CN116162822B - Ti-Mo alloy with ultrahigh strength and toughness harmonic structure - Google Patents
Ti-Mo alloy with ultrahigh strength and toughness harmonic structure Download PDFInfo
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- CN116162822B CN116162822B CN202310265857.5A CN202310265857A CN116162822B CN 116162822 B CN116162822 B CN 116162822B CN 202310265857 A CN202310265857 A CN 202310265857A CN 116162822 B CN116162822 B CN 116162822B
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 38
- 239000000956 alloy Substances 0.000 title claims abstract description 38
- 229910011214 Ti—Mo Inorganic materials 0.000 title claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000009826 distribution Methods 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 238000007731 hot pressing Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 229910001069 Ti alloy Inorganic materials 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 8
- 239000013074 reference sample Substances 0.000 description 12
- 239000000523 sample Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000004663 powder metallurgy Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
- C22C1/0458—Alloys based on titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses an ultrahigh-strength and high-toughness titanium alloy and a preparation method thereof, relates to a Ti-Mo alloy with a harmonic structure, and belongs to the technical field of new materials. The method is characterized in that: the alloy only contains Ti and Mo elements, and comprises the following components in percentage by weight: mo: 5. 5 wt to 20. 20 wt percent, and the balance of Ti and unavoidable impurities; the elemental and structural distribution characteristics of the alloy belong to the harmonic distribution. The room temperature tensile mechanical property indexes are respectively as follows: tensile strength R m: 1000-1400 MPa, yield strength R r0.2: 850-1100 MPa, elongation A: 5-10%, strong plastic product U T: 6000 to 12000 MPa percent. The alloy of the invention has the characteristics of harmonic distribution components and structures, ultra-high strength and good toughness.
Description
Technical Field
The invention relates to the technical fields of material science and nonferrous metals and alloys thereof. In particular to a high-strength and high-toughness Ti-Mo alloy with a harmonic structure.
Background
The titanium alloy has the good performances of high strength, high specific strength, low density, corrosion resistance, good medium temperature performance, no magnetism and the like, is an important metal structural material, and has very important application and application prospect in the fields of national defense, aviation, aerospace, high-end automobiles, submarines and the like. In recent decades, the development, preparation and application of titanium alloys have been increasingly emphasized in countries around the world. The world titanium industry is steadily increasing in titanium demand in the fields of aerospace, general industry, energy and petrochemical industry, etc. In 2015-2021, global titaniferous ore total demand has a fluctuating trend, increasing from 660 ten thousand tons in 2015 to 710 ten thousand tons in 2019. Global titanium ore in 2020 and 2021 is in a state of shortage of supply and demand, and the total demand of global titanium ore in 2021 reaches 771 ten thousand tons. In addition, since the aerospace industry requires a lightweight high-strength high-toughness titanium alloy, the high-strength high-toughness titanium alloy is one of the titanium alloy series that is being controversially developed in various countries. However, the strength and toughness of the existing titanium alloy cannot meet aviation requirements, so that the application of the titanium alloy is limited to a certain extent. The research and application current situation at home and abroad are combined, the problems of the high-strength and high-toughness (tensile strength R m≥1300MPa,KIC≥55MPa·m1/2) titanium alloy exist, and the development of the high-strength and high-toughness (tensile strength R m≥1300MPa,KIC≥55MPa·m1/2) titanium alloy still is one of the main trends of the current titanium alloy development. However, titanium alloys, like other metallic materials, have significantly lost toughness while having increased strength. Therefore, developing a titanium alloy with high strength or ultra-high strength while maintaining its good ductility and toughness has very important socioeconomic and political values to promote and expand the practical application fields of titanium alloys.
Both research and experiments show that heterostructure materials have the effect of simultaneously increasing the toughness of metal materials. The material with the harmonic structure (the distribution of alloy elements and tissues shows harmonic distribution characteristics) is used as a special heterostructure material, and has the effect of increasing the toughness of metal. The strength of the harmonic TC4 titanium alloy (Ti-6 Al-4V) was increased from 1050 MPa to 1431 MPa of the conventional structure TC4 and maintained an elongation of 4.5%, as prepared by powder metallurgy techniques. Metallic Mo element, which is a typical beta-stability element of titanium alloy, is often added to titanium alloys to adjust the microstructure and mechanical properties of the titanium alloy. Mo element is added to 40% of the high-strength titanium alloy mainly used at present. However, most titanium alloys have significantly reduced ductility and toughness after increased strength. The strength of the Ti-Mo binary alloy reported at present is rarely more than 800 MPa, and the elongation after fracture is not more than 10 percent, namely the strength is improved at the cost of plastic toughness. At present, the research on the high-strength high-toughness titanium alloy is still an important content and direction of the development of the titanium alloy, and has important social significance and economic value for the long-term safe service of the titanium alloy and the expansion of the application field of the titanium alloy.
Disclosure of Invention
The invention takes a Ti-Mo alloy system as an object, and adopts a powder metallurgy combined heat treatment method to obtain the Ti-Mo alloy system with ultrahigh strength and good toughness by designing and controlling the content of metallic element Mo in the alloy system.
