CN116219246A - Collaborative strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals, and preparation method and application thereof - Google Patents
Collaborative strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals, and preparation method and application thereof Download PDFInfo
- Publication number
- CN116219246A CN116219246A CN202211719719.1A CN202211719719A CN116219246A CN 116219246 A CN116219246 A CN 116219246A CN 202211719719 A CN202211719719 A CN 202211719719A CN 116219246 A CN116219246 A CN 116219246A
- Authority
- CN
- China
- Prior art keywords
- temperature
- powder
- alloy
- molybdenum alloy
- dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001182 Mo alloy Inorganic materials 0.000 title claims abstract description 68
- 238000005728 strengthening Methods 0.000 title claims abstract description 37
- 239000006104 solid solution Substances 0.000 title claims abstract description 27
- 239000013078 crystal Substances 0.000 title claims abstract description 22
- 239000007962 solid dispersion Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000956 alloy Substances 0.000 claims abstract description 70
- 239000000843 powder Substances 0.000 claims abstract description 60
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 56
- 238000005245 sintering Methods 0.000 claims abstract description 32
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 titanium hydride Chemical compound 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000010275 isothermal forging Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- 229910000568 zirconium hydride Inorganic materials 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000048 titanium hydride Inorganic materials 0.000 claims abstract description 11
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- 238000004663 powder metallurgy Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 3
- 150000001247 metal acetylides Chemical class 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000002195 synergetic effect Effects 0.000 abstract description 10
- 239000011812 mixed powder Substances 0.000 abstract description 5
- 238000009694 cold isostatic pressing Methods 0.000 abstract description 4
- 238000000227 grinding Methods 0.000 abstract 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910017583 La2O Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- QDHRWTNKRWVDBE-UHFFFAOYSA-N [C].[Zr].[Ti].[Mo] Chemical class [C].[Zr].[Ti].[Mo] QDHRWTNKRWVDBE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0005—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with at least one oxide and at least one of carbides, nitrides, borides or silicides as the main non-metallic constituents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a synergic strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals, and a preparation method and application thereof, wherein the alloy comprises the following components: ti:0.4 to 0.6 wt.%, zr:0.15 to 0.2 wt.%, B:0.01 to 0.03 wt.%; c:0.03 to 0.05 wt.%, la2O3:1 to 1.5 wt.% and the balance of Mo, and is prepared by adopting a powder metallurgy process, wherein the preparation process is as follows: pre-mixing the vacuum dried molybdenum powder, carbon powder, zirconium hydride powder, titanium hydride powder and rare earth lanthanum oxide powder according to the proportion of alloy components, fine grinding the pre-mixed powder in a planetary ball mill, fully mixing to obtain alloy mixed powder, performing cold isostatic pressing on the alloy mixed powder to obtain a green body, and pre-sintering and sintering the green body in a hydrogen atmosphere furnace at high temperature to obtain the molybdenum alloy rod. The molybdenum alloy prepared by the invention has excellent comprehensive high-temperature mechanical property and room-temperature mechanical property, and can meet the use requirement of a high-temperature isothermal forging die of 1200 ℃ and above.
Description
Technical Field
The invention belongs to the technical field of preparation and application of rare metal structural materials, and particularly relates to a collaborative strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals, and a preparation method and application thereof.
Background
With the vigorous development of national defense industries such as aviation, aerospace, navigation, military industry and the like in China, higher requirements are put forward on the requirements and high-temperature performance of materials which are difficult to deform. High-temperature isothermal forging is one of the most main processes for near-net forming of high-temperature difficult-to-deform materials such as powder high-temperature metallurgy. The die material is the key point of the high-temperature isothermal forging process of the whole high-temperature alloy material, so that the search and development of the high-temperature die material suitable for the high-temperature isothermal forging are gradually becoming research hot spots and key points.
