CN108165820B - Short-time ultrahigh-strength heat-resistant titanium alloy, alloy plate and preparation method - Google Patents
Short-time ultrahigh-strength heat-resistant titanium alloy, alloy plate and preparation method Download PDFInfo
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
- B21J5/002—Hybrid process, e.g. forging following casting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- 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
Abstract
The invention relates to a short-time ultrahigh-strength heat-resistant titanium alloy, an alloy plate and a preparation method thereof, belonging to the field of high-temperature titanium alloy materials. The alloy comprises the following components in percentage by weight: 6.0-8.0%, Sn: 2-4.5%, Zr: 2-4.5%, Mo: 0.5-5.0%, Fe: 0.5-2.0%, W: 0.5-2.0%, Si: 0.2-0.5%, and the balance Ti. The invention also discloses a plate prepared by adopting the short-time ultrahigh-strength heat-resistant titanium alloy and a preparation method thereof. The alloy and the alloy plate have excellent matching of room-temperature and high-temperature mechanical properties, and can meet the application requirements of titanium alloy under the conditions of short time, high temperature and high strength.
Description
Technical Field
The invention relates to a short-time ultrahigh-strength heat-resistant titanium alloy, an alloy plate and a preparation method thereof, belonging to the field of high-temperature titanium alloy materials.
Background
With the continuous improvement of the flight speed of the short-time high-speed aircraft, the aircraft can generate a strong gas heat effect in the ultrahigh-sound-speed flight, so that the surface temperature of the shell reaches 600-700 ℃ in a short time, and on the one hand, the shell material of the aircraft is required to have good high-temperature strength and long service life under large stress; on the other hand, the aircraft shell is a sheet metal component, and is required to have matched room temperature plasticity and process forming performance. In order to meet the above requirements and to ensure weight reduction of the aircraft, the design sector chooses high-temperature titanium alloys. The high-temperature titanium alloy (generally defined as long-time high-temperature titanium alloy) which is widely applied at present is mainly used for manufacturing aeroengines, has extremely high requirements on the structural stability and the oxidation resistance of materials at long-term service temperature, the working temperature of the high-temperature titanium alloy can reach 600 ℃, the high-temperature strength and the oxidation resistance of the alloy can be sharply reduced along with the further increase of the use temperature, and the use temperature and the high-temperature strength of the alloy can not be improved through the traditional processing and heat treatment process. To form an intermetallic compound Ti3Al and TiAl areThe base alloys have higher service temperature and high temperature strength, but the workability and plasticity of the alloys are poor, and the alloys cannot be suitable for sheet metal forming. Therefore, the development of new high-performance titanium alloys for short-time applications (short-time high-temperature titanium alloys) has received high attention. The main differences between long time high temperature titanium alloys and short time high temperature titanium alloys under the use conditions are listed in table 1. By comparison, it can be seen that short-time high-temperature titanium alloys place higher demands on the process plasticity of the material at room temperature, the instantaneous strength at temperatures above 600 ℃, and the long-term life under large stress (close to yield strength).
TABLE 1 Long-term high-temperature titanium alloys and short-term high-temperature titanium alloys
At the present stage, the main approaches for improving the service temperature and the high-temperature strength of the titanium alloy are as follows: 1) the component design of the titanium alloy is from few elements to many elements, from simple to complex, and the alloy strength is improved through multi-element composite reinforcement; 2) development of fine Ti3The titanium alloy based on the Al ordered phase dispersion distribution ensures plasticity and improves the alloy strength through second phase strengthening.
Disclosure of Invention
The invention aims to provide a Ti-Al-Sn-Zr-Mo-Fe-W-Si series ultrahigh-strength heat-resistant titanium alloy and an alloy plate which can be applied at 650-700 ℃ for a short time, and a preparation method thereof.
