CN110643877A - TiAl intermetallic compound containing W, Mn, Si, B, C and rare earth elements - Google Patents
TiAl intermetallic compound containing W, Mn, Si, B, C and rare earth elements Download PDFInfo
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Abstract
The invention provides a TiAl intermetallic compound containing W, Mn, Si, B, C and rare earth elements, belonging to the technical field of metal materials. The alloy elements comprise, by mole, 46-50% of Al, 1-3% of Cr, 1-5% of Nb, 0-2% of W, 0-3% of Mn, 0-1.8% of B, 0-1.5% of Si, 0-1.5% of C, 0-2% of rare earth elements and the balance of Ti and inevitable impurities. The cast alloy is mainly composed of alpha 2 phase, gamma phase and a small amount of B2/beta0Phase composition. The invention has the advantages that: based on Ti-48Al-2Cr-2Nb alloy, trace elements W, Mn,B. Si and C improve the high-temperature strength, creep resistance and oxidation resistance of the alloy, improve the casting performance and additive manufacturing process performance of the cast TiAl alloy, and meet the requirements of complex components with higher service strength and temperature on the novel TiAl alloy.
Description
Technical Field
The invention provides a TiAl intermetallic compound containing W, Mn, Si, B, C and rare earth elements, belonging to the technical field of metal materials.
Background
The TiAl alloy has the advantages of low density, high specific strength, high-temperature oxidation resistance, good creep resistance and the like, and becomes a novel high-temperature structural material in the field of military industry in the future and a future substitute material of the traditional high-temperature alloy. Currently, TiAl alloys have been widely used in aerospace, and Ti-48Al-2Cr-2Nb, TNM (Ti-43.5Al-4Nb-1Mo-0.1B), Ti45XD (Ti-45Al-2Mn-2Nb-0.8 vol.% Ti2B) alloys are respectively used in GE, MTU, Roro engine and aeronautical aircraft (HSCT) engine nozzles and aileron parts leading to NASA, indicating that the TiAl alloys have been widely accepted by European and American aeronautical engines. Besides the aerospace field, the application of titanium-aluminum alloy in the fields of automobiles, chemical engineering, weapons and the like is gradually increased, and TiAl alloy cast valves and turbochargers have been successfully applied to racing cars and car engines. The titanium-aluminum alloy has wide market and application prospect.
At present, Ti48Al2Cr2Nb (at.%) alloy still has the defects of poor room-temperature plasticity, low high-temperature strength, large difficulty in complete forming and the like, cannot meet the requirements of TiAl components on higher use temperature and high-temperature strength in the fields of aerospace and the like, and limits the engineering application of the TiAl components. In recent years, the problem of room temperature brittleness has been substantially solved by structure control and alloying, and some titanium-aluminum based alloys have been provided with conditions for engineering applications. The design of multi-component alloy is an important development trend of TiAl alloy. A great deal of research at home and abroad shows that the solidification path of the alloy can be controlled by adding trace elements, so that the solidification structure is refined, the plasticity and the strength of the alloy are improved, and the complete formability of the alloy is improved. The addition of B element in TiAl alloy can effectively refine the cast lamellar structure, change the ductile-brittle transition temperature of the alloy, and the formed boride can obviously improve the creep deformation and the endurance quality of the alloy. The W element is added, so that the TiAl alloy has various strengthening effects, and the high-temperature strength and the oxidation resistance of the alloy are improved; the addition of Mn element can effectively enhance the plasticity of the binary structure of the Ti4822 alloy and simultaneously improve the oxidation resistance of the alloy; the addition of Si element in the TiAl alloy can improve the flow type of TiAl alloy melt and improve the casting performance of the alloy on the one hand, and on the other hand, the precipitated fine silicide can be used as hard particles to be pinned on a lamellar interface and can play a role in stabilizing an alpha 2/gamma lamellar interface and strengthening a gamma/gamma interface at high temperature, so that the alloy has excellent high-temperature creep resistance; the rare earth element belongs to metal elements, has high reaction activity, improves the solidification and crystallization process, the microstructure and the mechanical property of the titanium-aluminum alloy by cooperating with other elements, for example, the Y element can refine crystal grains and improve the long-term oxidation resistance of the alloy, the Gd element can effectively reduce the oxygen content in a gamma phase and improve the high-temperature strength and the plasticity of the alloy at room temperature, and the Er element has strong internal oxidation effect and is beneficial to the twin crystal deformation of the alloy.
A great deal of work is done by Beijing aviation material research institute in the aspect of TiAl alloy component design, and a novel TiAl alloy with excellent mechanical property and casting property is obtained by compositely adding 0-2 at.% W, 0-3 at.% Mn, 0-1.8 at.% B, 0-1.5 at.% Si, 0-1.5 at.% C and rare earth elements into Ti- (46-50) Al- (1-3) Cr- (1-5) Nb (at.%), wherein the novel TiAl alloy contains high-melting-point refractory metals Nb and W, low-melting-point volatile Al elements and trace elements B, Si and C.
