CN110184519B - Preparation method of large-diameter special-shaped thin-wall tubular molybdenum-based alloy part - Google Patents
Preparation method of large-diameter special-shaped thin-wall tubular molybdenum-based alloy part Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 107
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 105
- 239000011733 molybdenum Substances 0.000 title claims abstract description 105
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 133
- 238000009987 spinning Methods 0.000 claims abstract description 41
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 36
- 238000005245 sintering Methods 0.000 claims abstract description 31
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 48
- 239000002131 composite material Substances 0.000 claims description 35
- -1 rare earth lanthanum nitrate Chemical class 0.000 claims description 35
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 35
- 238000000137 annealing Methods 0.000 claims description 32
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 20
- 238000003754 machining Methods 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 238000009659 non-destructive testing Methods 0.000 claims description 10
- 238000009694 cold isostatic pressing Methods 0.000 claims description 9
- 238000005056 compaction Methods 0.000 claims description 7
- 238000013329 compounding Methods 0.000 claims description 7
- 230000006698 induction Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 230000002950 deficient Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000000280 densification Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 238000005242 forging Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000004663 powder metallurgy Methods 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 238000002679 ablation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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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
-
- 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
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
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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
- B22F3/1017—Multiple heating or additional steps
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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
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- 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
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
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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
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- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
- B22F5/106—Tube or ring forms
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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
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
The invention relates to a preparation method of a large-diameter special-shaped thin-wall tubular molybdenum-based alloy part, which is characterized by sequentially comprising the following steps of: (1) selecting materials; (2) pretreating powder; (3) forming a prefabricated blank; (4) pre-sintering; (5) hot isostatic pressing densification; (6) spinning and forming; (7) and carrying out integral heat treatment and the like. The large-diameter special-shaped thin-wall tubular molybdenum-based alloy part prepared by the preparation method has the advantages of excellent room-temperature mechanical property, excellent high-temperature mechanical property and the like.
Description
Technical Field
The invention belongs to the technical field of powder metallurgy, and particularly relates to a preparation method of a large-diameter special-shaped thin-wall tubular molybdenum-based alloy part.
Background
The molybdenum and the molybdenum alloy material have high melting point (above 2600 ℃) and moderate density (10 g/cm)3) Good toughness and toughness, and is suitable for high-temp. erosion and ablation at more than 1600 deg.C, overload impact of more than 500g, 5X 106The above ideal structural material which is used in special environments such as high-frequency vibration and the like. Based on the strengthening and toughening mechanism of the alloy, La is added into the molybdenum2O3The rare earth oxide particles and carbide particles such as high-melting-point TiC can not only remarkably improve the room-temperature mechanical properties such as the bending strength of the alloy, but also greatly improve the high-temperature mechanical properties such as the high-temperature strength of the alloy and the high-temperature ablation property of the alloy.
At present, molybdenum-based alloy parts with proper amount of rare earth oxides and carbides are mainly formed by performing powder metallurgy on the molybdenum-based alloy parts into bars and then performing finish machining on the bars. The conventional method is mainly to form a molybdenum-based alloy bar blank by powder preparation, blank forming, high-temperature sintering and forging, and then form a molybdenum-based alloy part by subsequent machining. The forging process is mainly used for improving the toughness of the sintered molybdenum-base alloy bar. However, the method is generally only suitable for preparing molybdenum-based alloy rods with the diameter less than 100mm, and if the diameter is larger, the process is difficult to forge and toughen the central part of the rod, and the structural property uniformity of the rod is poor. For example, for a large-diameter (the outer diameter is larger than or equal to 100 mm) special-shaped (the special-shaped refers to that the wall thickness of the middle of a tube is thicker and the wall thickness of two ends of the tube is thinner) tubular molybdenum-based alloy part (the wall thickness range is generally 4-10 mm), if the method is adopted, because the content of particles such as hard and brittle phase oxides, carbides and the like in the molybdenum-based alloy is higher, forging defects such as cracking and layering of a bar blank are easy to occur in the large-deformation strengthening forging process of the bar blank, and the structure and performance of each part of the bar blank are very uneven due to the large diameter of the sintered molybdenum-based alloy bar blank and uneven forging deformation amount, the molybdenum-based alloy part has low room-temperature and high-temperature strengthening and toughening performance, and the service requirements under special environments such as high-temperature, high-overload impact. Therefore, a preparation method of a large-diameter special-shaped thin-wall tubular molybdenum-based alloy part with good obdurability and excellent high-temperature performance is needed to be developed, and a new approach and technical support are provided for the broad application of molybdenum-based alloy materials in special service environments.
