CN113564417A - High-strength titanium alloy and preparation method thereof - Google Patents
High-strength titanium alloy and preparation method thereof Download PDFInfo
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- CN113564417A CN113564417A CN202110650023.7A CN202110650023A CN113564417A CN 113564417 A CN113564417 A CN 113564417A CN 202110650023 A CN202110650023 A CN 202110650023A CN 113564417 A CN113564417 A CN 113564417A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C14/00—Alloys based on titanium
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
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- C22B9/20—Arc remelting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
Abstract
The invention provides a high-strength titanium alloy and a preparation method thereof, wherein the high-strength titanium alloy is Ti-Al-V-M high-strength titanium alloy and consists of the following raw materials in percentage by mass: al 5-6%, V1.0-2.0%, Mo 1-1.5%, Ni 0.5-1.0%, Sn 0.5-1.0%, Zr 0.5-1.0%, and the balance Ti. Experimental results show that compared with a comparative alloy obtained by the same treatment process, the yield strength of the alloy is improved by 9-22.43%, and the tensile strength of the alloy is improved by 8.62-34.71%.
Description
Technical Field
The invention belongs to the technical field of titanium alloy, and particularly relates to a high-strength titanium alloy and a preparation method thereof.
Background
Titanium and titanium alloy have excellent comprehensive properties such as high specific strength, corrosion resistance, low temperature resistance, no magnetism, good biocompatibility and the like, are widely applied in the fields of ocean engineering, biomedicine, aerospace, chemical engineering, metallurgy and the like, and are important strategic metals.
The structural titanium alloy is applied to the manufacturing aspects of parts with high strength and complex shapes in the aerospace industry, such as wing joint structural members of aviation airplanes, connecting frames of airframes and undercarriages, hanging engine joints and the like, and the manufacture of important or key force bearing parts with high requirements on strength and durability by virtue of excellent machinability and mechanical properties of the structural titanium alloy. However, as for the traditional titanium alloy of the aviation structure, the strength level of the titanium alloy still cannot meet increasingly strict industrial service standards, so that the titanium alloy aviation structure has a short service cycle and is limited in further application, and therefore, the development of the high-strength titanium alloy is a very significant work.
Disclosure of Invention
In view of the above, the present invention provides a high strength titanium alloy and a preparation method thereof, and the obtained alloy has high strength.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a high-strength titanium alloy is a Ti-Al-V-M high-strength titanium alloy and consists of the following raw materials in percentage by mass:
al 5-6%, V1.0-2.0%, Mo 1-1.5%, Ni 0.5-1.0%, Sn 0.5-1.0%, Zr 0.5-1.0%, and the balance Ti.
Further, the high-strength titanium alloy is a Widmannstatten structure with a basket characteristic, primary beta grains are clearly visible, and a lamella alpha phase and a residual fine beta phase are arranged inside the high-strength titanium alloy.
The invention also relates to a preparation method of the high-strength titanium alloy, which comprises the following steps:
(1) preparation of the raw materials
The raw material preparation of claim 1 or 2, wherein the raw material purity is higher than 99 wt%, the surface of the raw material is polished to remove oxide skin, then ultrasonic cleaning is carried out for at least 5min by acetone and ethanol respectively, and then the raw material is accurately weighed according to the mass fraction of each element for alloy smelting;
(2) melting of alloys
Using a vacuum non-consumable electric arc furnace, placing the cleaned raw materials in water-cooled copper crucibles, placing a pure titanium ingot in one of the crucibles, pumping the vacuum degree of the furnace body to be below 5Pa by using a mechanical pump, starting automatic vacuum, pumping the vacuum degree to be 5 multiplied by 10-3Below Pa, closing the automatic vacuum;
argon gas as protective atmosphere is filled until the air pressure in the furnace body is about 0.05 MPa, and meanwhile, the discharge in the smelting process is avoided; firstly, smelting a pure titanium ingot for a period of time to eliminate residual oxygen in a furnace chamber, then adjusting a tungsten electrode to be close to a raw material to start arc striking, continuously smelting after the raw material is completely molten into a liquid state, then closing current, and turning over the alloy after the alloy is cooled; the above operation is repeated several times to obtain an alloy with uniform composition.
