo alloy Inorganic materials 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- ULSAYCVVCOFSKH-UHFFFAOYSA-N N.[Re+4] Chemical compound N.[Re+4] ULSAYCVVCOFSKH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
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- B22F1/0003—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/18—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
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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
- 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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/18—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
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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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Abstract
The invention relates to a high-performance molybdenum-rhenium alloy bar which comprises the following components in percentage by mass: 5-50% of rhenium and the balance of molybdenum; the preparation method of the high-performance molybdenum-rhenium alloy bar sequentially comprises the following steps: step one, respectively weighing a molybdenum source and a rhenium source according to the component proportion of a molybdenum-rhenium alloy bar, and carrying out pretreatment to obtain molybdenum-rhenium alloy powder; secondly, filling molybdenum-rhenium alloy powder into a designed die cavity for compression molding treatment to obtain a pressed blank; step three, carrying out high-temperature sintering treatment on the pressed compact in reducing atmosphere, inert gas or vacuum condition to obtain a sintered blank; step four, carrying out rolling deformation treatment on the sintered blank to obtain a rolled bar blank; and fifthly, carrying out annealing heat treatment on the rolled bar billet to obtain the high-performance molybdenum-rhenium alloy bar. The molybdenum-rhenium alloy material prepared by the preparation method provided by the invention has the advantages of fine and uniform crystal grains, high density and high strength.
Description
Technical Field
The invention belongs to the technical field of powder metallurgy, and particularly relates to a preparation method of a high-performance molybdenum-rhenium alloy bar.
Background
The rhenium element is added into the pure molybdenum, so that the low-temperature brittleness of the molybdenum alloy can be improved, the recrystallization temperature can be increased, the room-temperature plasticity and the high-temperature strength can be improved, the plastic-brittleness transition temperature can be reduced, the machining performance of the material can be obviously improved, and the rhenium-based molybdenum alloy is more and more widely applied in the fields of aerospace, electronics, semiconductors, high-temperature furnace heating components and the like.
The current research on molybdenum-rhenium alloys is mainly focused on foils and pipes. Patent CN201310028339.8 and patent CN201410033997.0 respectively disclose a process for preparing molybdenum-rhenium alloy foil by a powder metallurgy method. Patent CN201610576775.2 discloses a method for preparing a molybdenum-rhenium tube, which comprises turning a molybdenum-rhenium billet to obtain a molybdenum-rhenium tube blank, and sintering and forging the molybdenum-rhenium tube blank to obtain a molybdenum-rhenium alloy tube. Although the method has simple process, the method cannot meet the requirements of molybdenum-rhenium alloy bars with different rhenium contents, large sizes and large single weight, and cannot meet the requirements of high compactness and high performance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the preparation method of the high-performance molybdenum-rhenium alloy bar, and the prepared molybdenum-rhenium alloy material has the advantages of fine and uniform grains, high density and high strength by adopting a powder metallurgy process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-performance molybdenum-rhenium alloy bar comprises the following components in percentage by mass: 5-50% of rhenium and the balance of molybdenum (namely the mass fraction of molybdenum is 50-95%).
The high-performance molybdenum-rhenium alloy bar consists of the following components in percentage by mass: rhenium accounts for 14-47.5% (such as 14%, 35%, 41%, 42%, 47.5%) and the balance molybdenum (namely the mass fraction of molybdenum is 52.5-86%).
The preparation method of the high-performance molybdenum-rhenium alloy bar sequentially comprises the following steps of:
step one, preparing molybdenum-rhenium alloy powder: respectively weighing a molybdenum source and a rhenium source according to the component proportion of the molybdenum-rhenium alloy bar, and carrying out pretreatment to obtain molybdenum-rhenium alloy powder;
step two, compression molding treatment: filling the molybdenum-rhenium alloy powder obtained in the step one into a designed die cavity according to the designed weight, and performing compression molding treatment to obtain a pressed blank;
step three, high-temperature sintering treatment: carrying out high-temperature sintering treatment on the pressed blank obtained in the step two under the reducing atmosphere, inert gas or vacuum condition to obtain a sintered blank;
step four, rolling deformation treatment: carrying out rolling deformation treatment on the sintered blank obtained in the step three to obtain a rolled bar blank;
step five, annealing heat treatment: and carrying out annealing heat treatment on the rolled bar billet obtained in the fourth step to obtain the high-performance molybdenum-rhenium alloy bar.