Disclosure of Invention
The invention aims to provide a preparation method of a large-diameter special-shaped thin-wall tubular molybdenum-based alloy part, and the large-diameter special-shaped thin-wall tubular molybdenum-based alloy part prepared by the preparation method has the advantages of excellent room-temperature mechanical property, excellent high-temperature mechanical property and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a large-diameter special-shaped thin-wall tubular molybdenum-based alloy part is characterized by sequentially comprising the following steps of:
(1) sorting
Selecting molybdenum dioxide powder, rare earth lanthanum nitrate and TiC carbide powder as raw materials;
(2) powder pretreatment
According to the mass percentage content of each raw material set by the molybdenum-based alloy part, the Mo-La is prepared by adopting a conventional liquid-solid doping method2O3Compounding powder, and mixing the TiC carbide powder with the Mo-La2O3Directly mixing the composite powder to prepare Mo-La2O3Mechanically sieving the-TiC composite powder to control Mo-La2O3The grain diameter of the-TiC composite powder is in a reasonable range;
(3) shaping of prefabricated blanks
The obtained Mo-La2O3Placing the TiC composite powder into a rubber sheath, and carrying out cold isostatic pressing at 180-220 MPa to prepare a molybdenum-based alloy prefabricated blank with uniform density;
(4) pre-sintering
Putting the obtained molybdenum-based alloy prefabricated blank into a sintering furnace, setting the heating rate to be 6-8 ℃/min, and carrying out two-stage segmented heating; wherein, the first section is heated to 850-900 ℃ and then is insulated for 90min, and the second section is heated to 1200-1300 ℃ and then is sintered for 90-120 min;
(5) hot isostatic compaction
Putting the pre-sintered body obtained in the step (4) into a hot isostatic pressing furnace, and preserving heat for a certain time at high temperature and high pressure to obtain the pre-sintered body with the density of 9.9g/cm3The hot isostatic pressed green body above;
(6) spin forming
Machining the inner surface and the outer surface of the obtained hot isostatic pressing billet, heating the machined hot isostatic pressing billet to 800-1000 ℃, and then carrying out spinning forming;
(7) bulk heat treatment
And (4) performing hydrogen protection stress relief annealing treatment on the molybdenum-based alloy blank obtained in the step (6) after spinning forming.
In the research and development process, the sheath is required to be used in the hot isostatic pressing process of the existing powder or green body with lower density to form pressure difference, so that the powder or green body with lower density can be densified better, however, the requirement on the sheath material applicable to the hot isostatic pressing process of refractory metals such as molybdenum-based alloy is high, only metal molybdenum plates and tungsten plates with high melting points can be used, but the metal molybdenum plates and tungsten plates have high cost, are difficult to weld and are easy to leak gas, and the experiment fails. According to the invention, a plurality of specific processes such as cold isostatic pressing, pre-sintering, hot isostatic pressing and spinning forming are organically combined, so that the whole preparation process can be smoothly carried out under the condition that a sheath is omitted in the hot isostatic pressing process, and the molybdenum-based alloy part prepared has the advantages of uniform structure performance, high density and the like.
As a further explanation, in the step (1), the amounts of the molybdenum dioxide powder, the rare earth lanthanum nitrate and the TiC carbide powder are respectively calculated according to the mass percentage, that is, the rare earth lanthanum nitrate: 1-3% of TiC carbide powder: 0.5-2.5% and the balance molybdenum dioxide powder.
As a further explanation, the above Mo-La is used in the above step (2)2O3The composite powder is prepared according to the following steps: firstly preparing a rare earth lanthanum nitrate solution, then uniformly doping the rare earth lanthanum nitrate solution into molybdenum dioxide powder in a liquid spraying mode, obtaining primary powder after vacuum drying, and finally reducing the primary powder in flowing dry hydrogen at high temperature to prepare the Mo-La2O3And (3) composite powder. The liquid-solid doping process is one of conventional preparation methods of molybdenum-based alloy powder, and the operation in each step is conventional operation and method.
As a further descriptionIn the step (2), the TiC carbide powder and the Mo-La are mixed2O3The composite powder is directly mixed, and the conventional mechanical powder mixing or ball milling powder mixing and other conventional operations and methods are adopted.