Object of the Invention
The invention aims to provide a Ti-Mo alloy structural material with ultrahigh strength and good toughness, and the components of the Ti-Mo alloy structural material can be expressed by the following formula: aTi-bMo. Wherein the Ti and Mo content (wt.%) varies in the range: a: 80-95 percent; b: 5-20, and the balance of unavoidable impurities contained in raw materials, wherein elements and tissues of the unavoidable impurities show harmonic distribution.
The invention aims at realizing the following scheme:
The method for preparing the alloy by adopting powder metallurgy combined heat treatment comprises the following steps: the high purity Ti powder (99.99 wt%) and Mo powder (99.5 wt%) are mixed thoroughly according to a certain proportion. The uniformly mixed powder is pre-pressed on a 30 ton cold press for 5 minutes to form a blank, and then transferred to a vacuum hot pressing device for hot pressing sintering, wherein the hot pressing process is 850 ℃,60 MPa and the pressure maintaining time is 3 minutes. And hot-pressing to obtain a sintered cylinder. The sintered body cylinder was subjected to a thermal diffusion treatment in an argon atmosphere at 900 ℃ for 8 hours. Finally, aging treatment is carried out at 500 ℃ for 4 hours. All previous operations were performed under vacuum or under argon. And (3) peeling and surface grinding the surface of the annealed/aged alloy sample to obtain a Ti-Mo alloy sample with a harmonic structure. And detecting the mechanical properties of the alloy. The room temperature mechanical properties of the alloy of the invention are: tensile strength R m: 1000-1400 MPa, yield strength R r0.2: 850-1100 MPa, elongation A: 5-10%, strong plastic product U T: 6000 to 12000 MPa percent.
The room temperature uniaxial tensile test was performed on a tensile tester at the tensile rate of: 5X 10 -4s-1. And the length change of the sample during the stretching process is tracked and measured by an extensometer.
The invention discloses the following technical effects:
The experimental conditions required in the preparation process of the invention are convenient, and the preparation method can be obtained by a traditional powder metallurgy combined heat treatment method. The elements and the structures of the alloy prepared by the invention are distributed in harmonic, and the mechanical properties of the alloy can be controlled by adjusting the content of alpha and beta phases and the microstructure distribution. The prepared alloy has ultrahigh strength and good toughness.
Drawings
FIG. 1 is a schematic representation of an alloy tensile specimen of the present invention.
FIG. 2 is a graph showing the engineering stress-engineering strain curve of the alloy and the reference sample prepared in examples 1-3 of the present invention.
FIG. 3 shows the results of the alloy and the reference sample prepared in examples 1-3 according to the present invention with a strong plastic product U T.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
Example 1
The high purity Ti powder (99.99 wt%) and Mo powder (99.5 wt%) were thoroughly mixed in a ratio of 90:10 by weight Ti to Mo. The uniformly mixed powder is pre-pressed on a 30 ton cold press for 5 minutes to form a blank, and then transferred to a vacuum hot pressing device for hot pressing sintering, wherein the hot pressing process is 850 ℃,60 MPa and the pressure maintaining time is 3 minutes. And hot-pressing to obtain a sintered cylinder. The sintered body cylinder was subjected to a thermal diffusion treatment in an argon atmosphere at 900 ℃ for 8 hours. All previous operations were performed under vacuum or under argon. And (3) peeling and surface grinding the surface of the alloy sample subjected to thermal diffusion annealing to obtain a Ti-Mo alloy sample with a harmonic structure. And processing into a sample for testing. The mechanical properties are tested in the data of example 1 in figures 2 and 3.
Example 2
Compared with the embodiment 1, the embodiment is characterized in that the weight ratio of Ti to Mo powder is different, and the specific process steps are consistent:
The high purity Ti powder (99.99 wt%) and Mo powder (99.5: 99.5 wt%) were thoroughly mixed in a ratio of 85:15 by weight Ti to Mo. The uniformly mixed powder is pre-pressed on a 30 ton cold press for 5 minutes to form a blank, and then transferred to a vacuum hot pressing device for hot pressing sintering, wherein the hot pressing process is 850 ℃,60 MPa and the pressure maintaining time is 3 minutes. And hot-pressing to obtain a sintered cylinder. The sintered body cylinder was subjected to a thermal diffusion treatment in an argon atmosphere at 900 ℃ for 8 hours. All previous operations were performed under vacuum or under argon. And (3) peeling and surface grinding the surface of the alloy sample subjected to thermal diffusion annealing to obtain a Ti-Mo alloy sample with a harmonic structure. And processing into a sample for testing. The mechanical properties are tested in the data of example 2 in figures 2 and 3.