The preparation method of the invention has the technical principle that: on one hand, molybdenum powder and ammonium rhenate powder are mixed, and proper reduction technology is adopted to prepare molybdenum-rhenium pre-alloy powder with special proportion; on the other hand, the single-fire large-deformation densification treatment of the alloy is realized through a continuous rolling deformation process, and compared with a free forging process, the method has the advantages of fine grains, high density and high qualified rate.
In the above preparation method, as a preferred embodiment, the preparation method further includes a machining step of machining the heat-treated high-performance molybdenum-rhenium alloy rod to obtain a finished high-performance molybdenum-rhenium alloy rod.
In the above preparation method, as a preferred embodiment, the molybdenum source is molybdenum powder, the rhenium source is ammonium rhenate powder or rhenium powder, the rhenium source is preferably ammonium rhenate, and ammonium rhenate is used as a rhenium source, so that the prepared molybdenum-rhenium pre-alloy powder is more uniform and consistent; the rhenium powder can also be directly used as a source for directly mixing materials, but the uniformity of the powder is not as good as that of the reduction process of the ammonium rhenate and the molybdenum powder. Further preferably, the Ferris particle size of the molybdenum source is 2.0-5.0 μm (such as 2.2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 4.8 μm).
In the above production method, as a preferred embodiment, in the first step, when the rhenium source is ammonium rhenate powder, the pretreatment includes a mixing treatment and a reduction treatment in this order; more preferably, the mixing time of the mixing treatment is 0.5-3h (such as 0.6h, 0.8h, 1.2h, 1.5h, 2h, 2.5h and 2.8h), the rotating speed is 10-25r/min (such as 12r/min, 15r/min, 18r/min, 20r/min and 23r/min), and the main effect of the mixing treatment is primary homogenization of raw materials, so that the alloy components can be more uniform; further preferably, the reduction treatment sequentially comprises: a first hydrogen reduction treatment and a second hydrogen reduction treatment; wherein the first hydrogen reduction treatment is carried out at 300-500 deg.C (such as 305 deg.C, 310 deg.C, 330 deg.C, 360 deg.C, 400 deg.C, 430 deg.C, 450 deg.C, 470 deg.C, 485 deg.C, 495 deg.C) for 20-60min (such as 22min, 25min, 30min, 40min, 50min, 55min, 58 min); the temperature of the second hydrogen reduction treatment is 700-900 ℃ (such as 705 ℃, 715 ℃, 730 ℃, 750 ℃, 780 ℃, 820 ℃, 850 ℃, 880 ℃, 890 ℃ and 895 ℃) and the time is 20-60min (such as 22min, 25min, 30min, 40min, 50min, 55min and 58 min); further preferably, in the first hydrogen reduction treatment and the second hydrogen reduction treatment, the hydrogen flow rate is 3-10L/min (for example, 3.5L/min, 4L/min, 5L/min, 6L/min, 7L/min, 8L/min, 9L/min, 9.5L/min). The molybdenum-rhenium pre-alloy powder prepared by adopting the multi-step reduction process is more beneficial to improving the uniformity of the powder.
In the preparation method, for the feasibility of subsequent processes, the particle size of the ammonium rhenate powder is-150 to-400 meshes (such as-200, -250, -300 and-350) as a preferred embodiment; the Fisher particle size of the rhenium powder is-150 to-400 meshes (such as-200, -250, -300 and-350). When the raw material powder is too fine, the moldability is poor, and when it is too coarse, the sintered density is low.
In the above preparation method, as a preferred embodiment, when the rhenium source is rhenium powder, the pretreatment is a mixing treatment; more preferably, the mixing time of the mixing treatment is 0.5-4h (such as 0.6h, 0.8h, 1.2h, 1.5h, 2h, 2.5h, 2.8h, 3h, 3.5h, 3.9h), and the rotation speed is 10-25r/min (such as 12r/min, 15r/min, 18r/min, 20r/min, 23 r/min).