Compared with the novel TiAl intermetallic compound containing W, Mn, Si, B, C and rare earth elements developed by GE, the novel TiAl intermetallic compound disclosed by the invention has the characteristics of higher working temperature, more excellent high-temperature mechanical property and casting property and the like, and the high-temperature strength is improved to 600MPa from 410 MPa. The alloy designed by the invention has uniform microstructure, no obvious segregation, no obvious crack and no non-metal inclusion defect.
Disclosure of Invention
The invention aims to provide a TiAl intermetallic compound which improves the high-temperature mechanical property, the oxidation resistance and the casting property of TiAl alloy by adding W, Mn, Si, B and C rare earth elements.
The technical problem to be solved by the invention is as follows: at present, the service temperature of Ti- (46-50) Al- (1-3) Cr- (1-5) Nb (at.%) alloy is difficult to be higher than 650 ℃, the problems of low room temperature and high temperature mechanical properties, poor casting performance and the like still exist, and the requirement of high-strength, high-toughness and thin-wall complex components used at the temperature of more than 650 ℃ on novel TiAl alloy is difficult to meet.
The technical scheme adopted by the invention for solving the technical problem is as follows: the TiAl intermetallic compound containing W, Mn, Si, B, C and rare earth elements is characterized in that the TiAl intermetallic compound contains 46-50% of Al, 1-3% of Cr, 1-5% of Nb, 0-2% of W, 0-3% of Mn, 0-1.8% of B, 0-1.5% of Si, 0-1.5% of C, 0-2% of rare earth elements and the balance of Ti by mole percentage.
47-49% of Al, 0.3% of W, 0-3% of Mn, not higher than 0.2% of Si, not higher than 0.2% of B and not higher than 0.3% of C.
The Al content is 48 mol%, the W content is 0.2 mol%, the Mn content is 2.0 mol%, the Si content is not higher than 0.2 mol%, the B content is not higher than 0.2 mol%, and the C content is not higher than 0.2 mol%.
The rare earth elements comprise La, Ce, Re, Y, Gd, Er and other elements.
The atomic mol percentage content of O in the TiAl intermetallic compound is less than 800 PPm.
The atomic mol percentage content of O in the TiAl intermetallic compound is less than 500 PPm.
The atomic mole percent content of the C in the TiAl intermetallic compound is less than 500 PPm.
The atomic mol percentage content of C in the TiAl intermetallic compound is less than 300 PPm.
The TiAl intermetallic compound has a cast structure mainly composed of an alpha 2 phase, a gamma phase and a small amount of B2/beta 0 phase.
The casting structure of the TiAl intermetallic compound is an equiaxial crystal structure or a columnar crystal structure.
The invention has the beneficial effects that: by adding rare earth elements such as W, Mn, Si, B and C into the Ti-48Al-2Cr-2Nb alloy, the novel TiAl alloy with excellent mechanical property and casting property is obtained, and the novel alloy contains refractory metals such as Nb and W with high melting point, volatile Al with low melting point and trace elements such as B, Si and C. Obviously improves the high-temperature strength, the lasting strength and the oxidation resistance of the original alloy, and effectively improves the casting fluidity, the filling property and the like of the alloy. The low-pressure turbine blade, the combustion chamber casing and other parts of the aero-engine can be applied; compared with Ti4822 alloy, the invention has the characteristics of higher working temperature, more excellent high-temperature mechanical property and casting property, and the like, and the high-temperature strength is improved from 410MPa to 600 MPa. The alloy designed by the invention has uniform microstructure, no obvious segregation, no obvious crack and no non-metal inclusion defect.
Drawings
FIG. 1a shows the metallographic structure of Ti-47Al-2Cr-2Nb-0.3W-0.2B-0.2Si-0.15C (at.%) alloy
FIG. 1B shows the metallographic structure of Ti-48Al-1Cr-2Nb-1Mn-0.2W-0.3B-0.1Si-0.08Y (at.%) alloy
FIG. 2a is an SEM photograph of a Ti-47Al-2Cr-2Nb-0.3W-0.2B-0.2Si (at.%) alloy.