In the existing high-temperature isothermal forging die materials, high-temperature alloys such as iron-based and nickel-based are the most widely used high-temperature alloy materials at the current temperature of 650-1200 ℃, and the use temperature is difficult to exceed 1200 ℃. Therefore, there is a need to develop high temperature alloys for use at temperatures above 1200 ℃ and even higher to meet the increasing demands of high temperature isothermal forging die materials.
At present, high-temperature alloy materials with the use temperature of 1200 ℃ and above are mainly concentrated on refractory/noble metal-based alloy materials such as molybdenum-based alloy materials, tungsten-based alloy materials, tantalum-based alloy materials, niobium-based alloy materials, platinum-based alloy materials and the like, but due to poor room temperature toughness of tungsten alloy materials, tantalum-based alloy materials, niobium-based alloy materials and platinum-based alloy materials are rare in resources and high in price, and are not suitable for large-scale isothermal forging die materials. The molybdenum alloy is the first choice of high-temperature die materials of 1200 ℃ and above because of high melting point, good thermal conductivity, low expansion coefficient, slow softening at high temperature, excellent high-low temperature strong hardness, high-temperature creep deformation and high-temperature toughness, rich earth storage and low price.
The main micro strengthening modes of the molybdenum alloy are three modes of solid solution strengthening (alloying), second phase particle strengthening (dispersion strengthening) and fine crystal strengthening. The addition of nonmetallic or metallic elements (B, C, si, K, al, W, re, ti, zr, hf, etc.) to molybdenum can form a solid-solution-strengthened molybdenum alloy, a dispersion-strengthened molybdenum alloy, or a fine-grain-strengthened molybdenum alloy. However, by means of the strengthening effect of a single strengthening mode, the comprehensive performance of the molybdenum alloy at high temperature and room temperature is improved to a limited extent, and the working requirements of the die in the high-temperature isothermal forging process are difficult to meet. For example, adding TiC, zrC, taC, hfC carbide particles into molybdenum, the obtained second phase particles strengthen the molybdenum alloy, and although the recrystallization temperature, high-temperature strength, hardness and other high-temperature performances of the molybdenum alloy are improved to a limited extent, the room-temperature toughness, oxidation resistance and ductile-brittle transition temperature of the molybdenum alloy are improved to a limited extent, and after the molybdenum alloy works in a high-temperature environment, the molybdenum alloy is easy to crack, oxidize and other phenomena, so that the service life of the molybdenum alloy and the working reliability of related structural members are greatly influenced. Currently, molybdenum-titanium-zirconium-carbon series alloy (TZM) is the most widely applied to high-temperature dies at 1200 ℃ and above in developed countries such as China and Europe and America, but the alloy is extremely easy to oxidize at 500 ℃ or above, so that the alloy is required to be used under the protection of vacuum or inert atmosphere, a special totally-enclosed isothermal forging press needs to be established, the running cost and the maintenance cost are extremely high, the TZM alloy die material replacement frequency is relatively high, and the component design of the molybdenum alloy needs to be further adjusted, and the additive types and the strengthening mode of the molybdenum alloy need to be optimized.
So far, the addition of different elements is not seen, and a synergistic strengthening high-temperature high-strength molybdenum alloy is prepared by three strengthening modes of solid solution strengthening, dispersion strengthening and fine crystal strengthening so as to meet the requirement of using a high-temperature isothermal forging die material of 1200 ℃ and above.
Disclosure of Invention
Aiming at the current situation that the high-temperature isothermal forging die material at 1200 ℃ and above is scarce and the market demand is met, the invention provides a synergic strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals, and a preparation method and application thereof, and specifically comprises the following contents:
the first part of the invention provides a collaborative strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals, wherein the molybdenum alloy comprises the following constituent elements in percentage by mass: ti:0.4 to 0.6 wt.%, zr:0.15 to 0.2 wt.%, B:0.01 to 0.03 wt.%, C:0.03 to 0.05 wt.%, la2O3:1 to 1.5 wt.% of Mo, the balance being unavoidable impurities, and the mass percentages of part of the constituent elements satisfy the following relationship: ti+Zr+B+C is less than or equal to 1 wt percent.