The short-time high-temperature titanium alloy has the working temperature of over 600 ℃ generally and short working time of between dozens of minutes and several hours generally, and has the requirements of good technological properties during material molding and matching of high-temperature instantaneous strength and durability under large stress. At present, the maximum service temperature of the high-temperature titanium alloy for aviation long time is 600 ℃, and the high-temperature titanium alloy is typically represented by IMI834, Ti-1100, BT36, Ti-60 and Ti-600. These alloys are almost all high [ Al ] of Ti-Al-Sn-Zr-Mo-Si system except BT36]eqThe near alpha type titanium alloy has low content of beta stable element in consideration of the structural stability of the alloy during long-term high-temperature work. If the increase of the p-alpha phase is continuedThe solid solution strengthening of (A) is a decisive alpha stabilizing element and neutral element, which easily leads to alpha2The alloy becomes brittle due to the precipitation of a large amount of phases, the technological performance of the material is reduced, and the metal plate forming is not facilitated. Therefore, in designing the composition of the short-time high-temperature titanium alloy, β -stable element should be selected for strengthening. Mo and W have the characteristics of high melting point, high strength, high thermal conductivity, small thermal expansion coefficient and the like, have atomic radius and electronegativity similar to those of Ti, have bcc structures, and have high solubility in beta-Ti, and the addition of the two elements can effectively strengthen beta phase and improve the high-temperature strength of the alloy. The Fe element has strong capability of stabilizing the beta phase, the price is low, the raw material cost can be reduced when the Fe element is added into the alloy, and a certain amount of beta phase can be reserved after the alloy is subjected to heat treatment while the Fe element is added to strengthen the beta phase, so that the processing technology performance of the titanium alloy is improved, and the sheet forming of the alloy is facilitated.
The short-time ultrahigh-strength heat-resistant titanium alloy comprises the following components in percentage by weight: 6.0-8.0%, Sn: 2-4.5%, Zr: 2-4.5%, Mo: 0.5-5.0%, Fe: 0.5-2.0%, W: 0.5-2.0%, Si: 0.2-0.5%, and the balance Ti.
The titanium alloy also contains O, and the weight percentages of the O and the O are as follows: o: 0.15 to 0.25 percent.
The content (weight percentage) of impurity elements N, H and C in the titanium alloy is as follows: n is less than 0.01 percent, H is less than 0.0015 percent, and C is less than 0.05 percent.
A preparation method of a short-time ultrahigh-strength heat-resistant titanium alloy comprises the following steps: the alloy adopts 0-grade sponge Ti, sponge Zr, metal Al beans and TiO as raw materials2Ti-Sn, Ti-Si, Al-Mo, Mo-Fe and Al-Mo-W-Ti master alloys; sponge Ti, sponge Zr, metallic Al beans and TiO2And after the intermediate alloy is weighed, performing layered material distribution, then pressing into an electrode, and preparing an ingot by three times of vacuum consumable arc melting.
A short-time ultrahigh-strength heat-resistant titanium alloy plate is made of the short-time ultrahigh-strength heat-resistant titanium alloy.
The alloy of the invention can be used for preparing plates by the following optimized processing technology.
A preparation method of a short-time ultrahigh-strength heat-resistant titanium alloy plate comprises the following steps: cogging the ingot prepared by the method above a phase transformation point, gradually cooling, performing intermediate forging to prepare a plate blank, fully heating the plate blank below the phase transformation point at 40-50 ℃, and rolling the plate blank on a rolling mill to form a plate with the thickness of 2.5-3 mm; and then carrying out integral heat treatment on the plate, wherein the heat treatment temperature is 20 ℃ below the phase transition point, the heat preservation time is 2h, and the cooling mode is air cooling.
The Ti-Al-Sn-Zr-Mo-Fe-W-Si alloy plate is prepared by adopting the processing technology, a room temperature bending test is carried out according to a GB/T232-2010 method, a room temperature tensile test is carried out according to a GB/T228.2-2010 method, a high temperature tensile test is carried out according to a GB/T4338-2006 method, and a high temperature durability test is carried out according to a GB/T2039-1997 method. The alloy of the invention has the following properties: the bending angle at room temperature is 180 degrees; the tensile strength at room temperature is not lower than 1200MPa, the yield strength is not lower than 1050MPa, and the elongation is not lower than 8%; the tensile strength at 600 ℃ is not lower than 800MPa, and the yield strength is not lower than 650 MPa; the tensile strength at 700 ℃ is not lower than 550MPa, and the yield strength is not lower than 400 MPa; the lasting breaking time is not less than 60min under the condition of 650 ℃/425 MPa. The Ti-Al-Sn-Zr-Mo-Fe-W-Si alloy and the alloy plate have excellent matching of room-temperature and high-temperature mechanical properties, and can meet the application requirements of the titanium alloy under the conditions of short time, high temperature and high strength.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the present invention is not limited thereto. The materials in the following examples were all commercially available, and the test methods used therein were all conventional methods unless otherwise specified.
