CN116516213A - Preparation method of Si-containing high Nb-TiAl alloy - Google Patents
Preparation method of Si-containing high Nb-TiAl alloy Download PDFInfo
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- CN116516213A CN116516213A CN202310470774.XA CN202310470774A CN116516213A CN 116516213 A CN116516213 A CN 116516213A CN 202310470774 A CN202310470774 A CN 202310470774A CN 116516213 A CN116516213 A CN 116516213A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 110
- 239000000956 alloy Substances 0.000 title claims abstract description 110
- 229910010038 TiAl Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000005266 casting Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 238000003723 Smelting Methods 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002474 experimental method Methods 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- QNTVPKHKFIYODU-UHFFFAOYSA-N aluminum niobium Chemical compound [Al].[Nb] QNTVPKHKFIYODU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011863 silicon-based powder Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910021332 silicide Inorganic materials 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 abstract 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 abstract 1
- 230000005923 long-lasting effect Effects 0.000 abstract 1
- 239000007769 metal material Substances 0.000 abstract 1
- 230000002093 peripheral effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005495 investment casting Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000012360 testing method Methods 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
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a preparation method of a Si-containing high Nb-TiAl alloy. Belonging to the field of high-temperature titanium-aluminum alloy. The metal material comprises the following components in percentage by mole: 44-46 at.%, nb: 5-9 at.%, si:0.8-1.8at.% and the balance of Ti and unavoidable impurity elements. The Si-containing high Nb-TiAl alloy disclosed by the invention overcomes the difficulty of insufficient comprehensive performance of cast TiAl alloy, has good casting performance, room temperature and high temperature tensile performance and creep resistance at 800 ℃, has room temperature tensile strength up to 600-900MPa, after-break elongation up to 0.1-0.5%, tensile strength up to 500-750MPa at 850 ℃, after-break elongation up to 0.5-12.5%, and long-lasting life up to more than 1000h at 800 ℃/300MPa, and is cast high Nb-TiAl alloy with excellent comprehensive mechanical properties. Can meet the application requirement of the high Nb-TiAl alloy at 800-850 ℃, and has great application value.
Description
Technical Field
The invention belongs to the field of TiAl alloy design and preparation, and relates to a Si-containing high Nb-TiAl alloy and a preparation method thereof.
Background
TiAl alloy is used as a light high-temperature structural material, and is the first choice of the high-temperature structural material for aviation and aerospace due to the advantages of low density, high specific strength, good oxidation resistance and the like. In particular to a low-pressure turbine blade for preparing an aeroengine, which can improve the thrust-weight ratio of the engine by reducing the weight and contributes to the improvement of the performance of a new generation of aerospace aircraft with high thrust-weight ratio. The prior forged TNM alloy has the use temperature of about 750 ℃ and cannot meet the requirement of a new generation of high thrust-weight ratio engine on the use temperature of TiAl alloy. Previous researches show that by adding more Nb elements into the TiAl alloy, the strength, creep resistance and oxidation resistance of the TiAl alloy at a higher temperature can be improved by improving the ordering temperature of the TiAl alloy, and then the TiAl alloy with high Nb content, namely the high Nb-TiAl alloy, is developed.
However, in the industrial production process using the casting process, the limited plasticity of the alloy and the fluidity of the alloy liquid in a molten state are deteriorated due to the large addition of the Nb element, so that the problems of coarse casting structure, component segregation, serious casting defects and the like of the alloy occur, and the high Nb-TiAl alloy produced by the casting process is subjected to brittle fracture in an elastic section when being stretched at room temperature, and is basically plastic-free and low in tensile strength. In addition, the high Nb-TiAl alloy has slightly insufficient tensile strength and creep resistance at high temperature of more than 800 ℃, and is not applied in industry in essence at present. Therefore, the method can improve the room temperature and high temperature mechanical properties of the cast high Nb-TiAl alloy while keeping low cost production by using a casting process, and obtain alloy components with good comprehensive mechanical properties and a preparation process, which are the directions of the development and efforts of the alloy system.
Microalloying is a common method for modifying TiAl alloy, and has the advantages of simple operation and no need of adding equipment and personnel. Research shows that the addition of the Si microalloy element can bring positive effects to the performance improvement of the TiAl alloy. The main reason is that the addition of Si element can improve the fluidity of TiAl alloy melt in a molten state, thereby reducing the solidification defect of cast ingot and improving the mechanical property of TiAl alloy. However, no report on the obvious improvement of the high Nb-TiAl performance by Si microalloying is seen.