As a further illustration of the invention, the molybdenum alloy comprises a molybdenum matrix, carbides, oxides, and a molybdenum alloy in a sintered state.
As a further illustration of the invention, the molybdenum alloy is prepared by a powder metallurgy process.
The second part of the invention provides the application of the synergistic strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals in the high-temperature vacuum isothermal forging die material with the temperature of 1200 ℃ and above.
The third part of the invention provides a preparation method of a collaborative strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals, which comprises the following steps:
(1) Vacuum drying molybdenum powder, carbon powder, zirconium hydride powder, titanium hydride powder and rare earth lanthanum oxide powder;
(2) Mixing the vacuum dried molybdenum powder, carbon powder, zirconium hydride powder, titanium hydride powder and rare earth lanthanum oxide powder according to the mass percentages of the constituent elements of the molybdenum alloy to obtain premixed powder;
(3) Ball milling, fully mixing and sieving the premixed powder to ensure that the powder granularity is less than or equal to 5 mu m to obtain mixed alloy powder;
(4) Holding the mixed alloy powder for 10-15 min under a cold isostatic press under 200-250 MPa, and pressing into a cylindrical green body;
(5) Placing the cylindrical green body in a hydrogen sintering furnace, and sintering under a hydrogen atmosphere;
(6) And after sintering, cooling the alloy rod blank to room temperature along with a furnace in a hydrogen atmosphere, and taking out to obtain the molybdenum alloy rod blank.
As a further illustration of the present invention, the purity of the raw materials in step (1) is: mo is more than or equal to 99.97%, tiH2 is more than or equal to 99.97%, ti is more than or equal to 99.59%, zr+Hf+H is more than or equal to 99.97% in ZrH2, and Zr+Hf is more than or equal to 97.6%; the boron powder and the graphite powder are all analytically pure, and the vacuum drying conditions are as follows: temperature: 100 ℃; vacuum degree: -0.1 MPa; drying time: 4 h.
As a further explanation of the invention, in the step (3), a planetary ball mill is adopted for ball milling, the ball milling time is 2 h, the rotating speed is 240 r/min, and the ball-material ratio is 2:1.
As a further illustration of the present invention, the diameter of the cylindrical green compact pressed in the step (4) is 40 mm, and the hydrogen gas in the step (4) is high purity hydrogen gas.
As a further illustration of the present invention, the sintering process in the step (5) specifically includes: firstly, raising the temperature to 200 ℃ from room temperature in a gradient way, and then preserving heat to sufficiently remove free water in the mixed powder; then quickly heating to 900 ℃ and preserving heat to remove volatile impurities in the mixed powder and reduce the reaction of Mo and O in the powder; slowly heating to 1200 ℃ after the heat preservation at 900 ℃ is finished, so as to further remove part of impurities; then slowly heating to 1900 ℃ and sintering at high temperature 4 h to promote the formation of alloy, and cooling along with a furnace after the high-temperature sintering is finished to obtain a sintered alloy rod. The specific sintering process is shown in fig. 1.