Example 1
Preparing Ti-6Al-4.5Sn-4.5Zr-5Mo-0.5Fe-0.5W-0.2Si alloy with O content of 0.15 wt%, and raw materials of 0-grade sponge Ti, sponge Zr, metallic Al beans and TiO2Sponge Ti, sponge Zr, metal Al beans and TiO are mixed according to the weight ratio of the components of Ti-Sn, Ti-Si, Al-Mo, Mo-Fe and Al-Mo-W-Ti intermediate alloy2After the intermediate alloy is weighed, the material is distributed in layers and pressed into electrodesAnd carrying out three times of smelting in a vacuum consumable arc furnace to prepare a Ti-6Al-4.5Sn-4.5Zr-5Mo-0.5Fe-0.5W-0.2Si alloy ingot.
The phase transition point of the ingot was found to be 965 ℃ by metallographic measurement. Cogging the cast ingot at 1100 ℃, then forging the cast ingot into a slab through intermediate forging, wherein the forging heating temperature is gradually reduced from 1050 ℃ to 1000 ℃, the intermediate forging is completed by 3 times of fire, and the deformation amount of each time of fire is not less than 50%; the slab was then heated sufficiently at 920 ℃ and rolled on a rolling mill to a 3mm thick plate.
The prepared plate is subjected to 945 ℃/2h and AC (air cooling) solution treatment. And taking an experimental sample from the heat-treated plate for testing the mechanical property. The bending angle performance test is carried out according to GB/T232-; the room temperature tensile property test is carried out on an MTS universal tensile testing machine, an YYU-10/50 type electronic extensometer is adopted, the test standard is in accordance with GB/T228.2-2010 metal material room temperature tensile test method, and the tensile speed before yielding and after yielding is 2 mm/min. The high-temperature tensile property test is carried out on an MTS universal tensile tester provided with a high-temperature tensile furnace, and an Epsilon 3348-036M-050 type high-temperature tensile extensometer is adopted, the test standard is in accordance with GB/T4338-2006 Metal material high-temperature tensile test method, the test temperature is 600 ℃ and 700 ℃, the tensile speed before yielding is 0.3mm/min, and the tensile speed after yielding is 2 mm/min. The high-temperature endurance performance test is carried out on an RD2-3 type endurance tester, the test condition is 650 ℃/425MPa, and the test standard is in accordance with GB/T2039-1997 Metal tensile creep and endurance test method. The measured material properties are shown in table 2.
TABLE 2 mechanical properties of Ti-6Al-4.5Sn-4.5Zr-5Mo-0.5Fe-0.5W-0.2Si alloy sheet
Example 2
Preparing Ti-8Al-2Sn-3Zr-0.5Mo-2Fe-2W-0.5Si alloy, wherein the O content is 0.25 wt%, the raw materials comprise 0-grade sponge Ti, sponge Zr, metal Al beans, Ti-Sn, Ti-Si, Al-Mo, Mo-Fe and Al-Mo-W-Ti intermediate alloy, and sponge Ti are mixed according to the weight ratioCotton Zr, metal Al bean, TiO2And after the intermediate alloy is weighed, performing layered material distribution, pressing into an electrode, and smelting for three times in a vacuum consumable arc furnace to prepare a Ti-8Al-2Sn-3Zr-0.5Mo-2Fe-2W-0.5Si alloy ingot.
The phase transition point of the ingot was 990 ℃ as measured by a metallographic method. Cogging the cast ingot at 1130 ℃, then forging the cast ingot into a slab through intermediate forging, wherein the forging heating temperature is gradually reduced from 1080 ℃ to 1030 ℃, the intermediate forging is completed for 3 times, and the deformation amount of each time is not less than 50%; the slab was then heated sufficiently at 940 ℃ and rolled on a rolling mill to form a 2.5mm thick plate.