In the above production method, as a preferred embodiment, in the second step, the press forming is a cold isostatic press forming process; more preferably, the cold isostatic pressing treatment has a pressing pressure of 150 to 250MPa (such as 155MPa, 165MPa, 180MPa, 200MPa, 220MPa, 240MPa and 245MPa), a dwell time of 0 to 30s (such as 2s, 5s, 10s, 15s, 20s, 25s and 28s), and cannot be formed when the pressure is too low, and cracks are easily generated when the pressure is too high; preferably, the relative density of the molded blank is 55-65% (such as 56%, 58%, 60%, 62%, 64%), and the relative density of the molded blank is not too high, otherwise, the subsequent sintering process is not favorable for exhausting and removing impurities.
In the above preparation method, as a preferred embodiment, in step three, the high-temperature sintering treatment is performed in a reducing atmosphere, and may be further performed by exhausting and removing impurities, and may be performed under an inert gas or vacuum condition, but the exhausting and removing impurities are not as effective as in the reducing atmosphere; more preferably, the sintering treatment is carried out in a hydrogen atmosphere, wherein the hydrogen has the functions of reduction, degassing and impurity removal, and moreover, the sintering hydrogen also has the functions of protection and workpiece oxidation prevention, and the hydrogen is cheap and widely used; further preferably, the flow rate of the hydrogen is 20-60L/min (such as 22L/min, 25L/min, 30L/min, 35L/min, 40L/min, 45L/min, 50L/min, 55L/min, 58L/min).
In the above preparation method, as a preferred embodiment, in step three, in the sintering treatment, the sintering temperature is 1950-2350 ℃ (such as 1960 ℃, 1980 ℃, 2000 ℃, 2020 ℃, 2050 ℃, 2100 ℃, 2150 ℃, 2200 ℃, 2250 ℃, 2300 ℃, 2330 ℃ and 2345 ℃), and the holding time is 3-6 h (such as 3.2h, 3.5h, 4h, 4.5h, 5h, 5.5h and 5.8 h); preferably, the relative density of the sintered blank is more than or equal to 90 percent, namely the density of the sintered blank reaches more than 90 percent of the theoretical density. In the step, if the sintering temperature is too low, the density of the sintered blank is insufficient, which is not beneficial to subsequent deformation processing, and if the sintering temperature is too high, the crystal grains are easy to grow up, and the product cost is increased sharply.
In the above manufacturing method, as a preferred embodiment, the rolling deformation treatment in the fourth step includes a heating treatment and a rolling treatment in this order, the heating temperature of the heating treatment is 1300 to 1500 ℃ (such as 1320 ℃, 1350 ℃, 1400 ℃, 1420 ℃, 1450 ℃, 1475 ℃ and 1490 ℃), and the holding time is 20 to 90min (such as 25min, 30min, 45min, 60min, 75min and 85 min); during rolling treatment, the initial rolling temperature is the heating temperature of the heating treatment, the rolling speed is 1-2.5 m/s (such as 1.2m/s, 1.5m/s, 1.8m/s, 2m/s and 2.3m/s), the rolling pass is 5-12 passes (such as 6 passes, 7 passes, 8 passes, 9 passes, 10 passes and 11 passes), and the total rolling deformation is not less than 60%. The pass deformation is moderate, and if the pass deformation is too large, the deformation resistance is increased, so that the bar material is clamped in the roller, the smooth rolling cannot be realized, or the blank is torn; preferably, the first pass deformation is 30-40% (e.g., 32%, 34%, 36%, 38%), the last pass deformation is 8-12% (e.g., 9%, 10%, 11%), and the intermediate pass deformation is gradually reduced; more preferably, the first pass deformation is 34-36%, the last pass deformation is 10%, and the intermediate pass deformation is gradually reduced. The deformation in the application refers to the deformation of the cross section area of the bar, namely: the deformation amount is (cross-sectional area before rolling-sectional area after rolling)/cross-sectional area before rolling. The main purpose of continuous rolling is to refine the grains, reduce the number of thermal cycles in deformation processing and avoid the occurrence of recrystallization behavior in processing.