The Chinese patent application with publication number of CN114921735A discloses a thermal regulation method for improving mechanical properties of high Nb-TiAl alloy for casting, wherein the alloy is strengthened after hot isostatic pressing and aging treatment, but the alloy has no obvious room temperature plasticity, is difficult to meet engineering application requirements, has long whole production flow, needs numerous equipment, is time-consuming and long, and is not beneficial to low-cost production.
The Chinese patent application with publication number of CN104878452A discloses a high-temperature high-strength TiAl-Nb monocrystal and a preparation method thereof, and the high-temperature high-strength TiAl-Nb monocrystal is prepared by light suspension directional solidification equipment, but the problems of expensive preparation equipment and smaller size of production materials are still faced.
Therefore, the components of the high Nb-TiAl alloy are designed to obtain good comprehensive mechanical properties, and the high Nb-TiAl alloy can be prepared and processed in a production mode with short process flow and low production cost, so that the high Nb-TiAl alloy becomes an effort direction for obtaining application.
Disclosure of Invention
The invention aims to provide a high Nb-TiAl alloy component proportion with good comprehensive mechanical properties and a low-cost production method thereof.
In order to achieve the above object, the subject group of the present invention has found through a large number of experimental studies that adding a trace amount of silicon into a high Nb-TiAl alloy can greatly improve the strength, creep resistance and oxidation resistance of the high Nb-TiAl alloy at a service temperature of 800 to 850 ℃. The specific implementation mode is as follows:
a preparation method of a Si-containing high Nb-TiAl alloy is characterized in that the content of Al in the TiAl alloy is 44-46 at%, the content of Nb is 5-9 at%, the content of Si is 0.8-1.8 at%, the balance is Ti and unavoidable impurity elements, and the alloy is cast after smelting, and the oxygen content in an ingot is not higher than 1000ppm.
The preparation method of the Si-containing high Nb-TiAl alloy comprises the following specific implementation steps:
firstly, weighing sponge titanium, high-purity aluminum, silicon powder and aluminum-niobium intermediate alloy according to a proportion;
step two, uniformly distributing the raw materials obtained in the step one in a water-cooled copper crucible for smelting, and naturally cooling in the crucible after smelting is completed;
taking out the primary smelting alloy cast ingot obtained in the step two, inversely placing the primary smelting alloy cast ingot in a water-cooling copper crucible vacuum induction smelting furnace for secondary smelting, and pouring the primary smelting alloy cast ingot into a die after smelting is completed to obtain the alloy cast ingot with good comprehensive mechanical properties.
Further, the tensile strength of the alloy at room temperature is 530-900MPa, the elongation after break is 0.1-0.5%, the tensile strength at a high temperature of 850 ℃ is 500-750MPa, the elongation after break is 0.3-12.5%, and the durable life at 800 ℃/300MPa is more than 1000 h.
Further, the as-cast structure of the component high Nb-TiAl alloy is mainly composed of alpha 2 And a near-full lamellar structure consisting of gamma phase, and a large amount of in-situ precipitated micron-sized and nano-sized silicide is distributed in the alloy structure, and the second phase strengthening greatly improves the comprehensive mechanical property of the alloy.
Further, the atomic percentage of the alloy components is Ti-45Al-8Nb-1.3Si, the alloy casting structure is shown in figure 1, the peripheral material close to the circumference of the alloy ingot is taken for high-temperature stretching experiment at the temperature of 850 ℃, and the room-temperature stretching rate is 1.0x10 -4 s -1 High temperature stretching rate of 5.0X10 -4 s -1 The tensile strength of the high Nb-TiAl alloy at room temperature is 894MPa, the elongation after fracture is 0.50%, the tensile curve is shown in figure 2, and the plastic deformation stage is obvious; the high-temperature tensile strength at 850 ℃ is 747MPa, the elongation after fracture is 12.34 percent, and the tensile strength is improvedThe extension curve is shown in figure 3; the permanent measurement is carried out under the creep condition of 800 ℃ and 300MPa, and the fracture is not generated for 1000 hours.