The prepared plate is subjected to 970 ℃/2h and AC solution treatment. And taking an experimental sample from the heat-treated plate for testing the mechanical property. The bending angle performance test is carried out according to GB/T232-; the room temperature tensile property test is carried out on an MTS universal tensile testing machine, an YYU-10/50 type electronic extensometer is adopted, the test standard is in accordance with GB/T228.2-2010 metal material room temperature tensile test method, and the tensile speed before yielding and after yielding is 2 mm/min. The high-temperature tensile property test is carried out on an MTS universal tensile tester provided with a high-temperature tensile furnace, and an Epsilon 3348-036M-050 type high-temperature tensile extensometer is adopted, the test standard is in accordance with GB/T4338-2006 Metal material high-temperature tensile test method, the test temperature is 600 ℃ and 700 ℃, the tensile speed before yielding is 0.3mm/min, and the tensile speed after yielding is 2 mm/min. The high-temperature endurance performance test is carried out on an RD2-3 type endurance tester, the test condition is 650 ℃/425MPa, and the test standard is in accordance with GB/T2039-1997 Metal tensile creep and endurance test method. The measured material properties are shown in table 3.
TABLE 3 mechanical properties of Ti-6Al-4.5Sn-4.5Zr-0.5Mo-2Fe-2W-0.2Si alloy sheet
Example 3
Preparing Ti-6.5Al-2Sn-4Zr-4Mo-1Fe-1W-0.2Si alloy, wherein the O content is 0.2 wt%, and the raw materials comprise 0-grade sponge Ti, sponge Zr, metal Al beans and TiO2Sponge Ti, sponge Zr, metal Al beans and TiO are mixed according to the weight ratio of the components of Ti-Sn, Ti-Si, Al-Mo, Mo-Fe and Al-Mo-W-Ti intermediate alloy2And after the intermediate alloy is weighed, performing layered material distribution, pressing into an electrode, and smelting for three times in a vacuum consumable arc furnace to prepare a Ti-6.5Al-2Sn-4Zr-4Mo-1Fe-1W-0.2Si alloy ingot.
The phase transition point of the ingot was 970 ℃ as measured by the metallographic method. Cogging the cast ingot at 1110 ℃, then forging the cast ingot into a slab through intermediate forging, gradually reducing the forging heating temperature from 1070 ℃ to 1020 ℃, and finishing the intermediate forging for 3 times, wherein the deformation amount of each time is not less than 50%; the slab was then heated sufficiently at 920 ℃ and rolled on a rolling mill to form a 2.5mm thick plate.
And (3) carrying out 950 ℃/2h and AC solution treatment on the prepared plate. And taking an experimental sample from the heat-treated plate for testing the mechanical property. The bending angle performance test is carried out according to GB/T232-; the room temperature tensile property test is carried out on an MTS universal tensile testing machine, an YYU-10/50 type electronic extensometer is adopted, the test standard is in accordance with GB/T228.2-2010 metal material room temperature tensile test method, and the tensile speed before yielding and after yielding is 2 mm/min. The high-temperature tensile property test is carried out on an MTS universal tensile tester provided with a high-temperature tensile furnace, and an Epsilon 3348-036M-050 type high-temperature tensile extensometer is adopted, the test standard is in accordance with GB/T4338-2006 Metal material high-temperature tensile test method, the test temperature is 600 ℃ and 700 ℃, the tensile speed before yielding is 0.3mm/min, and the tensile speed after yielding is 2 mm/min. The high-temperature endurance performance test is carried out on an RD2-3 type endurance tester, the test condition is 650 ℃/425MPa, and the test standard is in accordance with GB/T2039-1997 Metal tensile creep and endurance test method. The measured material properties are shown in table 4.
TABLE 4 mechanical Properties of Ti-6.5Al-2Sn-4Zr-4Mo-1Fe-1W-0.2Si alloy plate
Example 4
Preparation of Ti-6Al-2Sn-4Zr-1Mo-0.5Fe-0.5W-0.2Si alloy, the O content is 0.25 wt%, and the raw materials are 0-grade sponge Ti, sponge Zr, metal Al beans and TiO2Sponge Ti, sponge Zr, metal Al beans and TiO are mixed according to the weight ratio of the components of Ti-Sn, Ti-Si, Al-Mo, Mo-Fe and Al-Mo-W-Ti intermediate alloy2And after the intermediate alloy is weighed, performing layered material distribution, pressing into an electrode, and preparing a Ti-6Al-2Sn-4Zr-1Mo-0.5Fe-0.5W-0.2Si alloy ingot by three times of smelting in a vacuum consumable arc furnace.