Further, pure titanium ingots are smelted for 3min to eliminate residual oxygen in the furnace chamber, and then the tungsten electrode is adjusted to be about 1-2mm away from the raw materials to start arc striking.
Further, the smelting temperature is 2500-3000 ℃.
Further, continuously smelting for 2-4 min.
Further, the melting is repeated 6 to 10 times to ensure that the components of the obtained cast ingot are uniform.
The invention obtains the as-cast alloy ingot after smelting the alloy raw materials. In the invention, the purity of the alloy raw materials is higher than 99 wt%. Before smelting, respectively carrying out ultrasonic cleaning on the alloy raw materials for at least 5min by using acetone and ethanol; the present invention does not require special embodiments of the ultrasonic cleaning, and may be practiced as is known to those skilled in the art.
In the invention, the smelting is vacuum non-consumable arc smelting. When vacuum non-consumable arc melting is adopted, firstly, the vacuum degree in the furnace cavity is pumped to 5 multiplied by 10-3Introducing argon to 0.05 MPa after Pa is lower; the smelting temperature is preferably 2500-3000 ℃; the smelting time is preferably 2-4 min.
The present invention does not require special embodiments of the vacuum arc melting process, as will be appreciated by those skilled in the art. The invention repeatedly carries out smelting for 6-10 times to ensure that the components of the obtained cast ingot are uniform.
The invention fills argon as protective atmosphere until the air pressure in the furnace body is about 0.05 MPa, so as to prevent the metal material from being oxidized and ensure that the discharge cannot occur in the smelting process.
The smelting temperature is 2500-3000 ℃, the temperature range is selected to ensure that the alloy raw materials can be fully melted, the incomplete smelting phenomenon can occur when the temperature is lower than the temperature range, on the contrary, the burning loss of part of the metal raw materials can be caused when the temperature is higher than the temperature range, the alloy components are inaccurate, similarly, the smelting time is preferably 2-4 min, the alloy is fully smelted, the components are uniform, the smelting is insufficient when the time is too short, and the alloy elements can be burnt and lost when the time is too long.
Compared with the prior art, the invention has the following advantages:
(1) the invention provides a high-strength titanium alloy which comprises, by mass, 5-6% of Al, 1.0-2.0% of V, 1-1.5% of Mo, 0.5-1.0% of Ni, 0.5-1.0% of Sn, 0.5-1.0% of Zr and the balance Ti. . The invention strictly controls the content of each element and improves the mechanical property of the titanium alloy, wherein Al is the most main strengthening element in the titanium alloy. Aluminum is the most obvious element with solid solution strengthening effect in alpha stabilizing elements, the solid solubility of the aluminum in alpha-Ti is greater than that of beta-Ti, the temperature of mutual transformation of alpha and beta can be improved, and an alpha phase region is enlarged; v and Mo are elements that lower the β -transus temperature. The position on the periodic table is close to Ti and has the same lattice type with beta Ti, the lattice type is infinitely mutually soluble with the beta Ti, the lattice type has limited solubility in the alpha Ti, and the lattice type can also play a role in strengthening the alloy; the addition of Ni, Sn and Zr elements can cause lattice distortion, and the defects can cause that nucleation points are increased and the nucleation density is increased in the nucleation process, so that the effect of grain refinement is achieved, and fine grain strengthening is realized. Experimental results show that compared with a comparative alloy obtained by the same treatment process, the yield strength of the titanium alloy obtained by the invention is improved by 9-22.43%, and the tensile strength of the titanium alloy is improved by 8.62-34.71%.
(2) The invention has low cost and simple operation process.
Drawings
FIG. 1 is a microstructure of a titanium alloy obtained by the method of example 1;
FIG. 2 is a microstructure of a titanium alloy produced by the method of example 2;
FIG. 3 is a microstructure of a titanium alloy obtained by the method of example 3;
FIG. 4 is a microstructure of a titanium alloy obtained by the method of example 4;
FIG. 5 is a graph showing the dimensions of tensile specimens used in the tensile testing of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available by purchase.
All percentages are expressed as mass fractions unless otherwise indicated. The proportion is mass proportion, and the concentration is mass concentration.