As a further illustration of the present invention, the molybdenum alloy in step (6) has a relative density of greater than 98% after high temperature sintering.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the high-strength high-temperature molybdenum alloy designed and prepared by the invention consists of a molybdenum matrix, carbide, oxide, molybdenum and other alloys, wherein the recrystallization starting temperature is more than or equal to 1400 ℃, and the high-strength high-temperature molybdenum alloy has excellent comprehensive mechanical properties of yield strength more than or equal to 510 MPa, tensile strength more than or equal to 590 MPa and plastic deformation of about 15 percent at 1200 ℃;
2. according to the high-temperature high-strength molybdenum alloy designed and prepared by the invention, through adding Ti, zr, B, C and other elements, grains are refined through the strong pinning effect of formed TiC, zrC, B C and other carbides on dislocation, and fine grain reinforcement is generated; and Ti, zr, B and a small amount of solid solution formed by corresponding carbide and molybdenum generate solid solution strengthening, and Ti, zr, B and a second phase particle formed by corresponding carbide and oxide generate dispersion strengthening, so that the high-temperature toughness performance of the molybdenum alloy can be remarkably improved, the high-temperature working condition requirement of a high-temperature isothermal forging die at 1200 ℃ and above is met, meanwhile, the generation and expansion of cracks of the alloy in a working state are slowed down, the room-temperature brittleness of the molybdenum alloy is greatly improved, the ductile-brittle transition temperature of the molybdenum alloy is effectively reduced, and the recrystallization starting temperature of the molybdenum alloy is also improved;
3. the high-temperature high-strength molybdenum alloy prepared by the design of the invention can refine molybdenum alloy grains and generate fine grain reinforcement by adding rare earth La2O 3; and form second phase particles to produce dispersion strengthening, and can greatly improve the high temperature mechanical property and oxidation resistance of the molybdenum alloy. The alloy material is directly processed under the sintering state cooling condition of sintering into a rod, and solid solution and aging processes are not needed, so that the preparation is simple, the energy consumption is low, and the efficiency is high.
Drawings
FIG. 1 is a sintering process diagram of a cooperatively reinforced high-temperature high-strength molybdenum alloy reinforced by solid solution, dispersion and fine crystals.
Detailed Description
In order to make the technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. The described embodiments are only some, but not all, embodiments of the invention. The alloy structure and properties of the embodiments of the present application illustrated in the drawings herein may be tailored and designed in a variety of different compositional configurations, and thus the following detailed description of the embodiments of the present application provided in the drawings is not intended to limit the scope of the application as claimed, but is merely representative of selected embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The technical scheme of the present application will be explained in connection with specific embodiments.
Example 1
Providing a synergic strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals, wherein the alloy consists of carbon, zirconium, titanium, lanthanum, oxygen and molybdenum elements; wherein the mass percentage ranges are as follows: ti:0.45 wt.%, zr:0.18 wt.%, B:0.02 wt.%; c:0.04 wt.%, la2O3:1. 1 wt wt.%, the balance Mo and unavoidable impurities, all in mass percent.
The preparation method of the synergetic enhanced high-temperature high-strength molybdenum alloy comprises the following steps:
step one: vacuum drying molybdenum powder, carbon powder, boron powder, zirconium hydride powder, titanium hydride powder and rare earth lanthanum oxide powder (the raw material purity is that Mo is more than or equal to 99.97%, tiH2 is more than or equal to 99.97%, ti is more than or equal to 99.59%, zr+Hf+H is more than or equal to 99.97%, zr+Hf is more than or equal to 97.6%, and both boron powder and graphite powder are analytically pure); the vacuum drying conditions are as follows: temperature: 100 ℃; vacuum degree: -0.1 MPa; drying time: 4 h.
Step two: mixing the vacuum dried molybdenum powder, carbon powder, zirconium hydride powder, titanium hydride powder and rare earth lanthanum oxide powder according to the preset composition proportion to obtain premixed powder;
step three: placing the premixed powder into a planetary ball mill for ball milling, fully mixing and sieving to ensure that the powder granularity is less than or equal to 5 mu m, and obtaining mixed alloy powder;
step four: cold isostatic pressing the mixed alloy powder for 10 min under 250 MPa to prepare a cylindrical green body with the diameter of 40 mm;
step five: placing the cylindrical green body in a hydrogen sintering furnace, and performing high-temperature hydrogen sintering under the hydrogen atmosphere according to the sintering process shown in fig. 1 to prepare a molybdenum alloy bar blank;
step six: and after sintering, cooling the alloy rod blank to room temperature along with a furnace under the hydrogen atmosphere, and taking out the alloy rod blank to obtain the alloy rod blank.