Therefore, a large amount of micro-nano fine second-phase reinforced alloy can be separated out by adding a specific amount of silicon element into the high Nb-TiAl alloy. In addition, the Si element can improve the fluidity of the TiAl alloy melt in a molten state, so that the solidification defect of an ingot is reduced, and the mechanical property of the TiAl alloy is improved; and the elongation after fracture of the blade can be kept under the premise of small change of the high-temperature tensile strength at 850 ℃, so that the high-temperature deformation of the blade is reduced. (Note that during use, the blade must be controlled in terms of elongation after fracture, not only to prevent the high Nb-TiAl alloy blade from breaking at high temperatures, but also to keep the blade less prone to deformation).
By adopting the technical means, the invention has the following advantages:
(1) The components of the high Nb-TiAl alloy are designed and optimized to obtain the cast high Nb-TiAl alloy with excellent high temperature and high temperature tensile properties, and the alloy structure of micro-nano precipitated phases is provided, so that the tensile strength of the alloy at room temperature is 530-900MPa, the elongation after break is 0.1-0.5%, the tensile strength at high temperature of 850 ℃ is 500-750MPa, the elongation after break is 0.3-12.5%, and the durable service life at 800 ℃/300MPa is more than 1000 hours, thereby being the cast high-strength high Nb-TiAl alloy with excellent comprehensive mechanical properties.
(2) The high Nb-TiAl alloy of the component meets the requirements of high Nb-TiAl alloy precision casting fluidity, filling property, strength at the use temperature of 800-850 ℃, creep resistance, antioxidation and the like, can be applied to components such as a combustion chamber casing of an aeroengine, a low-pressure turbine blade of the engine, a booster turbine of an automobile engine and the like, and has great popularization value;
(3) Simple production equipment, simple and convenient operation, short process flow and low production cost.
Drawings
Fig. 1: ti-45Al-8Nb-1.3Si high Nb-TiAl alloy casting structure;
fig. 2: room temperature tensile curve of Ti-45Al-8Nb-1.3Si high Nb-TiAl alloy;
fig. 3: high temperature tensile curve of Ti-45Al-8Nb-1.3Si high Nb-TiAl alloy at 850 ℃.
Detailed description of the preferred embodiments
The technical scheme of the present invention will be further described with reference to examples, but the present invention is not limited to the following examples.
Example 1
Firstly, respectively weighing high Nb-TiAl alloy raw materials of titanium sponge, high-purity aluminum, silicon powder and aluminum-niobium intermediate alloy according to the proportion of Ti-45Al-8Nb-0.8Si (atomic percent);
step two, the raw materials obtained in the step one are respectively and uniformly distributed in a water-cooled copper crucible for smelting, and the raw materials are cooled in the crucible after smelting is completed;
taking out the primary smelting alloy cast ingot obtained in the step two, respectively inverting the primary smelting alloy cast ingot into a water-cooling copper crucible vacuum induction smelting furnace for secondary smelting, and pouring the primary smelting alloy cast ingot into a die after smelting is completed to obtain the alloy cast ingot.
Room temperature stretching experiment is carried out on the peripheral material close to the circumference of the alloy ingot, and the stretching rate is 1.0x10 -4 s -1 The tensile strength is 587MPa, and the elongation after fracture is 0.13%; high temperature stretching test at 850 ℃ with stretching rate of 5.0X10 -4 s -1 The tensile strength is 554MPa, the elongation after break is 0.35 percent,
example 2
By adopting the same preparation method as in example 1, the alloy composition is changed to Ti-45Al-8Nb-1.0Si (atomic percent), and a high-temperature stretching experiment is carried out at the temperature of 850 ℃ by taking a peripheral material close to the circumference of an alloy ingot, wherein the room-temperature stretching rate is 1.0x10 -4 s -1 High temperature stretching rate of 5.0X10 -4 s -1 The tensile strength of the high Nb-TiAl alloy at room temperature is 536MPa, the elongation after fracture is 0.11%, the high-temperature tensile strength at 850 ℃ is 527MPa, and the elongation after fracture is 0.31%.
Example 3
The same preparation method as in example 1 is adopted, the alloy composition is changed to Ti-45Al-8Nb-1.3Si (atomic percent), the alloy casting structure is shown in figure 1, the alloy ingot circumference peripheral material is taken to be subjected to high-temperature stretching experiment at the temperature of 850 ℃, and the room-temperature stretching rate is 1.0x10 -4 s -1 High temperature stretching rate of 5.0X10 -4 s -1 The tensile strength of the high Nb-TiAl alloy at room temperature is 894MPa, the elongation after fracture is 0.50%, the tensile curve is shown in figure 2, and the plastic deformation stage is obvious; the high-temperature tensile strength at 850 ℃ is 747MPa, the elongation after fracture is 12.34%, and the tensile curve is shown in figure 3; the permanent measurement is carried out under the creep condition of 800 ℃ and 300MPa, and the fracture is not generated for 1000 hours.