Example 1
As shown in fig. 1, the Ti-Al-V-M high-strength titanium alloy of the present embodiment is composed of the following raw materials by mass: 6% of Al, 2% of V, 1.5% of Mo, 0.5% of Zr and the balance of Ti.
The Ti-Al-V-M high-strength titanium alloy comprises the following steps:
(1) preparation of the raw materials
Preparing the components according to the weight percentage, wherein the purity of the raw materials is higher than 99 wt%, polishing the surfaces of the raw materials to remove oxide skins, respectively carrying out ultrasonic cleaning for 10min by using acetone and ethanol, and accurately weighing the components according to the mass fraction of each element for alloy smelting.
(2) Melting of alloys
Placing the cleaned raw materials in a vacuum non-consumable arc furnacePlacing a pure titanium ingot in one of the water-cooled copper crucibles, pumping the vacuum degree of the furnace body to be below 5Pa by using a mechanical pump, starting automatic vacuum, and pumping the vacuum degree to be 5 multiplied by 10-3Below Pa, closing the automatic vacuum;
argon gas as protective atmosphere is filled until the pressure in the furnace body is close to 0.05 MPa, and meanwhile, the discharge in the smelting process is avoided; firstly, smelting a pure titanium ingot for 3min to eliminate residual oxygen in a furnace chamber, then adjusting a tungsten electrode to be 1mm away from the raw material, and starting arc striking. After the raw materials are completely melted into liquid, continuously melting for 2min, then closing the current, and turning over the alloy after the alloy is cooled; the above operation was repeated 6 times in this manner to ensure that the composition of the obtained ingot was uniform to obtain an alloy having a uniform composition. The temperature of the melting was 2500 ℃.
Example 2
As shown in fig. 2, the Ti-Al-V-M high-strength titanium alloy of the present embodiment is composed of the following raw materials by mass: 6% of Al, 1.5% of V, 1.5% of Mo, 0.5% of Sn, 0.5% of Zr and the balance of Ti.
The Ti-Al-V-M high-strength titanium alloy comprises the following steps:
(1) preparation of the raw materials
Preparing the components according to the weight percentage, wherein the purity of the raw materials is higher than 99 wt%, polishing the surfaces of the raw materials to remove oxide skins, respectively carrying out ultrasonic cleaning for 15min by using acetone and ethanol, and accurately weighing the components according to the mass fraction of each element for alloy smelting.
(2) Melting of alloys
Using a vacuum non-consumable electric arc furnace, placing the cleaned raw materials in water-cooled copper crucibles, placing a pure titanium ingot in one of the crucibles, pumping the vacuum degree of the furnace body to be below 5Pa by using a mechanical pump, starting automatic vacuum, pumping the vacuum degree to be 5 multiplied by 10-3Below Pa, closing the automatic vacuum;
argon gas as protective atmosphere is filled until the air pressure in the furnace body is about 0.05 MPa, and meanwhile, the discharge in the smelting process is avoided; firstly, smelting a pure titanium ingot for 3min to eliminate residual oxygen in a furnace chamber, then adjusting a tungsten electrode to be 2mm away from the raw material, and starting arc striking. After the raw materials are completely melted into liquid, continuously melting for 3min, then closing the current, and turning over the alloy after the alloy is cooled; the above operation was repeated 8 times in this manner to ensure that the composition of the obtained ingot was uniform to obtain an alloy having a uniform composition. The temperature of the melting was 2800 ℃.
Example 3
As shown in fig. 3, the Ti-Al-V-M high-strength titanium alloy of the present embodiment is composed of the following raw materials by mass: 6% of Al, 2% of V, 1% of Ni, 0.5% of Sn, 0.5% of Zr and the balance of Ti.
The Ti-Al-V-M high-strength titanium alloy comprises the following steps:
(1) preparation of the raw materials
Preparing the components according to the weight percentage, wherein the purity of the raw materials is higher than 99 wt%, polishing the surfaces of the raw materials to remove oxide skins, respectively carrying out ultrasonic cleaning for 6min by using acetone and ethanol, and accurately weighing the components according to the mass fraction of each element for alloy smelting.