The phase transition point of the ingot was determined to be 1030 ℃ by metallographic methods. Cogging the cast ingot at 1150 ℃, then forging the cast ingot into a slab through intermediate forging, wherein the forging heating temperature is gradually reduced from 1110 ℃ to 1050 ℃, the intermediate forging is completed by 3 times of fire, and the deformation amount of each time of fire is not less than 50%; the slab was then heated sufficiently at 980 ℃ and rolled on a rolling mill to form a 2.5mm thick plate.
And (3) carrying out solution treatment on the prepared plate at 1010 ℃/2h and AC. And taking an experimental sample from the heat-treated plate for testing the mechanical property. The bending angle performance test is carried out according to GB/T232-; the room temperature tensile property test is carried out on an MTS universal tensile testing machine, an YYU-10/50 type electronic extensometer is adopted, the test standard is in accordance with GB/T228.2-2010 metal material room temperature tensile test method, and the tensile speed before yielding and after yielding is 2 mm/min. The high-temperature tensile property test is carried out on an MTS universal tensile tester provided with a high-temperature tensile furnace, and an Epsilon 3348-036M-050 type high-temperature tensile extensometer is adopted, the test standard is in accordance with GB/T4338-2006 Metal material high-temperature tensile test method, the test temperature is 600 ℃ and 700 ℃, the tensile speed before yielding is 0.3mm/min, and the tensile speed after yielding is 2 mm/min. The high-temperature endurance performance test is carried out on an RD2-3 type endurance tester, the test condition is 650 ℃/425MPa, and the test standard is in accordance with GB/T2039-1997 Metal tensile creep and endurance test method. The measured material properties are shown in table 5.
TABLE 5 mechanical Properties of Ti-6Al-2Sn-4Zr-1Mo-0.5Fe-0.5W-0.2Si alloy plate
The content (weight percentage) of impurity elements in the titanium alloy is as follows: o: 0.15-0.25%, N less than 0.01%, H less than 0.0015%, C less than 0.05%.
The Ti-Al-Sn-Zr-Mo-Fe-W-Si alloy and the alloy plate have excellent matching of room-temperature and high-temperature mechanical properties, and can meet the application requirements of the titanium alloy under the conditions of short time, high temperature and high strength.
Claims (5)
1. A short-time ultrahigh-strength heat-resistant titanium alloy is characterized in that: the alloy comprises the following components in percentage by weight: 6.0-8.0%, Sn: 2-4.5%, Zr: 2-4.5%, Mo: 0.5-5.0%, Fe: 0.5-2.0%, W: 0.5-2.0%, Si: 0.2-0.5%, and the balance Ti.
2. The short term ultra high strength heat resistant titanium alloy of claim 1, wherein: the titanium alloy also contains O, and the weight percentage of the O is 0.15-0.25%.
3. The method for preparing the short-term ultrahigh-strength heat-resistant titanium alloy according to claim 1 or 2, comprising the steps of: the alloy adopts 0-grade sponge Ti, sponge Zr, metal Al beans and TiO as raw materials2Ti-Sn, Ti-Si, Al-Mo, Mo-Fe and Al-Mo-W-Ti master alloys; sponge Ti, sponge Zr, metallic Al beans and TiO2And after the intermediate alloy is weighed, performing layered material distribution, then pressing into an electrode, and preparing the ingot by three times of vacuum consumable arc melting.
4. A short-time ultrahigh-strength heat-resistant titanium alloy plate is characterized in that: the short-time ultrahigh-strength heat-resistant titanium alloy is made of the short-time ultrahigh-strength heat-resistant titanium alloy as claimed in claim 1 or 2.
5. A preparation method of a short-time ultrahigh-strength heat-resistant titanium alloy plate comprises the following steps: the ingot produced by the method for producing a short-term ultrahigh-strength heat-resistant titanium alloy according to claim 3, which is cogging at a temperature higher than the transformation point, is gradually cooled and is subjected to intermediate forging to produce a slab, and the slab is sufficiently heated at a temperature of 40 to 50 ℃ lower than the transformation point and then is rolled on a rolling mill to produce a plate having a thickness of 2.5 to 3 mm; and then carrying out heat treatment on the plate, wherein the heat treatment temperature is 20 ℃ below the phase transition point, the heat preservation time is 2h, and the cooling mode is air cooling.
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