FIG. 2B is an SEM photograph of Ti-48Al-1Cr-2Nb-1Mn-0.2W-0.3B-0.1Si-0.08Y (at.%) alloy
The specific implementation mode is as follows:
the present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1a novel TiAl intermetallic material with a composition of Ti-47Al-2Cr-2Nb-0.3W-0.2B-0.2Si-0.15C (at.%). The alloy is realized by the following steps: firstly, weighing sponge titanium, high-purity aluminum, aluminum-chromium intermediate alloy, aluminum-niobium intermediate alloy, aluminum-tungsten-niobium intermediate alloy, aluminum-titanium-boron, pure boron powder and pure silicon according to a ratio; secondly, adding the raw materials weighed in the step one into a press device, and carrying out pressure forming, wherein the weight of the single electrode is 150 kg; thirdly, putting the electrode block obtained in the second step into a vacuum consumable electrode smelting furnace, wherein the main smelting process parameters are as follows: the vacuum degree is 2Pa, the smelting current is 30KA, the smelting voltage is 40V, then smelting is carried out for 200s under constant power, the melt is uniformly mixed, the mixture is cast into a water-cooled copper crucible, and the mixture is cooled along with the furnace to obtain a primary alloy ingot; fifthly, placing the primary consumable electrode in the fourth step into a vacuum consumable arc furnace for secondary smelting, wherein the main smelting process parameters are as follows: the vacuum degree is 2Pa, the smelting current is 28KA, the smelting voltage is 35V, then smelting is carried out for 200s under constant power, and a novel TiAl intermetallic compound secondary ingot containing W, Si, B and C is obtained after furnace cooling.
Observing the microstructure of the alloy by using a metallographic microscope to find that the structure of the alloy is an equiaxial grain structure, which is shown in figure 1; the microscopic structure of the alloy is a full lamellar structure by SEM observation, and is shown in figure 2; the novel alloy has good comprehensive performance, and the room high-temperature mechanical properties are as follows:
the room-temperature tensile property sigma b is more than or equal to 730MPa, sigma p0.2 is more than or equal to 670MPa, delta 5 is more than or equal to 4 percent, and psi is more than or equal to 5 percent;
the tensile property sigma b at 700 ℃ is more than or equal to 650MPa, sigma p0.2 is more than or equal to 600MPa, delta 5 is more than or equal to 12 percent, and psi is more than or equal to 17 percent;
the residual deformation under the conditions of high-temperature creep property of 700 ℃/100Mpa/100h is less than or equal to 0.2 percent.
In the embodiment, the alloy casting fluidity and the comprehensive mechanical property are improved by adding the alloy elements of W, Si, B and C into the Ti48Al-2Cr-2Nb alloy and by the solid solution strengthening of the element of W and the combined action of the elements of Si, B and C.
Example 2Ti-48Al-1Cr-2Nb-1Mn-0.2W-0.3B-0.1Si (at.%), melting in a vacuum induction melting furnace
The Ti-48Al-1Cr-2Nb-1Mn-0.2W-0.3B-0.1Si (at.%) intermetallic material preparation of this example was achieved by the following steps: firstly, sponge titanium, high-purity aluminum, an aluminum-niobium intermediate alloy, an aluminum-chromium intermediate alloy, an aluminum-manganese intermediate alloy, an aluminum-titanium-boron intermediate alloy, an aluminum-tungsten-niobium intermediate alloy, pure boron powder, pure silicon and pure yttrium powder are mixed according to parts by weight; secondly, adding the raw materials weighed in the step one into a press device, and carrying out pressure forming, wherein the weight of the single electrode is 140 kg; thirdly, putting the electrode block obtained in the second step into a vacuum consumable electrode smelting furnace, wherein the main smelting process parameters are as follows: the vacuum degree is 2Pa, the smelting current is 30KA, the smelting voltage is 40V, then smelting is carried out for 200s under constant power, and primary alloy ingot casting is obtained by furnace cooling in a water-cooled copper crucible; fourthly, the primary alloy ingot obtained in the third step is placed into a water-cooled copper crucible vacuum induction smelting furnace, after the smelting power is increased to 500kw, the titanium-aluminum alloy melt is obtained by smelting for 150s, and the titanium-aluminum alloy melt is cast into a rod-shaped graphite mold to obtain Ti-48Al-1Cr-2Nb-1Mn-0.2W-0.3B-0.1Si-0.08Y cast ingot.
The microstructure of the alloy ingot is observed by a metallographic microscope and a scanning electron microscope, the structure of the novel alloy is an equiaxial full-lamellar structure, as shown in fig. 1a and 1b, and as shown in fig. 2a and 2b, the mechanical properties at room temperature are as follows:
the room-temperature tensile property sigma b is more than or equal to 780MPa, sigma p0.2 is more than or equal to 850MPa, delta 5 is more than or equal to 7 percent, and psi is more than or equal to 10 percent;
the tensile property sigma b at 700 ℃ is more than or equal to 690MPa, sigma p0.2 is more than or equal to 770MPa, delta 5 is more than or equal to 15 percent, and psi is more than or equal to 19 percent;
the residual deformation under the conditions of high-temperature creep property of 700 ℃/100Mpa/100h is less than or equal to 0.3 percent.