(2) Melting of alloys
Using a vacuum non-consumable electric arc furnace, placing the cleaned raw materials in water-cooled copper crucibles, placing a pure titanium ingot in one of the crucibles, pumping the vacuum degree of the furnace body to be below 5Pa by using a mechanical pump, starting automatic vacuum, pumping the vacuum degree to be 5 multiplied by 10-3Below Pa, closing the automatic vacuum;
argon gas as protective atmosphere is filled until the air pressure in the furnace body is about 0.05 MPa, and meanwhile, the discharge in the smelting process is avoided; firstly, smelting a pure titanium ingot for 3min to eliminate residual oxygen in a furnace chamber, then adjusting a tungsten electrode to be 1mm away from the raw material, and starting arc striking. After the raw materials are completely melted into liquid, continuously melting for 2-4 min, then closing the current, and turning over the alloy after the alloy is cooled; the above operation is repeated 6 to 10 times to ensure that the obtained ingot has uniform components so as to obtain an alloy with uniform components. The smelting temperature is 2500-3000 ℃.
Example 4
As shown in fig. 4, the Ti-Al-V-M high-strength titanium alloy of the present embodiment is composed of the following raw materials by mass: 6% of Al, 1.5% of Mo, 1% of V, 1.0% of Nb, 0.5% of Sn and the balance of Ti.
The Ti-Al-V-M high-strength titanium alloy comprises the following steps:
(1) preparation of the raw materials
Preparing the components according to the weight percentage, wherein the purity of the raw materials is higher than 99 wt%, polishing the surfaces of the raw materials to remove oxide skins, respectively carrying out ultrasonic cleaning for 12min by using acetone and ethanol, and accurately weighing the components according to the mass fraction of each element for alloy smelting.
(2) Melting of alloys
Using a vacuum non-consumable electric arc furnace, placing the cleaned raw materials in water-cooled copper crucibles, placing a pure titanium ingot in one of the crucibles, pumping the vacuum degree of the furnace body to be below 5Pa by using a mechanical pump, starting automatic vacuum, pumping the vacuum degree to be 5 multiplied by 10-3Below Pa, closing the automatic vacuum;
argon gas as protective atmosphere is filled until the air pressure in the furnace body is about 0.05 MPa, and meanwhile, the discharge in the smelting process is avoided; pure titanium ingots were first smelted for 3min to eliminate residual oxygen in the furnace chamber, and then the tungsten electrode was adjusted to 1mm from the raw material to start arc striking. After the raw materials are completely melted into liquid, continuously melting for 3min, then closing the current, and turning over the alloy after the alloy is cooled; the above operation was repeated 10 times in this manner to ensure that the composition of the obtained ingot was uniform to obtain an alloy having a uniform composition. The temperature of the melting is 3000 ℃.
In all examples, the specific implementation of ultrasonic cleaning is not particularly required, and may be as known to those skilled in the art. The embodiment of vacuum arc melting is not particularly limited and may be any known to those skilled in the art.
Comparative example 1:
an alloy composition of Ti-6Al-2V titanium alloy was prepared in the manner of example 1.
Comparative example 2:
the melting temperature was 1500 ℃ and the same as in example 1 was repeated.
Comparative example 3:
the melting temperature was 3500 ℃ and the same operation as in example 1 was repeated.
Comparative example 4:
the melting time was 6min, and the rest was the same as in example 1.
The alloys obtained in examples 1 to 4 and comparative example were analyzed as follows:
(1) analysis of mechanical Properties
Tensile specimens as shown in FIG. 5 were cut out of the titanium alloys of examples 1 to 4 and comparative examples 1 to 4 by wire cutting. At least 5 tensile specimens were cut out of each specimen to ensure reproducibility of the data, and the measurement was carried out by room-temperature uniaxial tensile test using an AGXplus Universal Material testing machine (manufacturer: Shimadzu, Japan) whose tensile displacement was monitored with an extensometer over the course of the test at a tensile rate of 5X 10-3s-1And obtaining the relevant data of the mechanical property thereof, wherein the test result is shown in the table 1.