Step seven: the obtained alloy rod blank is sampled to carry out high-temperature mechanical property and hardness test, the tensile strength of the alloy rod blank at 1200 ℃ is 515.6 MPa, the yield strength of the alloy rod blank is 594 MPa, the elongation of the alloy rod blank is 16.3%, and the recrystallization starting temperature of the alloy rod blank is more than 1400 ℃.
Example 2
Providing a synergic strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals, wherein the alloy consists of carbon, zirconium, titanium, lanthanum, oxygen and molybdenum elements; wherein the mass percentage ranges are as follows: ti:0.5 wt.%, zr:0.18 wt.%, B:0.02 wt.%; c:0.04 wt.%, la2O3:1.2 wt.%, balance Mo and unavoidable impurities, all in mass%.
The preparation method of the synergetic enhanced high-temperature high-strength molybdenum alloy comprises the following steps:
step one: vacuum drying molybdenum powder, carbon powder, boron powder, zirconium hydride powder, titanium hydride powder and rare earth lanthanum oxide powder (the raw material purity is that Mo is more than or equal to 99.97%, tiH2 is more than or equal to 99.97%, ti is more than or equal to 99.59%, zr+Hf+H is more than or equal to 99.97%, zr+Hf is more than or equal to 97.6%, and both boron powder and graphite powder are analytically pure); the vacuum drying conditions are as follows: temperature: 100 ℃; vacuum degree: -0.1 MPa; drying time: 4 h.
Step two: mixing the vacuum dried molybdenum powder, carbon powder, zirconium hydride powder, titanium hydride powder and rare earth lanthanum oxide powder according to the preset composition proportion to obtain premixed powder;
step three: placing the premixed powder into a planetary ball mill for ball milling, fully mixing and sieving to ensure that the powder granularity is less than or equal to 5 mu m, and obtaining mixed alloy powder;
step four: cold isostatic pressing the mixed alloy powder for 15 min under 250 MPa to prepare a cylindrical green body with the diameter of 40 mm;
step five: placing the cylindrical green body in a hydrogen sintering furnace, and performing high-temperature hydrogen sintering under the hydrogen atmosphere according to the sintering process shown in fig. 1 to prepare a molybdenum alloy bar blank;
step six: and after sintering, cooling the alloy rod blank to room temperature along with a furnace under the hydrogen atmosphere, and taking out the alloy rod blank to obtain the alloy rod blank.
Step seven: the obtained alloy rod blank is sampled to carry out high-temperature mechanical property and hardness test, the tensile strength of the alloy rod blank at 1200 ℃ is 565.8 MPa, the yield strength of the alloy rod blank is 643.4 MPa, the elongation of the alloy rod blank is 21.5%, and the recrystallization starting temperature of the alloy rod blank is more than 1400 ℃.
Example 3
Providing a synergic strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals, wherein the alloy consists of carbon, zirconium, titanium, lanthanum, oxygen and molybdenum elements; wherein the mass percentage ranges are as follows: ti:0.6 wt.%, zr:0.2 wt.%, B:0.3 wt.%; c:0.05 wt.%, la2O3:1.5 wt.%, balance Mo and unavoidable impurities, all in mass%.
The preparation method of the synergetic enhanced high-temperature high-strength molybdenum alloy comprises the following steps:
step one: vacuum drying molybdenum powder, carbon powder, boron powder, zirconium hydride powder, titanium hydride powder and rare earth lanthanum oxide powder (the raw material purity is that Mo is more than or equal to 99.97%, tiH2 is more than or equal to 99.97%, ti is more than or equal to 99.59%, zr+Hf+H is more than or equal to 99.97%, zr+Hf is more than or equal to 97.6%, and both boron powder and graphite powder are analytically pure); the vacuum drying conditions are as follows: temperature: 100 ℃; vacuum degree: -0.1 MPa; drying time: 4 h.