In the above preparation method, as a preferred embodiment, in the annealing heat treatment in the fifth step, the annealing temperature is 800 to 1400 ℃ (such as 850 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃), and the heat preservation time is 30 to 120min (such as 35min, 50min, 60min, 80min, 90min, 100min, 110min, 115 min). The annealing heat treatment mainly aims at removing internal stress caused by rolling deformation, the stress can not be eliminated when the temperature is too low, and crystal grain growth is easy to occur when the temperature is too high.
Compared with the prior art, the invention has the following beneficial effects:
1) the molybdenum-rhenium alloy provided by the invention has the excellent performances of fine grains, uniform structure, high compactness, high strength and the like;
2) according to the preparation method, on one hand, molybdenum powder and rhenium ammonium acid powder are preferably mixed and reduced to prepare molybdenum-rhenium alloy powder, so that the preparation of more uniform mixed powder is realized; on the other hand, the single-fire large-deformation densification treatment of the alloy is realized through a continuous rolling deformation process, and the effects of fine grains, high density and uniform and consistent structure are realized. The molybdenum-rhenium alloy material prepared by the preparation method provided by the invention has the advantages of fine and uniform crystal grains, high density and high strength.
Drawings
FIG. 1 is a cross-sectional metallographic structure photograph of a high-performance molybdenum-rhenium alloy bar prepared by the preparation method provided by the invention;
FIG. 2 is a longitudinal cross-sectional metallographic structure photograph of a high-performance molybdenum-rhenium alloy bar prepared by the preparation method provided by the invention.
Detailed Description
The molybdenum-rhenium alloy bar and the preparation method thereof are described below with reference to the accompanying drawings and examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. It should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the appended claims.
The starting materials used in the following examples are all commercially available.
Example 1
(1) Preparation of molybdenum-rhenium alloy powder: weighing 38000g of molybdenum powder with a Fisher particle size of 3.4 mu m and a purity of 99.95 percent and 2880g of ammonium rhenate powder with a purity of 99.99 percent and sieved by a 200-mesh sieve respectively, and then adding the ammonium rhenate powder into a mixer filled with the molybdenum powder for mixing at a rotation speed of 20r/min for 1 hour; after being mixed evenly, the mixture is subjected to first hydrogen reduction treatment, namely, the mixture reacts for 40min at the temperature of 420 ℃; then carrying out second hydrogen reduction treatment, namely reacting for 35min at 850 ℃; in the hydrogen reduction treatment process, the hydrogen flow is 7L/min; after completion of the reduction reaction, 40000g of molybdenum-rhenium alloy powder (Mo-5Re) was obtained.
(2) Cold isostatic pressing: 40000g of the molybdenum-rhenium alloy powder prepared in the step (1) is placed in a die, and then the pressure is maintained for 20s under the pressure of 200MPa, so that a forming blank with the relative density of 60% is obtained.
(3) And (3) high-temperature sintering: and (3) sintering the formed blank obtained in the step (2) in a medium-frequency high-temperature hydrogen sintering furnace, wherein the flow rate of hydrogen is 30L/min, the highest sintering temperature is 2320 ℃, and the temperature is kept at the highest temperature for 6 hours to obtain a sintered blank with the relative density of 93% and the diameter of 85 mm.
(4) Rolling deformation processing: and (4) carrying out rolling deformation processing on the sintered blank obtained in the step (3), wherein the heating temperature is 1350 ℃, the heat preservation time is 60min, then carrying out 6-pass continuous rolling to obtain a rolled blank with the diameter of 40mm, the rolling speed is 2m/s, the first-pass deformation is 35%, the last-pass deformation is 10%, and the intermediate-pass deformation is gradually reduced.
(5) Annealing heat treatment: and (4) placing the rolled blank obtained in the step (4) in a hydrogen protection heating furnace for annealing heat treatment, wherein the annealing temperature is 900 ℃, and the heat preservation time is 50 min.