The new alloy Ti-48Al-1Cr-2Nb-1Mn-0.2W-0.3B-0.1Si-0.08Y (at.%) designed in the embodiment greatly improves the mechanical properties of the alloy through the combined action of W, Mn elements, Si, B and rare earth elements.
Example 3Ti-48Al-1Cr-2Nb-1Mn-0.2W-0.2B-0.15C (at.%), additive manufacturing
The method is characterized in that a novel powder TiAl alloy with the particle size of 0-35 mu m is adopted, the powder formula is Ti-48Al-1Cr-2Nb-1Mn-0.2W-0.2B-0.15C (at.%), additive manufacturing is carried out, and the method comprises the following steps:
firstly, selecting a stainless steel substrate of 200mm multiplied by 150mm, and cleaning the stainless steel substrate to be clean and free of oil stain, dust, rust and the like; and secondly, carrying a laser by adopting an industrial robot, and connecting the laser cladding powder feeding system in the selected area. Drying and sieving the powder, filling the powder into a powder paving system, and paving a first layer of powder on a substrate by a scraper in the powder paving system; setting a 3D model of a cube array with the side length of 30mm in software, and converting the 3D model into a scanning path file; setting the powder spreading thickness to be 30 microns, the laser spot diameter to be 60 microns, the laser power to be 200W, the laser scanning speed to be 1000mm/s and the laser scanning interval to be 50 microns, scanning by a given path, controlling the base plate to descend by one layer by the computer after scanning one layer, and simultaneously spreading a new layer of alloy powder by a powder spreading mechanism; and fifthly, after all the scanning is finished and the substrate is cooled, separating the workpiece and the substrate by using a linear cutting method.
Claims (10)
1. The TiAl intermetallic compound containing W, Mn, Si, B, C and rare earth elements is characterized in that the TiAl intermetallic compound contains 46-50% of Al, 1-3% of Cr, 1-5% of Nb, 0-2% of W, 0-3% of Mn, 0-1.8% of B, 0-1.5% of Si, 0-1.5% of C, 0-2% of rare earth elements and the balance of Ti by mole percentage.
2. The TiAl intermetallic compound containing W, Mn, Si, B, C and rare earth elements according to claim 1, wherein Al is 47-49 mol%, W is 0.3 mol%, Mn is 0-3 mol%, Si is not more than 0.2 mol%, B is not more than 0.2 mol%, and C is not more than 0.3 mol%.
3. The TiAl intermetallic compound containing W, Mn, Si, B, C and rare earth elements according to claim 1, wherein Al is 48 mol%, W is 0.2 mol%, Mn is 2.0 mol%, Si is not more than 0.2 mol%, B is not more than 0.2 mol%, and C is not more than 0.2 mol%.
4. The TiAl intermetallic compound containing W, Mn, Si, B, C and rare earth elements according to claim 1, where the rare earth elements include La, Ce, Re, Y, Gd, Er and the like.
5. The TiAl intermetallic compound comprising W, Mn, Si, B, C and rare earth elements according to claim 1, wherein the atomic mole percent of O in the TiAl intermetallic compound is less than 800 PPm.
6. The TiAl intermetallic compound comprising W, Mn, Si, B, C and rare earth elements according to claim 1, wherein the atomic mole percent of O in the TiAl intermetallic compound is less than 500 PPm.
7. The TiAl intermetallic compound comprising W, Mn, Si, B, C and rare earth elements according to claim 1, wherein the atomic mole percent of C in the TiAl intermetallic compound is less than 500 PPm.
8. The TiAl intermetallic compound comprising W, Mn, Si, B, C and rare earth elements according to claim 1, wherein the atomic mole percent of C in the TiAl intermetallic compound is less than 300 PPm.
9. The TiAl intermetallic compound containing W, Mn, Si, B, C and a rare earth element according to claim 1, wherein the cast structure of the TiAl intermetallic compound is mainly composed of α 2 phase, γ phase and a small amount of B2/β 0 phase.
10. The TiAl intermetallic compound containing W, Mn, Si, B, C and a rare earth element according to claim 1, wherein the cast structure of the TiAl intermetallic compound is an equiaxed or columnar structure.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112658268A (en) * | 2020-12-11 | 2021-04-16 | 长沙新材料产业研究院有限公司 | Rare earth modified TiAl alloy powder for additive manufacturing and preparation method thereof |
| CN112756624A (en) * | 2020-12-11 | 2021-05-07 | 丹阳层现三维科技有限公司 | Method for reducing cracks in selective laser melting printing titanium-aluminum alloy |
| CN115627386A (en) * | 2022-11-07 | 2023-01-20 | 西北工业大学 | TiAlRe alloy suitable for rolling deformation and rolling method thereof |
| CN116334447A (en) * | 2023-03-23 | 2023-06-27 | 北京科技大学 | Preparation method of C-containing high Nb-TiAl alloy |
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