Step two: mixing the vacuum dried molybdenum powder, carbon powder, zirconium hydride powder, titanium hydride powder and rare earth lanthanum oxide powder according to the preset composition proportion to obtain premixed powder;
step three: placing the premixed powder into a planetary ball mill for ball milling, fully mixing and sieving to ensure that the powder granularity is less than or equal to 5 mu m, and obtaining mixed alloy powder;
step four: cold isostatic pressing the mixed alloy powder for 15 min under 250 MPa to prepare a cylindrical green body with the diameter of 40 mm;
step five: placing the cylindrical green body in a hydrogen sintering furnace, and performing high-temperature hydrogen sintering under the hydrogen atmosphere according to the sintering process shown in fig. 1 to prepare a molybdenum alloy bar blank;
step six: and after sintering, cooling the alloy rod blank to room temperature along with a furnace under the hydrogen atmosphere, and taking out the alloy rod blank to obtain the alloy rod blank.
Step seven: the obtained alloy rod blank is sampled to carry out high-temperature mechanical property and hardness test, the tensile strength of the alloy rod blank at 1200 ℃ is 588 MPa, the yield strength of the alloy rod blank is 677.4 MPa, the elongation of the alloy rod blank is 25.7%, and the recrystallization starting temperature of the alloy rod blank is more than 1400 ℃.
Finally, it should be noted that the above-mentioned embodiments are merely for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The high-temperature high-strength molybdenum alloy reinforced by solid solution, dispersion and fine crystals is characterized by comprising the following component elements in percentage by mass: ti:0.4 to 0.6 wt.%, zr:0.15 to 0.2 wt.%, B:0.01 to 0.03 wt.%, C:0.03 to 0.05 wt.%, la2O3:1 to 1.5 wt.% of Mo, the balance being unavoidable impurities, and the mass percentages of part of the constituent elements satisfy the following relationship: ti+Zr+B+C is less than or equal to 1 wt percent.
2. The co-strengthening high temperature high strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals according to claim 1, wherein the molybdenum alloy comprises a molybdenum matrix, carbides, oxides and molybdenum alloy in a sintered state.
3. The synergistically strengthened high temperature, high strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals according to claim 1, wherein said molybdenum alloy is prepared by a powder metallurgy process.
4. Use of a co-strengthening high temperature high strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals as claimed in any one of claims 1 to 3 in high temperature vacuum isothermal forging die material at 1200 ℃ and above.
5. The preparation method of the collaborative strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals is characterized by comprising the following steps:
(1) Vacuum drying molybdenum powder, carbon powder, zirconium hydride powder, titanium hydride powder and rare earth lanthanum oxide powder;
(2) Mixing the vacuum dried molybdenum powder, carbon powder, zirconium hydride powder, titanium hydride powder and rare earth lanthanum oxide powder according to the mass percentages of the constituent elements of the molybdenum alloy as defined in claim 1 to obtain premixed powder;
(3) Ball milling, fully mixing and sieving the premixed powder to ensure that the powder granularity is less than or equal to 5 mu m to obtain mixed alloy powder;
(4) Holding the mixed alloy powder for 10-15 min under a cold isostatic press under 200-250 MPa, and pressing into a cylindrical green body;
(5) Placing the cylindrical green body in a hydrogen sintering furnace, and sintering under a hydrogen atmosphere;
(6) And after sintering, cooling the alloy rod blank to room temperature along with a furnace in a hydrogen atmosphere, and taking out to obtain the molybdenum alloy rod blank.
6. The method for preparing a co-strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals according to claim 5, wherein the raw material purity in the step (1) is: mo is more than or equal to 99.97%, tiH2 is more than or equal to 99.97%, ti is more than or equal to 99.59%, zr+Hf+H is more than or equal to 99.97% in ZrH2, and Zr+Hf is more than or equal to 97.6%; the vacuum drying conditions are as follows: temperature: 100 ℃; vacuum degree: -0.1 MPa; drying time: 4 h.