Example 4
By adopting the same preparation method as in example 1, the alloy composition is changed to Ti-45Al-8Nb-1.5Si (atomic percent), and a high-temperature stretching experiment is carried out at the temperature of 850 ℃ by taking a peripheral material close to the circumference of an alloy ingot, wherein the room-temperature stretching rate is 1.0x10 -4 s -1 High temperature stretching rate of 5.0X10 -4 s -1 The tensile result shows that the tensile strength of the high Nb-TiAl alloy at room temperature is 740MPa, the elongation after fracture is 0.23%, the high-temperature tensile strength at 850 ℃ is 682MPa, and the elongation after fracture is 1.12%.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above examples, but particularly from the viewpoint of the smelting method, it is not excluded that the high Nb-TiAl alloy produced by the man skilled in the art in the present invention by other smelting methods than the water-cooled copper crucible is within the scope of the present invention, and that the present invention also falls within the scope of protection of the present invention if the composition combination changes are made within the scope of the present invention.
Comparative examples
The same preparation method as in example 1 was used to prepare a Ti-45Al-8Nb (atomic percent) alloy having a room temperature tensile strength of only 515MPa, a post-fracture elongation of only 0.03%, a high temperature tensile strength of only 524MPa at 850℃and a post-fracture elongation of 1.32%.
Claims (5)
1. A preparation method of a Si-containing high Nb-TiAl alloy is characterized in that the content of Al in the TiAl alloy is 44-46 at%, the content of Nb is 5-9 at%, the content of Si is 0.8-1.8 at%, and the balance is Ti and unavoidable impurity elements, wherein the oxygen content in an ingot is not higher than 1000ppm; the alloy is cast after being smelted by a vacuum induction suspension smelting furnace.
2. The method for preparing the Si-containing high Nb-TiAl alloy as recited in claim 1, wherein the preparation of the high Nb-TiAl alloy ingot is realized by the following steps:
firstly, weighing sponge titanium, high-purity aluminum, silicon powder and aluminum-niobium intermediate alloy according to a proportion;
step two, uniformly distributing the raw materials obtained in the step one in a water-cooled copper crucible for smelting, and cooling in the crucible after smelting is completed;
taking out the primary smelting alloy cast ingot obtained in the step two, inverting the primary smelting alloy cast ingot into a water-cooling copper crucible vacuum induction smelting furnace for secondary smelting, pouring the primary smelting alloy cast ingot into a mould to obtain an alloy cast ingot, and cooling the alloy cast ingot along with the furnace to obtain the alloy cast ingot with excellent comprehensive mechanical properties.
3. The method for producing Si-containing high Nb-TiAl alloy as recited in claim 2, wherein the TiAl alloy casting structure consists essentially of alpha 2 And a near-full lamellar structure composed of gamma phase, and a large number of in-situ precipitated micron-sized and nano-sized silicides are distributed in the alloy structure.
4. The method for preparing the Si-containing high Nb-TiAl alloy according to claim 2, wherein the tensile strength of the alloy at room temperature is 530-900MPa, the elongation after break is 0.1-0.5%, the tensile strength at high temperature of 850 ℃ is 500-750MPa, the elongation after break is 0.3-12.5%, and the durable life at 800 ℃/300MPa is more than 1000 h.
5. The method for preparing the Si-containing high Nb-TiAl alloy as claimed in claim 2, wherein the alloy comprises the following components in atomic percent of Ti-45Al-8Nb-1.3Si, the material near the circumference of the alloy ingot is taken for high-temperature stretching experiments at the temperature of 850 ℃, and the room-temperature stretching rate is 1.0x10% -4 s -1 High temperature stretching rate of 5.0X10 -4 s -1 The tensile strength of the high Nb-TiAl alloy at room temperature is 894MPa, and the elongation after fracture is0.50%, high temperature tensile strength at 850 ℃ is 747MPa, and elongation after break is 12.34%.
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| CN114921735A (en) * | 2022-06-02 | 2022-08-19 | 中国航发北京航空材料研究院 | Thermal regulation and control method for improving mechanical property of high Nb-TiAl alloy for casting |
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- 2023-04-27 CN CN202310470774.XA patent/CN116516213B/en active Active
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