TABLE 1 mechanical property test results of titanium alloys obtained in examples 1 to 4 and comparative example 1
As can be seen from Table 1, the titanium alloy obtained by the present invention has a yield strength increase of 22.43% and a tensile strength increase of 34.71% compared to the comparative alloy, because the titanium alloy obtained by the present invention contains a finer lamellar alpha phase and a higher proportion of residual beta phase, and the addition of the element has a solid solution strengthening effect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A high-strength titanium alloy is characterized in that: the high-strength titanium alloy is Ti-Al-V-M and consists of the following raw materials in percentage by mass:
al 5-6%, V1.0-2.0%, Mo 1-1.5%, Ni 0.5-1.0%, Sn 0.5-1.0%, Zr 0.5-1.0%, and the balance Ti.
2. A high strength titanium alloy according to claim 1, wherein: the high-strength titanium alloy is a widmannstatten structure with basket characteristics, primary beta grains are clearly visible, and a lamella alpha phase and a residual fine beta phase are arranged inside the high-strength titanium alloy.
3. A preparation method of a high-strength titanium alloy is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of the raw materials
The raw material preparation of claim 1 or 2, wherein the raw material purity is higher than 99 wt%, the surface of the raw material is polished to remove oxide skin, then ultrasonic cleaning is carried out for at least 5min by acetone and ethanol respectively, and then the raw material is accurately weighed according to the mass fraction of each element for alloy smelting;
(2) melting of alloys
Using a vacuum non-consumable electric arc furnace, placing the cleaned raw materials in water-cooled copper crucibles, placing a pure titanium ingot in one of the crucibles, pumping the vacuum degree of the furnace body to be below 5Pa by using a mechanical pump, starting automatic vacuum, pumping the vacuum degree to be 5 multiplied by 10-3Below Pa, closing the automatic vacuum;
argon gas as protective atmosphere is filled until the air pressure in the furnace body is about 0.05 MPa, and meanwhile, the discharge in the smelting process is avoided; firstly, smelting a pure titanium ingot for a period of time to eliminate residual oxygen in a furnace chamber, then adjusting a tungsten electrode to be close to a raw material to start arc striking, continuously smelting after the raw material is completely molten into a liquid state, then closing current, and turning over the alloy after the alloy is cooled; the above operation is repeated several times to obtain an alloy with uniform composition.
4. The production method according to claim 3, characterized in that: pure titanium ingots are smelted for 3min to eliminate residual oxygen in the furnace chamber, and then the tungsten electrode is adjusted to be about 1-2mm away from the raw materials to start arc striking.
5. The production method according to claim 3, characterized in that: the smelting temperature is 2500-3000 ℃.
6. The production method according to claim 3, characterized in that: and continuously smelting for 2-4 min.
7. The production method according to claim 3, characterized in that: and the smelting is repeated for 6-10 times, so that the components of the obtained cast ingot are uniform.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107058800A (en) * | 2017-03-02 | 2017-08-18 | 中国船舶重工集团公司第七二五研究所 | A kind of anti-corrosion solderable crack arrest titanium alloy of middle intensity and preparation method thereof |
| CN108486411A (en) * | 2018-06-06 | 2018-09-04 | 哈尔滨工业大学 | A kind of high strength anti-corrosion titanium alloy and preparation method thereof of Ni elements enhancing |
| CN110218908A (en) * | 2019-07-25 | 2019-09-10 | 哈尔滨工业大学 | A kind of Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy and preparation method thereof |
| CN111593230A (en) * | 2020-04-30 | 2020-08-28 | 中国石油天然气集团有限公司 | Pipe for 930 MPa-level ultrahigh-strength titanium alloy drill rod and manufacturing method thereof |
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- 2021-06-10 CN CN202110650023.7A patent/CN113564417A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107058800A (en) * | 2017-03-02 | 2017-08-18 | 中国船舶重工集团公司第七二五研究所 | A kind of anti-corrosion solderable crack arrest titanium alloy of middle intensity and preparation method thereof |
| CN108486411A (en) * | 2018-06-06 | 2018-09-04 | 哈尔滨工业大学 | A kind of high strength anti-corrosion titanium alloy and preparation method thereof of Ni elements enhancing |
| CN110218908A (en) * | 2019-07-25 | 2019-09-10 | 哈尔滨工业大学 | A kind of Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy and preparation method thereof |
| CN111593230A (en) * | 2020-04-30 | 2020-08-28 | 中国石油天然气集团有限公司 | Pipe for 930 MPa-level ultrahigh-strength titanium alloy drill rod and manufacturing method thereof |
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Application publication date: 20211029 |