7. The method for preparing the collaborative strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals according to claim 5, wherein the ball milling is carried out by adopting a planetary ball mill in the step (3), the ball milling time is 2 h, the rotating speed is 240 r/min, and the ball-to-material ratio is 2:1.
8. The method for producing a co-strengthening high-temperature high-strength molybdenum alloy by solid solution, dispersion and fine grain strengthening according to claim 5, wherein the diameter of the cylindrical green compact pressed in the step (4) is 40 mm.
9. The method for producing a co-strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals according to claim 5, wherein the sintering process in step (5) is specifically: the temperature is firstly increased to 200 ℃ in a gradient way from room temperature, then the temperature is kept, then the temperature is increased to 900 ℃ rapidly, the temperature is kept at 900 ℃, the temperature is increased to 1200 ℃ slowly after the temperature is kept at 900 ℃, then the temperature is increased to 1900 ℃ slowly, the high-temperature sintering is carried out for 4 h, and the sintered alloy rod is obtained after the high-temperature sintering is finished and is cooled along with a furnace.
10. The method for producing a co-strengthening high-temperature high-strength molybdenum alloy by solid solution, dispersion and fine grain strengthening according to claim 5, wherein the relative density of the alloy rod obtained after the high-temperature sintering of the molybdenum alloy in the step (6) is more than 98%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211719719.1A CN116219246A (en) | 2022-12-30 | 2022-12-30 | Collaborative strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211719719.1A CN116219246A (en) | 2022-12-30 | 2022-12-30 | Collaborative strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116219246A true CN116219246A (en) | 2023-06-06 |
Family
ID=86575976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211719719.1A Pending CN116219246A (en) | 2022-12-30 | 2022-12-30 | Collaborative strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116219246A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060048866A1 (en) * | 2002-03-29 | 2006-03-09 | Jun Takada | High strength high toughness mo alloy worked material and method for production tehreof |
| JP2006299384A (en) * | 2005-04-25 | 2006-11-02 | Allied Material Corp | High heat-resistant molybdenum alloy and producing method therefor |
| CN102534334A (en) * | 2012-02-21 | 2012-07-04 | 西安建筑科技大学 | High-strength and high-toughness molybdenum alloy and preparation method thereof |
| CN102534333A (en) * | 2012-01-05 | 2012-07-04 | 西安建筑科技大学 | Method for preparing fine-grain high-density TZM (Titanium-Zirconium-Molybdenum Allo) alloy |
| CN102703788A (en) * | 2012-06-26 | 2012-10-03 | 洛阳爱科麦钨钼制品有限公司 | Boron-doped TZM (molybdenum-titanium-zirconium) alloy and preparation method thereof |
| CN104511591A (en) * | 2014-12-27 | 2015-04-15 | 金堆城钼业股份有限公司 | Preparation method of composite rare earth oxide reinforced molybdenum alloy piercing mandrel |
| CN108866413A (en) * | 2018-06-11 | 2018-11-23 | 西安建筑科技大学 | A kind of tough molybdenum alloy of composite high-strength and preparation method |
| CN114951639A (en) * | 2022-05-10 | 2022-08-30 | 厦门虹鹭钨钼工业有限公司 | High-density fine-grain structure molybdenum alloy plug and preparation method thereof |
-
2022
- 2022-12-30 CN CN202211719719.1A patent/CN116219246A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060048866A1 (en) * | 2002-03-29 | 2006-03-09 | Jun Takada | High strength high toughness mo alloy worked material and method for production tehreof |
| JP2006299384A (en) * | 2005-04-25 | 2006-11-02 | Allied Material Corp | High heat-resistant molybdenum alloy and producing method therefor |
| CN102534333A (en) * | 2012-01-05 | 2012-07-04 | 西安建筑科技大学 | Method for preparing fine-grain high-density TZM (Titanium-Zirconium-Molybdenum Allo) alloy |