(6) And (3) machining: and (5) machining the bar blank obtained in the step (5), and turning off oxide skins on the surface to obtain the required high-performance molybdenum-rhenium alloy bar.
Fig. 1 is a cross-sectional metallographic structure photograph of the high-performance molybdenum-rhenium alloy bar prepared in this embodiment, and fig. 2 is a longitudinal-sectional metallographic structure photograph of the high-performance molybdenum-rhenium alloy bar prepared in this embodiment, and it can be seen from the photographs that the molybdenum-rhenium layer has fine and uniform grains and forms an obvious fibrous structure in the longitudinal direction. After a tensile test (the room temperature tensile test is carried out according to GB/T228.1-2010 part 1 room temperature test method of the metal material tensile test), and the high temperature tensile test is carried out according to GB/T4338-; the tensile strength at high temperature of 1600 ℃ reaches 90MPa, and the elongation is 35 percent; the average density was 10.38g/cm3(ii) a The qualification rate of the experimental production is 98 percent.
Example 2
(1) Preparation of molybdenum-rhenium alloy powder: respectively weighing 25800g of molybdenum powder with Fisher granularity of 4.0 mu m and purity of 99.95 percent and 6048g of ammonium rhenate powder with purity of 99.99 percent, which is ground and sieved by a 200-mesh sieve, and then adding the ammonium rhenate powder into a mixer filled with the molybdenum powder for mixing at the rotating speed of 15r/min for 1 hour; after being uniformly mixed, the mixture is subjected to first hydrogen reduction treatment, namely reaction at 400 ℃ for 35min, and then subjected to second hydrogen reduction treatment, namely reaction at 800 ℃ for 45 min; in the hydrogen reduction treatment process, the hydrogen flow is 6L/min. After the reduction reaction was completed, 30000g of molybdenum-rhenium alloy powder (i.e., Mo-14Re) was obtained.
(2) Cold isostatic pressing: 30000g of the molybdenum-rhenium alloy powder prepared in the step (1) is placed into a die, and then the pressure is maintained for 10s under the pressure of 250MPa, so that a forming blank with the relative density of 65% is obtained.
(3) And (3) high-temperature sintering: and (3) sintering the formed blank obtained in the step (2) in a medium-frequency high-temperature hydrogen sintering furnace, wherein the flow rate of hydrogen is 50L/min, the highest sintering temperature is 2250 ℃, and the temperature is kept at the highest temperature for 5 hours to obtain a sintered blank with the relative density of 92% and the diameter of 60 mm.
(4) Rolling deformation processing: and (4) carrying out rolling deformation processing on the sintered blank obtained in the step (3), wherein the heating temperature is 1400 ℃, the heat preservation time is 50min, then carrying out 7-pass continuous rolling to obtain a rolled blank with the diameter of 20mm, the rolling speed is 1.8m/s, the deformation of the first pass is 32%, the deformation of the last pass is 12%, and the deformation of the middle pass is gradually reduced.
(5) Annealing heat treatment: and (4) placing the rolled blank obtained in the step (4) in a hydrogen protection heating furnace for annealing heat treatment, wherein the annealing temperature is 1000 ℃, and the temperature is kept for 45 min.
(6) And (3) machining: and (5) machining the bar blank obtained in the step (5), and turning off oxide skins on the surface to obtain the required high-performance molybdenum-rhenium alloy bar.
The metallographic structure of the bar prepared in this example was similar to that of the bar prepared in example 1. Through tensile test, the tensile strength at room temperature reaches 750MPa, the elongation is 25 percent, and the tensile strength at high temperature of 1600 ℃ reaches 105MPa and the elongation is 38 percent; mean densityThe degree is 10.9g/cm3(ii) a The qualification rate of the experimental production is 95 percent.