As a further explanation, in the step (2), the Mo-La is mentioned above2O3The grain diameter of-TiC composite powder is less than or equal to 3 mu m.
As a further explanation, the sintering furnace used for the temperature rise in the step (4) is preferably a medium frequency induction sintering furnace, and the parameter setting can be directly performed on the medium frequency induction sintering furnace.
Specifically, the step (5) is to place the pre-sintered blank obtained in the step (4) into a hot isostatic pressing furnace, and sinter the pre-sintered blank for 1 to 2 hours at a heating temperature of 1650 to 1750 ℃ and a pressure of 160 to 180 MPa.
To explain further, in the spinning in the step (6), the amount of spinning deformation in the wall thickness direction is controlled to be larger than 10%.
As a further illustration, the specific conditions of the annealing treatment in the step (7) are that the annealing temperature is 700-800 ℃ and the annealing time is 60-90 min.
More specifically, the preparation method of the large-diameter special-shaped thin-wall tubular molybdenum-based alloy part sequentially comprises the following steps:
(1) sorting
Selecting molybdenum dioxide powder, rare earth lanthanum nitrate and TiC carbide powder as raw materials; the dosage ratio of the molybdenum dioxide powder, the rare earth lanthanum nitrate and the TiC carbide powder is respectively calculated according to the mass percentage that the rare earth lanthanum nitrate: 1-3% of TiC carbide powder: 0.5-2.5% and the balance molybdenum dioxide powder;
(2) powder pretreatment
According to the mass percentage content of the raw materials, preparing a rare earth lanthanum nitrate solution, uniformly doping the rare earth lanthanum nitrate solution into molybdenum dioxide powder in a liquid spraying mode, drying in vacuum to obtain primary powder, and finally reducing the primary powder in flowing dry hydrogen at high temperature to prepare the Mo-La2O3Compounding powder, and mixing the TiC carbide powder with the Mo-La2O3The Mo-La is prepared by directly mixing the composite powder by conventional mechanical powder mixing or ball milling powder mixing and other conventional operations and methods2O3Mechanically sieving the-TiC composite powder to control Mo-La2O3The grain diameter of-TiC composite powder is less than or equal to 3 mu m;
(3) shaping of prefabricated blanks
The obtained Mo-La2O3Putting the TiC composite powder into a rubber sheath, and performing conventional cold isostatic pressing at 180-220 MPa to prepare a molybdenum-based alloy prefabricated blank with uniform density;
(4) pre-sintering
Putting the obtained molybdenum-based alloy prefabricated blank into a medium-frequency induction sintering furnace, setting the heating rate to be 6-8 ℃/min, and carrying out two-stage temperature rise; wherein, the first section is heated to 850-900 ℃ and then is insulated for 90min, and the second section is heated to 1200-1300 ℃ and then is sintered for 90-120 min to seal the channels such as holes in the molybdenum-based alloy prefabricated blank body, thereby facilitating the subsequent hot isostatic pressing densification of the blank body;
(5) hot isostatic compaction
Putting the pre-sintered blank obtained in the step (4) into a hot isostatic pressing furnace, sintering for 1-2 h at the heating temperature of 1650-1750 ℃ and the pressure of 160-180 MPa to obtain the pre-sintered blank with the density of 9.9g/cm3The hot isostatic pressed green body above;
(6) spin forming
Turning the inner and outer surfaces of the obtained hot isostatic pressing blank, heating the hot isostatic pressing blank after machining to 800-1000 ℃, and then carrying out spinning forming, wherein the spinning deformation in the wall thickness direction is controlled to be more than 10% during spinning forming so as to further refine grains and improve the mechanical property of the molybdenum-based alloy blank;
(7) bulk heat treatment
Performing hydrogen protection stress relief annealing treatment on the molybdenum-based alloy blank obtained in the step (6) after spinning forming, wherein the annealing temperature is 700-800 ℃, and the annealing time is 60-90 min;
(8) nondestructive testing
Performing ultrasonic nondestructive testing on the molybdenum-based alloy part obtained in the step (7) to remove defective parts;
(9) finish machining
And performing finish machining on the defect-free molybdenum-based alloy part blank according to the structural size of the part.
The invention has the following beneficial effects:
the invention provides a preparation method of a large-diameter special-shaped thin-walled tubular molybdenum-based alloy part, which organically combines a plurality of specific processes such as cold isostatic pressing, pre-sintering, hot isostatic pressing, spinning forming and the like, so that the whole preparation process can be still smoothly carried out under the condition of omitting a sheath in the hot isostatic pressing process, the problems of large structure and poor mechanical property of the conventional powder metallurgy large-diameter special-shaped thin-walled tubular molybdenum-based alloy part are solved, and the large-diameter special-shaped thin-walled tubular molybdenum-based alloy part with uniform structure distribution and excellent performance is prepared; meanwhile, compared with the prior powder metallurgy technology, the method reduces the sintering temperature, shortens the sintering time and the subsequent high-temperature forging times, inhibits the growth of crystal grains, obtains the fine-grain large-diameter special-shaped thin-wall tubular molybdenum-based alloy part with the crystal grain size smaller than 8um, and has the excellent characteristic of high density; the room-temperature tensile strength of the prepared large-diameter special-shaped thin-wall tubular molybdenum-based alloy part reaches 520-630 MPa, the elongation is more than or equal to 10%, the consistency is good, and compared with the existing powder metallurgy sintered part, the elongation is improved by 30%.
Drawings
Fig. 1 is a schematic structural view of the mechanical tube according to the present invention.
FIG. 2 is a high magnification (500X) microstructure photograph of the molybdenum-based alloy part prepared in example 2 of the present invention.
FIG. 3 is a photograph of a low magnification (50X) microstructure of a molybdenum-based alloy part produced in example 2 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a special-shaped thin-wall tubular molybdenum-based alloy part with the outer diameter of 100mm and the maximum wall thickness of 5mm sequentially comprises the following steps:
(1) sorting
Selecting molybdenum dioxide powder, rare earth lanthanum nitrate and TiC carbide powder as raw materials; the molybdenum dioxide powder, the rare earth lanthanum nitrate and the TiC carbide powder are mixed according to the mass percentage, wherein the rare earth lanthanum nitrate: 0.5%, TiC carbide powder: 2.5 percent of molybdenum dioxide powder;
(2) powder pretreatment
Preparing a rare earth lanthanum nitrate solution according to the mass percentage content of each raw material, uniformly doping the rare earth lanthanum nitrate solution into molybdenum dioxide powder in a liquid spraying mode, drying in vacuum to obtain primary powder, and finally reducing the primary powder in flowing dry hydrogen at high temperature to prepare Mo-La2O3Compounding powder, and mixing TiC carbide powder with Mo-La2O3The Mo-La is prepared by directly mixing the composite powder by adopting conventional mechanical mixed powder2O3Mechanically sieving the-TiC composite powder to control Mo-La2O3The grain diameter of-TiC composite powder is less than or equal to 3 mu m;
(3) shaping of prefabricated blanks
The obtained Mo-La2O3Placing the TiC composite powder into a rubber sheath, and keeping the pressure at 180MPa for 5min for conventional cold isostatic pressing to prepare a molybdenum-based alloy prefabricated blank with uniform density;
(4) pre-sintering
Putting the obtained molybdenum-based alloy prefabricated blank into a medium-frequency induction sintering furnace, setting the heating rate to be 6 ℃/min, and carrying out two-stage segmented heating; wherein, the temperature is kept for 90min after the first section is heated to 850 ℃, and the temperature is kept for 90min after the second section is heated to 1200 ℃, so as to seal channels such as holes in the molybdenum-based alloy prefabricated blank and the like, thereby facilitating the subsequent hot isostatic pressing densification of the blank;
(5) hot isostatic compaction
Placing the pre-sintered blank obtained in the step (4) into a hot isostatic pressing furnace for heating tungsten wires, and sintering for 90min at the heating temperature of 1650 ℃ and the pressure of 160MPa to obtain the density of 9.92g/cm3The hot isostatic pressed green body of (1);
(6) spin forming
Turning the inner surface and the outer surface of the obtained hot isostatic pressing blank, heating the hot isostatic pressing blank to 800 ℃, and then carrying out spinning forming, wherein the total spinning deformation in the wall thickness direction is controlled to be 10.2 percent, so that the crystal grains are further refined, and the mechanical property of the molybdenum-based alloy blank is improved; the spinning forming can be carried out according to the spinning forming device and the using method thereof disclosed in the patent 201310199170.2, and other conventional spinning forming equipment can also be adopted;
(7) bulk heat treatment
Performing hydrogen protection stress relief annealing treatment on the molybdenum-based alloy blank obtained in the step (6) after spinning forming, wherein the annealing temperature is 700 ℃, and the annealing time is 60 min;
(8) nondestructive testing
Performing ultrasonic nondestructive testing on the molybdenum-based alloy part obtained in the step (7), and removing the molybdenum-based alloy part with defects such as holes;
(9) finish machining
And performing conventional finish machining on the defect-free molybdenum-based alloy part blank according to the structural size of the part.
The molybdenum-based alloy part obtained in this example had a room-temperature tensile strength of 520MPa, an elongation of 11% and a grain size of less than 8 μm.
Example 2
A preparation method of a special-shaped thin-wall tubular molybdenum-based alloy part with the outer diameter of 135mm and the maximum wall thickness of 7mm sequentially comprises the following steps:
(1) sorting
Selecting molybdenum dioxide powder, rare earth lanthanum nitrate and TiC carbide powder as raw materials; the molybdenum dioxide powder, the rare earth lanthanum nitrate and the TiC carbide powder are mixed according to the mass percentage, wherein the rare earth lanthanum nitrate: 1.5%, TiC carbide powder: 1.0 percent, and the balance of molybdenum dioxide powder;
(2) powder pretreatment
Preparing a rare earth lanthanum nitrate solution according to the mass percentage content of each raw material, uniformly doping the rare earth lanthanum nitrate solution into molybdenum dioxide powder in a liquid spraying mode, drying in vacuum to obtain primary powder, and finally reducing the primary powder in flowing dry hydrogen at high temperature to prepare Mo-La2O3Compounding powder, and mixing TiC carbide powder with Mo-La2O3The Mo-La is prepared by directly mixing the composite powder by adopting conventional mechanical mixed powder2O3Mechanically sieving the-TiC composite powder to control Mo-La2O3The grain diameter of-TiC composite powder is less than or equal to 3 mu m;
(3) shaping of prefabricated blanks
The obtained Mo-La2O3Placing the TiC composite powder into a rubber sheath, and keeping the pressure for 10min at 200MPa for conventional cold isostatic pressing to prepare a molybdenum-based alloy prefabricated blank with uniform density;
(4) pre-sintering
Putting the obtained molybdenum-based alloy prefabricated blank into a medium-frequency induction sintering furnace, setting the heating rate to be 7 ℃/min, and carrying out two-stage segmented heating; wherein, the temperature is kept for 90min after the first section is heated to 900 ℃, and the temperature is kept for 120min after the second section is heated to 1250 ℃, so as to seal channels such as holes and the like in the molybdenum-based alloy prefabricated blank, and facilitate the subsequent hot isostatic pressing densification of the blank;
(5) hot isostatic compaction
Putting the pre-sintered blank obtained in the step (4) into a hot isostatic pressing furnace for heating a tungsten wire, and sintering for 90min at the heating temperature of 1700 ℃ and the pressure of 170MPa to obtain the density of 9.92g/cm3The hot isostatic pressed green body of (1);
(6) spin forming
Turning the inner surface and the outer surface of the obtained hot isostatic pressing blank, heating the hot isostatic pressing blank to 950 ℃, and then carrying out spinning forming, wherein the total spinning deformation in the wall thickness direction is controlled to be 10.5 percent, so that the crystal grains are further refined, and the mechanical property of the molybdenum-based alloy blank is improved;
(7) bulk heat treatment
Performing hydrogen protection stress relief annealing treatment on the molybdenum-based alloy blank obtained in the step (6) after spinning forming, wherein the annealing temperature is 800 ℃, and the annealing time is 90min;
(8) nondestructive testing
Performing ultrasonic nondestructive testing on the molybdenum-based alloy part obtained in the step (7), and removing the molybdenum-based alloy part with defects such as holes;
(9) finish machining
And performing conventional finish machining on the defect-free molybdenum-based alloy part blank according to the structural size of the part.
The room-temperature tensile strength of the molybdenum-based alloy part prepared in the example is 585MPa, the elongation is 10.6%, and the grain size is smaller than 8 um; according to the high-power (500X) microstructure photo of the molybdenum-based alloy part shown in the attached figure 2, the structure of the molybdenum-based alloy part is uniformly distributed; according to the low-magnification (50X) microstructure photo of the molybdenum-based alloy part shown in the attached figure 3, the molybdenum-based alloy part has high compactness.
Example 3
A preparation method of a special-shaped thin-wall tubular molybdenum-based alloy part with the outer diameter of 160mm and the maximum wall thickness of 8mm sequentially comprises the following steps:
(1) sorting
Selecting molybdenum dioxide powder, rare earth lanthanum nitrate and TiC carbide powder as raw materials; the molybdenum dioxide powder, the rare earth lanthanum nitrate and the TiC carbide powder are mixed according to the mass percentage, wherein the rare earth lanthanum nitrate: 3.0%, TiC carbide powder: 0.5 percent of molybdenum dioxide powder and the balance of molybdenum dioxide powder;
(2) powder pretreatment
According to the mass percentage content of each raw material, preparing a rare earth lanthanum nitrate solution, and then adopting a liquid spraying modeUniformly doping a rare earth lanthanum nitrate solution into molybdenum dioxide powder, drying in vacuum to obtain primary powder, and finally reducing the primary powder in flowing dry hydrogen at high temperature to prepare Mo-La2O3Compounding powder, and mixing TiC carbide powder with Mo-La2O3The Mo-La is prepared by directly mixing the composite powder by adopting conventional mechanical mixed powder2O3Mechanically sieving the-TiC composite powder to control Mo-La2O3The grain diameter of-TiC composite powder is less than or equal to 3 mu m;
(3) shaping of prefabricated blanks
The obtained Mo-La2O3Placing the TiC composite powder into a rubber sheath, and keeping the pressure for 10min at 220MPa for conventional cold isostatic pressing to prepare a molybdenum-based alloy prefabricated blank with uniform density;
(4) pre-sintering
Putting the obtained molybdenum-based alloy prefabricated blank into a medium-frequency induction sintering furnace, setting the heating rate to be 8 ℃/min, and carrying out two-stage segmented heating; wherein, the temperature of the first section is increased to 900 ℃ and then is preserved for 90min, and the temperature of the second section is increased to 1300 ℃ and then is sintered for 120min to seal channels such as holes in the molybdenum-based alloy prefabricated blank body, thereby facilitating the subsequent hot isostatic pressing densification of the blank body;
(5) hot isostatic compaction
Putting the pre-sintered blank obtained in the step (4) into a hot isostatic pressing furnace for heating tungsten wires, and sintering for 120min at the heating temperature of 1750 ℃ and the pressure of 180MPa to obtain the pre-sintered blank with the density of 9.9g/cm3The hot isostatic pressed green body of (1);
(6) spin forming
Turning the inner surface and the outer surface of the obtained hot isostatic pressing blank, heating the hot isostatic pressing blank to 1000 ℃, and then carrying out spinning forming, wherein the total spinning deformation in the wall thickness direction is controlled to be 10.8 percent, so that the crystal grains are further refined, and the mechanical property of the molybdenum-based alloy blank is improved;
(7) bulk heat treatment
Performing hydrogen protection stress relief annealing treatment on the molybdenum-based alloy blank obtained in the step (6) after spinning forming, wherein the annealing temperature is 800 ℃, and the annealing time is 90min;
(8) nondestructive testing
Performing ultrasonic nondestructive testing on the molybdenum-based alloy part obtained in the step (7), and removing the molybdenum-based alloy part with defects such as holes;
(9) finish machining
And performing conventional finish machining on the defect-free molybdenum-based alloy part blank according to the structural size of the part.
The molybdenum-based alloy part obtained in this example had a room-temperature tensile strength of 630MPa, an elongation of 10.2% and a grain size of less than 8 μm.
Claims (18)
1. A preparation method of a large-diameter special-shaped thin-wall tubular molybdenum-based alloy part is characterized by sequentially comprising the following steps of:
(1) sorting
Selecting molybdenum dioxide powder, rare earth lanthanum nitrate and TiC carbide powder as raw materials;
(2) powder pretreatment
According to the mass percentage content of each raw material set by the molybdenum-based alloy part, Mo-La is prepared by adopting a liquid-solid doping method2O3Compounding powder, and mixing the TiC carbide powder and the Mo-La2O3Directly mixing the composite powder to prepare Mo-La2O3Mechanically sieving TiC composite powder;
(3) shaping of prefabricated blanks
The obtained Mo-La2O3Placing the TiC composite powder into a rubber sheath, and carrying out cold isostatic pressing at 180-220 MPa to prepare a molybdenum-based alloy prefabricated blank with uniform density;
(4) pre-sintering
Putting the obtained molybdenum-based alloy prefabricated blank into a sintering furnace, setting the heating rate to be 6-8 ℃/min, and carrying out two-stage segmented heating;
(5) hot isostatic compaction
Putting the pre-sintered body obtained in the step (4) into a hot isostatic pressing furnace, and preserving heat for a certain time at high temperature and high pressure to obtain the pre-sintered body with the density of 9.9g/cm3The hot isostatic pressed green body above;
(6) spin forming
Machining the inner surface and the outer surface of the obtained hot isostatic pressing billet, heating the machined hot isostatic pressing billet to 800-1000 ℃, and then carrying out spinning forming;
(7) bulk heat treatment
And (4) performing hydrogen protection stress relief annealing treatment on the molybdenum-based alloy blank obtained in the step (6) after spinning forming.