Example 3
Compared with example 2, this example is different in the heat treatment process. The specific process steps are consistent:
The high purity Ti powder (99.99 wt%) and Mo powder (99.5: 99.5 wt%) were thoroughly mixed in a ratio of 85:15 by weight Ti to Mo. The uniformly mixed powder is pre-pressed on a 30 ton cold press for 5 minutes to form a blank, and then transferred to a vacuum hot pressing device for hot pressing sintering, wherein the hot pressing process is 850 ℃,60 MPa and the pressure maintaining time is 3 minutes. And hot-pressing to obtain a sintered cylinder. The sintered body cylinder was subjected to a thermal diffusion treatment in an argon atmosphere at 900 ℃ for 8 hours. Finally, aging treatment is carried out at 500 ℃ for 4 hours. All previous operations were performed under vacuum or under argon. And (3) peeling and surface grinding the surface of the alloy sample subjected to aging treatment to obtain a Ti-Mo alloy sample with a harmonic structure. And processing into a sample for testing. The mechanical properties are shown in the data of example 3 in fig. 2 and 3.
Effect example 1
A reference sample was prepared from pure titanium powder according to the procedure of example 1 and a tensile test was performed. Engineering stress-engineering strain curves of the Ti-Mo series alloy with the harmonic structure prepared by the reference sample and the examples 1-3 are shown in figure 2. It can be seen from fig. 2 that the strength and shape of the different samples are different. Wherein the tensile strength R m = 607 MPa、Rr0.2 = 442 MPa of the reference sample, the elongation after break is a = 17.3%, and the tensile strengths R m of the samples of examples 1-3 are respectively: 1069, 1002 and 1397MPa, 176%,167% and 230% of the reference sample, respectively; the yield strengths R r0.2 of the samples of examples 1 to 3 were respectively: 941, 875 and 1017 MPa, 213%,198% and 230% of the reference sample, respectively; the post-break elongation A of the samples of examples 1-3 was 9.27%,7.56% and 4.53%, respectively, 53%,43% and 25% of the reference sample, respectively.
Effect example 2
A reference sample was prepared from pure titanium powder according to the procedure of example 1 and a tensile test was performed. The results of the strong plastic products of the reference sample and the Ti-Mo series alloy with the harmonic structure prepared in the examples 1-3 are shown in the attached figure 3. As can be seen from FIG. 3, the strength and elongation products are different for different samples. Wherein the strong plastic product U T = 10246 MPa DEG of the reference sample, the strong plastic products U T of the samples of examples 1-3 are respectively: 11380, 7701 and 6020 MPa%. The strength-plastic product is 111%,75.1% and 58.8% of the reference sample respectively.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (2)
1. A Ti-Mo alloy with ultra-high toughness is characterized in that: the alloy elements and the weight percentage composition are as follows: metallic molybdenum: 5 wt-20 wt%, the balance being titanium and unavoidable impurities; the preparation process comprises the following steps: fully mixing 99.99wt% of Ti powder and 99.5wt% of Mo powder according to a determined proportion, prepressing the uniformly mixed powder on a 30-ton cold press for 5 minutes to form a blank, transferring the blank to vacuum hot press equipment for hot press sintering, obtaining a sintered body cylinder after hot pressing, wherein the hot press process is 850 ℃, the pressure maintaining time is 3 minutes, carrying out heat diffusion treatment on the sintered body cylinder in an argon environment at 900 ℃ for 8 hours, and finally carrying out aging treatment at 500 ℃ for 4 hours; the element and structure distribution characteristics of the Ti-Mo series alloy belong to harmonic distribution.
2. The Ti-Mo based alloy with ultra-high toughness according to claim 1, wherein: the room temperature tensile mechanical properties of the alloy are respectively that the tensile strength R m: 1000-1400 MPa, yield strength R r0.2: 850-1100 MPa, elongation A: 5-10%, strong plastic product U T: 6000 to 12000 MPa percent.
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EP1695676A1 (en) * | 2005-02-25 | 2006-08-30 | WALDEMAR LINK GmbH & Co. KG | Method of producing a medical implant made of a beta-Titanium-Molybdenum-alloy and according implant |
EP2679694B1 (en) * | 2011-02-23 | 2017-09-06 | National Institute for Materials Science | Ti-mo alloy and method for producing same |
KR20160087424A (en) * | 2015-01-13 | 2016-07-22 | 포항공과대학교 산학협력단 | Harmonic structure powder for powder metallurgy, manufactureing method thereof and powder compacting method using harmonic structure powder |
CN109957678B (en) * | 2017-12-25 | 2021-07-09 | 西部超导材料科技股份有限公司 | Preparation method of medical Ti-15Mo alloy ingot |
CN114836650B (en) * | 2022-04-27 | 2022-11-18 | 北京航空航天大学 | Titanium alloy with complete equiaxed crystal structure and ultrahigh yield strength |
CN115404382B (en) * | 2022-09-22 | 2023-06-06 | 东南大学 | High-strength high-plasticity titanium alloy and preparation method thereof |
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Title |
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3种工艺制备医用钛钼合金性能的对比分析;赵明威;殷海荣;王晓江;;陕西科技大学学报(自然科学版);20081225(06);第16-19页 * |
粉末冶金Ti-Mo合金的显微组织及力学性能;林迎午;路新;孙博;刘程程;曲选辉;;稀有金属材料与工程;20170515(05);第1387-1392页 * |
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