Example 3
(1) Preparation of molybdenum-rhenium alloy powder: 13000g of molybdenum powder with Fisher particle size of 3.0 mu m and purity of 99.95 percent and 10080g of ammonium rhenate powder with purity of 99.99 percent, which is ground and sieved by a 200-mesh sieve, are respectively weighed, and then the ammonium rhenate powder is added into a mixer filled with the molybdenum powder for mixing at the rotating speed of 25r/min for 2 hours; after being uniformly mixed, the mixture is subjected to first hydrogen reduction treatment, namely reaction at 450 ℃ for 45min, and then subjected to second hydrogen reduction treatment, namely reaction at 750 ℃ for 35 min; in the hydrogen reduction treatment process, the hydrogen flow is 10L/min. After the reduction reaction was completed, 20000g of molybdenum-rhenium alloy powder (i.e., Mo-35Re) was obtained.
(2) Cold isostatic pressing: 20000g of the molybdenum-rhenium alloy powder prepared in the step (1) is placed in a die, and then the pressure is maintained for 20s under the pressure of 180MPa, so that a forming blank with the relative density of 62% is obtained.
(3) And (3) high-temperature sintering: and (3) sintering the formed blank obtained in the step (2) in a medium-frequency high-temperature hydrogen sintering furnace, wherein the flow rate of hydrogen is 60L/min, the highest sintering temperature is 2320 ℃, and the temperature is kept at the highest temperature for 6 hours to obtain a sintered blank with the relative density of 95% and the diameter of 50 mm.
(4) Rolling deformation processing: and (4) carrying out rolling deformation processing on the sintered blank obtained in the step (3), wherein the heating temperature is 1450 ℃, the heat preservation time is 60min, then carrying out 8-pass continuous rolling to obtain a rolled blank with the diameter of 30mm, the rolling speed is 1.5m/s, the deformation of the first pass is 38%, the deformation of the last pass is 10%, and the deformation of the middle pass is gradually reduced.
(5) Annealing heat treatment: and (4) placing the rolled bar billet obtained in the step (4) in a hydrogen protection heating furnace for annealing heat treatment, wherein the annealing temperature is 1200 ℃, and the heat preservation time is 60 min.
(6) And (3) machining: and (5) machining the bar blank obtained in the step (5), and turning off oxide skins on the surface to obtain the required high-performance molybdenum-rhenium alloy bar.
The metallographic structure of the bar prepared in this example was similar to that of the bar prepared in example 1. Through a tensile testTesting, wherein the room temperature tensile strength is 1150MPa, and the elongation is 35%; the tensile strength at high temperature of 1600 ℃ reaches 115MPa, and the elongation is 42%; the average density was 12.40g/cm3(ii) a The qualified rate of the experimental production is 92 percent.
Example 4
(1) Preparation of molybdenum-rhenium alloy powder: 8400g of molybdenum powder with Fisher granularity of 4.0 mu m and purity of 99.95 percent and 10944g of ammonium rhenate powder with purity of 99.99 percent, which is ground and sieved by a 200-mesh sieve, are respectively weighed, and then the ammonium rhenate powder is added into a mixer filled with the molybdenum powder to be mixed at the rotating speed of 25r/min for 1 hour; after being uniformly mixed, the mixture is subjected to first hydrogen reduction treatment, namely reaction at 400 ℃ for 50min, and then subjected to second hydrogen reduction treatment, namely reaction at 850 ℃ for 40 min; in the hydrogen reduction treatment process, the hydrogen flow is 3L/min. After the reduction reaction was completed, 16000g of molybdenum-rhenium alloy powder (i.e., Mo-47.5Re) was obtained.
(2) Cold isostatic pressing: firstly, 16000g of the molybdenum-rhenium alloy powder prepared in the step (1) is placed into a die, and then the pressure is maintained for 10s under the pressure of 200MPa, so that a forming blank with the relative density of 65% is obtained.
(3) And (3) high-temperature sintering: and (3) sintering the molded blank obtained in the step (2) in a medium-frequency high-temperature hydrogen sintering furnace, wherein the flow rate of hydrogen is 60L/min, the highest sintering temperature is 2350 ℃, and the temperature is kept at the highest temperature for 6 hours to obtain a sintered rod blank with the relative density of 95% and the diameter of 40 mm.
(4) Rolling deformation processing: and (4) carrying out rolling deformation processing on the sintered bar blank obtained in the step (3), wherein the heating temperature is 1500 ℃, the heat preservation time is 45min, then carrying out 8-pass continuous rolling to obtain a rolled blank with the diameter of 15mm, the rolling speed is 2.2m/s, the deformation of the first pass is 30%, the deformation of the last pass is 8%, and the deformation of the middle pass is gradually reduced.
(5) Annealing heat treatment: and (4) placing the rolled blank obtained in the step (4) in a hydrogen protection heating furnace for annealing heat treatment, wherein the annealing temperature is 1350 ℃, and the temperature is kept for 30 min.
(6) And (3) machining: and (5) machining the bar blank obtained in the step (5), and turning off oxide skins on the surface to obtain the required high-performance molybdenum-rhenium alloy bar.
The metallographic structure of the bar prepared in this example was similar to that of the bar prepared in example 1. Through tensile test, the room temperature tensile strength is 1200MPa, the elongation is 38 percent, and the high temperature tensile strength at 1600 ℃ reaches 120MPa, and the elongation is 45 percent; the average density was 13.4g/cm3(ii) a The qualified rate of the experimental production is 90 percent.
Examples 5 to 7
The processes and parameters of examples 5 to 7 were the same as those of example 2, except that the high-temperature sintering process was different from that of example 2. See table 1 for the high temperature sintering process and rod properties for examples 5-7.
TABLE 1 high temperature sintering Process conditions and Bar Properties of examples 5-7
Examples 8 to 12
The processes and parameters of examples 8 to 12 were the same as those of example 2, except that the rolling deformation process was different from that of example 2. The rolling deformation process of examples 8-12 is shown in Table 2, and the properties of the rods produced in examples 8-12 are shown in Table 3.
TABLE 2 Rolling deformation Process conditions for examples 8-12
Table 3 properties of bars prepared in examples 8-12
Examples 13 to 15
The processes and parameters of examples 13 to 15 were the same as those of example 2 except that the annealing heat treatment process was different from that of example 2. See table 4 for the annealing heat treatment process and bar properties for examples 13-15.
TABLE 4 annealing Heat treatment Process conditions and Bar Properties of examples 13-15
Claims (15)
1. The preparation method of the high-performance molybdenum-rhenium alloy bar is characterized in that the molybdenum-rhenium alloy bar comprises the following components in percentage by mass: 5-50% of rhenium and the balance of molybdenum;
the preparation method sequentially comprises the following steps:
step one, preparing molybdenum-rhenium alloy powder: respectively weighing a molybdenum source and a rhenium source according to the component proportion of the molybdenum-rhenium alloy bar, and carrying out pretreatment to obtain molybdenum-rhenium alloy powder;
step two, compression molding treatment: filling the molybdenum-rhenium alloy powder obtained in the step one into a designed die cavity according to the designed weight, and performing compression molding treatment to obtain a pressed blank;
step three, high-temperature sintering treatment: carrying out high-temperature sintering treatment on the pressed blank obtained in the step two under the reducing atmosphere, inert gas or vacuum condition to obtain a sintered blank;
step four, rolling deformation treatment: carrying out rolling deformation treatment on the sintered blank obtained in the step three to obtain a rolled bar blank;
step five, annealing heat treatment: annealing heat treatment is carried out on the rolled bar billet obtained in the fourth step, so that the high-performance molybdenum-rhenium alloy bar is obtained;
in the fourth step, the rolling deformation treatment sequentially comprises heating treatment and rolling treatment; the heating temperature of the heating treatment is 1300-1500 ℃, and the heat preservation time is 20-90 min; during rolling treatment, the initial rolling temperature is the heating temperature of the heating treatment, the rolling speed is 1-2.5 m/s, the rolling passes are 5-12 passes, the total rolling deformation is not less than 60%, the first pass deformation is 30-40%, the last pass deformation is 8-12%, and the intermediate pass deformation is gradually reduced.
2. The preparation method of claim 1, wherein the high-performance molybdenum-rhenium alloy bar consists of the following components in percentage by mass: 14-47.5% of rhenium, and the balance of molybdenum.
3. The preparation method according to claim 1 or 2, characterized by further comprising a machining step of machining the high-performance molybdenum-rhenium alloy bar subjected to the annealing heat treatment to obtain a finished high-performance molybdenum-rhenium alloy bar.
4. The production method according to claim 1 or 2, wherein the molybdenum source is molybdenum powder, and the rhenium source is ammonium rhenate powder or rhenium powder.
5. The preparation method of the ammonium rhenate powder of the catalyst of claim 4, wherein the ammonium rhenate powder is undersize powder, and the mesh number of the screen is 150-400 meshes; the rhenium powder is undersize powder, and the mesh number of the screen is 150-400 meshes; the Ferris particle size of the molybdenum source is 2.0-5.0 mu m.
6. The preparation method according to claim 4, wherein in the first step, when the rhenium source is ammonium rhenate powder, the pretreatment sequentially comprises a mixing treatment and a reduction treatment; the mixing time of the mixing treatment is 0.5-3h, and the rotating speed is 10-25 r/min; the reduction treatment sequentially comprises: a first hydrogen reduction treatment and a second hydrogen reduction treatment; wherein the temperature of the first hydrogen reduction treatment is 300-500 ℃, and the time is 20-60 min; the temperature of the second hydrogen reduction treatment is 700-900 ℃, and the time is 20-60 min.
7. The preparation method according to claim 6, wherein the hydrogen flow rate in the first hydrogen reduction treatment and the second hydrogen reduction treatment is 3 to 10L/min.
8. The preparation method according to claim 7, characterized in that after the reduction treatment is completed, a second mixing treatment is carried out, the mixing time is 4-8h, and the rotating speed is 10-30 r/min; the second mixing treatment is carried out by a double-motion mixer.
9. The preparation method according to claim 4, wherein in the first step, when the rhenium source is rhenium powder, the pretreatment is a mixing treatment; the mixing time of the mixing treatment is 0.5-3h, and the rotating speed is 10-25 r/min.
10. The production method according to claim 1 or 2, wherein in the second step, the press forming is a cold isostatic press forming process; the pressing pressure of the cold isostatic pressing treatment is 150-250 MPa, and the pressure maintaining time is 0-30 s.
11. The method according to claim 10, wherein the green compact has a relative density of 55 to 65%.
12. The preparation method according to claim 1 or 2, wherein in the third step, the sintering treatment is performed in a hydrogen atmosphere, and the flow rate of the hydrogen is 20-60L/min; in the sintering treatment, the sintering temperature is 1950-2350 ℃, and the heat preservation time is 3-6 h.
13. The method according to claim 12, wherein the relative density of the sintered compact is 90% or more.
14. The method according to claim 1 or 2, wherein in the fourth step, the rolling process is performed such that the first pass deformation is 34-36%, the last pass deformation is 10%, and the intermediate pass deformation is gradually reduced.
15. The preparation method according to claim 1 or 2, wherein in the fifth step, the annealing temperature is 800 to 1400 ℃ and the heat preservation time is 30 to 120 min.
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| CN110000387B (en) * | 2019-05-20 | 2021-06-01 | 安泰天龙钨钼科技有限公司 | Large-size fine-grain tungsten rod and two-roller rolling preparation method thereof |
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| CN111020330B (en) * | 2019-12-13 | 2021-06-01 | 安泰天龙钨钼科技有限公司 | Preparation method of molybdenum-rhenium alloy section bar |
| CN111112641A (en) * | 2019-12-16 | 2020-05-08 | 重庆材料研究院有限公司 | Preparation method of nano molybdenum-rhenium alloy powder |
| CN111155017B (en) * | 2020-01-21 | 2021-12-10 | 安泰天龙钨钼科技有限公司 | Molybdenum-rhenium alloy gradient material and preparation method thereof |
| CN111155018B (en) * | 2020-01-21 | 2021-12-10 | 安泰天龙钨钼科技有限公司 | Preparation method of molybdenum-rhenium alloy gradient material |
| CN114934260B (en) * | 2022-05-23 | 2024-02-13 | 安泰天龙钨钼科技有限公司 | Molybdenum alloy target material and preparation method and application thereof |
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