2. The method for preparing the large-diameter special-shaped thin-wall tubular molybdenum-based alloy part as claimed in claim 1, wherein the method comprises the following steps: the dosage ratios of the molybdenum dioxide powder, the rare earth lanthanum nitrate and the TiC carbide powder in the step (1) are respectively calculated according to the mass percentage that the rare earth lanthanum nitrate: 1-3% of TiC carbide powder: 0.5-2.5% and the balance molybdenum dioxide powder.
3. The method for preparing large-diameter profiled thin-walled tubular molybdenum-based alloy part according to claim 1 or 2, wherein the Mo-La is used in the step (2)2O3The composite powder is prepared according to the following steps: firstly preparing a rare earth lanthanum nitrate solution, then uniformly doping the rare earth lanthanum nitrate solution into molybdenum dioxide powder in a liquid spraying mode, obtaining primary powder after vacuum drying, and finally reducing the primary powder in flowing dry hydrogen at high temperature to prepare the Mo-La2O3And (3) composite powder.
4. The method for preparing the large-diameter profiled thin-walled tubular molybdenum-based alloy part as claimed in claim 1 or 2, wherein: in the step (2), the TiC carbide powder and the Mo-La are mixed2O3Directly mixing the composite powder by adopting mechanical powder mixing or ball milling powder mixing; the Mo-La in the step (2)2O3The grain diameter of-TiC composite powder is less than or equal to 3 mu m.
5. The method for preparing the large-diameter profiled thin-walled tubular molybdenum-based alloy part as claimed in claim 1 or 2, wherein: and (5) specifically, putting the pre-sintered blank obtained in the step (4) into a hot isostatic pressing furnace, and sintering for 1-2 h at the heating temperature of 1650-1750 ℃ and the pressure of 160-180 MPa.
6. The method for preparing the large-diameter special-shaped thin-wall tubular molybdenum-based alloy part as claimed in claim 3, wherein the method comprises the following steps: and (5) specifically, putting the pre-sintered blank obtained in the step (4) into a hot isostatic pressing furnace, and sintering for 1-2 h at the heating temperature of 1650-1750 ℃ and the pressure of 160-180 MPa.
7. The method for preparing the large-diameter special-shaped thin-wall tubular molybdenum-based alloy part as claimed in claim 4, wherein the method comprises the following steps: and (5) specifically, putting the pre-sintered blank obtained in the step (4) into a hot isostatic pressing furnace, and sintering for 1-2 h at the heating temperature of 1650-1750 ℃ and the pressure of 160-180 MPa.
8. The method for preparing the large-diameter profiled thin-walled tubular molybdenum-based alloy part as claimed in claim 1 or 2, wherein: and (4) controlling the spinning deformation amount in the wall thickness direction to be more than 10% during spinning forming in the step (6).
9. The method for preparing the large-diameter special-shaped thin-wall tubular molybdenum-based alloy part as claimed in claim 3, wherein the method comprises the following steps: and (4) controlling the spinning deformation amount in the wall thickness direction to be more than 10% during spinning forming in the step (6).
10. The method for preparing the large-diameter special-shaped thin-wall tubular molybdenum-based alloy part as claimed in claim 4, wherein the method comprises the following steps: and (4) controlling the spinning deformation amount in the wall thickness direction to be more than 10% during spinning forming in the step (6).
11. The method for preparing the large-diameter special-shaped thin-wall tubular molybdenum-based alloy part as claimed in claim 5, wherein the method comprises the following steps: and (4) controlling the spinning deformation amount in the wall thickness direction to be more than 10% during spinning forming in the step (6).
12. The method for preparing the large-diameter special-shaped thin-wall tubular molybdenum-based alloy part as claimed in claim 6, wherein the method comprises the following steps: and (4) controlling the spinning deformation amount in the wall thickness direction to be more than 10% during spinning forming in the step (6).
13. The method for preparing the large-diameter special-shaped thin-walled tubular molybdenum-based alloy part as claimed in claim 7, wherein the method comprises the following steps: and (4) controlling the spinning deformation amount in the wall thickness direction to be more than 10% during spinning forming in the step (6).
14. The method for preparing the large-diameter profiled thin-walled tubular molybdenum-based alloy part as claimed in claim 1 or 2, wherein: the specific conditions of the annealing treatment in the step (7) are that the annealing temperature is 700-800 ℃, and the annealing time is 60-90 min.
15. The method for preparing the large-diameter special-shaped thin-wall tubular molybdenum-based alloy part as claimed in claim 3, wherein the method comprises the following steps: the specific conditions of the annealing treatment in the step (7) are that the annealing temperature is 700-800 ℃, and the annealing time is 60-90 min.
16. The method for preparing the large-diameter special-shaped thin-wall tubular molybdenum-based alloy part as claimed in claim 4, wherein the method comprises the following steps: the specific conditions of the annealing treatment in the step (7) are that the annealing temperature is 700-800 ℃, and the annealing time is 60-90 min.
17. The method for preparing the large-diameter profiled thin-walled tubular molybdenum-based alloy part as claimed in claim 13, wherein: the specific conditions of the annealing treatment in the step (7) are that the annealing temperature is 700-800 ℃, and the annealing time is 60-90 min.
18. The method for preparing the large-diameter profiled thin-walled tubular molybdenum-based alloy part as claimed in claim 1, wherein the method comprises the following steps in sequence:
(1) sorting
Selecting molybdenum dioxide powder, rare earth lanthanum nitrate and TiC carbide powder as raw materials; the molybdenum dioxide powder, the rare earth lanthanum nitrate and the TiC carbide powder are mixed according to the mass percentage that the rare earth lanthanum nitrate: 1-3% of TiC carbide powder: 0.5-2.5% and the balance molybdenum dioxide powder;
(2) powder pretreatment
According to the mass percentage content of the raw materials, preparing a rare earth lanthanum nitrate solution, uniformly doping the rare earth lanthanum nitrate solution into molybdenum dioxide powder in a liquid spraying mode, drying in vacuum to obtain primary powder, and finally reducing the primary powder in flowing dry hydrogen at high temperature to prepare the Mo-La2O3Compounding powder, and mixing the TiC carbide powder and the Mo-La2O3The composite powder is directly mixed by adopting mechanical mixed powder or ball milling mixed powder to prepare Mo-La2O3Mechanically sieving the-TiC composite powder to control Mo-La2O3The grain diameter of-TiC composite powder is less than or equal to 3 mu m;
(3) shaping of prefabricated blanks
The obtained Mo-La2O3the-TiC composite powder is put into a rubber sheath, and conventional cold isostatic pressing is carried out under the pressure of 180 MPa-220 MPa;
(4) pre-sintering
Putting the obtained molybdenum-based alloy prefabricated blank into a medium-frequency induction sintering furnace, setting the heating rate to be 6-8 ℃/min, and carrying out two-stage temperature rise;
(5) hot isostatic compaction
Putting the pre-sintered blank obtained in the step (4) into a hot isostatic pressing furnace, sintering for 1-2 h at the heating temperature of 1650-1750 ℃ and the pressure of 160-180 MPa to obtain the pre-sintered blank with the density of 9.9g/cm3The hot isostatic pressed green body above;
(6) spin forming
Turning the inner surface and the outer surface of the obtained hot isostatic pressing blank, heating the hot isostatic pressing blank after machining to 800-1000 ℃, and then carrying out spinning forming, wherein the spinning deformation in the wall thickness direction is controlled to be more than 10% during spinning forming;
(7) bulk heat treatment
Performing hydrogen protection stress relief annealing treatment on the molybdenum-based alloy blank obtained in the step (6) after spinning forming, wherein the annealing temperature is 700-800 ℃, and the annealing time is 60-90 min;
(8) nondestructive testing
Performing ultrasonic nondestructive testing on the molybdenum-based alloy part obtained in the step (7) to remove defective parts;
(9) finish machining
And performing finish machining on the defect-free molybdenum-based alloy part blank according to the structural size of the part.
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