| CN102534334A (en) * | 2012-02-21 | 2012-07-04 | 西安建筑科技大学 | High-strength and high-toughness molybdenum alloy and preparation method thereof |
| CN102703788A (en) * | 2012-06-26 | 2012-10-03 | 洛阳爱科麦钨钼制品有限公司 | Boron-doped TZM (molybdenum-titanium-zirconium) alloy and preparation method thereof |
| CN104511591A (en) * | 2014-12-27 | 2015-04-15 | 金堆城钼业股份有限公司 | Preparation method of composite rare earth oxide reinforced molybdenum alloy piercing mandrel |
| CN108866413A (en) * | 2018-06-11 | 2018-11-23 | 西安建筑科技大学 | A kind of tough molybdenum alloy of composite high-strength and preparation method |
| CN114951639A (en) * | 2022-05-10 | 2022-08-30 | 厦门虹鹭钨钼工业有限公司 | High-density fine-grain structure molybdenum alloy plug and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| BO-LIANG HU 等: "Secondary phases formation in lanthanum-doped titanium-zirconium-molybdenum alloy", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 757, 15 August 2018 (2018-08-15), pages 340 - 347 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109706363B (en) | Eutectic high-entropy alloy and preparation method thereof | |
| CN102534334B (en) | Preparation method of high-strength and high-toughness molybdenum alloy | |
| CN110273092B (en) | CoCrNi particle reinforced magnesium-based composite material and preparation method thereof | |
| CN109338172A (en) | A kind of 2024 aluminum matrix composites and preparation method thereof of high-entropy alloy enhancing | |
| CN101956093B (en) | Oxide dispersion reinforced platinum-based alloy and preparation method thereof | |
| CN112063907B (en) | Multi-principal-element high-temperature alloy and preparation method thereof | |
| CN112063869B (en) | Preparation method of hydrogen-assisted powder metallurgy titanium-based composite material | |
| CN114645180B (en) | Double-phase reinforced aluminum alloy and preparation method thereof | |
| CN101392347B (en) | In-situ synthesized Al2O3 reinforced molybdenum based composite material and preparation method thereof | |
| CN113862540B (en) | MAX phase added molybdenum alloy and preparation method thereof | |
| CN116200622B (en) | Preparation method of superfine crystal TiAl alloy and composite material thereof | |
| CN103160701A (en) | Preparation method for high-temperature-resistant Mo-Si-B alloy | |
| CN114164367A (en) | High-toughness fine-grain molybdenum alloy and preparation method thereof | |
| CN113549801A (en) | Second-phase reinforced high-entropy binder hard alloy and preparation method thereof | |
| CN114799155B (en) | Preparation method of ceramic particle reinforced refractory high-entropy alloy | |
| CN114774727B (en) | Preparation method of nano zirconium dioxide reinforced NbMoTaW refractory high-entropy alloy | |
| CN114959406A (en) | Oscillatory pressure sintering ultrahigh-temperature medium-entropy ceramic reinforced refractory fine-grain medium-entropy alloy composite material | |
| CN109332717B (en) | Preparation method of spherical molybdenum titanium zirconium alloy powder | |
| CN108251670B (en) | Preparation method of high-temperature-resistant intermetallic compound alloy | |
| CN116287833A (en) | Preparation method of in-situ authigenic two-dimensional carbide dispersion strengthening and toughening molybdenum alloy | |
| CN108486402B (en) | TiN particle reinforced nickel-based composite material and preparation method thereof | |
| CN116219246A (en) | Collaborative strengthening high-temperature high-strength molybdenum alloy strengthened by solid solution, dispersion and fine crystals, and preparation method and application thereof | |
| CN116463523A (en) | In-situ self-generated nano oxide carbide synergistic toughening fine-grain molybdenum alloy and preparation method thereof | |
| CN112941391B (en) | NbC-containing high-density composite metal ceramic material and preparation method thereof | |
| CN114672712A (en) | Layered Mo2TiAlC2Toughened molybdenum-silicon-boron alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |