CN112222674A - High-entropy alloy for brazing TiAl and nickel-based high-temperature alloy and preparation method thereof - Google Patents
High-entropy alloy for brazing TiAl and nickel-based high-temperature alloy and preparation method thereof Download PDFInfo
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- CN112222674A CN112222674A CN202011012296.0A CN202011012296A CN112222674A CN 112222674 A CN112222674 A CN 112222674A CN 202011012296 A CN202011012296 A CN 202011012296A CN 112222674 A CN112222674 A CN 112222674A
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- entropy alloy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
- B23K35/286—Al as the principal constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Abstract
The invention relates to a high-entropy alloy for brazing TiAl and nickel-based high-temperature alloy and a preparation method thereof, wherein the high-entropy alloy comprises the following chemical components in atomic percentage: al: 15% -25%, Cu: 10% -20%, Co: 10-20%, Fe: 10-20%, Cr: 10% -20%, Ni: 5% -15%, Ti: 5 to 15 percent. The preparation method comprises the following steps: weighing raw materials required by smelting according to the components of the brazing filler metal; smelting the raw materials to obtain a high-entropy alloy brazing filler metal ingot; the high-entropy alloy amorphous foil strip is prepared by utilizing a vacuum quenching rapid solidification technology, or the high-entropy alloy brazing filler metal powder is prepared by adopting a vacuum gas atomization technology. The high-entropy alloy solder has high mixed entropy, the structure of the high-entropy alloy solder is mainly solid solution structure, the high-entropy alloy solder can be used for braze welding connection between two extremely different materials of TiAl alloy and nickel-based high-temperature alloy, and can simultaneously keep good compatibility with the two welded base metals and obtain high connection strength.
Description
Technical Field
The invention relates to a high-entropy alloy for brazing TiAl and a nickel-based high-temperature alloy and a preparation method thereof, belonging to the technical field of welding.
Background
The TiAl alloy has low density, high specific strength and good high-temperature oxidation resistance and creep resistance, is a light high-temperature-resistant structural material with development prospect, can be used at a high temperature of 750-860 ℃, is known as a substitute material of titanium alloy and high-temperature alloy, and has good application prospect in the fields of aviation, aerospace, nuclear industry, weapons, automobiles and the like.
For the TiAl alloy, in order to expand the engineering application range, the welding technology will be very important, especially for the connection of the TiAl alloy and other metals. For example, in the field of aviation, the metallic thermal protection structure of a hypersonic aircraft needs to meet the use requirement of 700-800 ℃, and the structural weight can be greatly reduced by adopting the scheme of a double-alloy honeycomb thermal structure consisting of TiAl alloy and nickel-based superalloy. The brazing is one of the methods suitable for welding the double-alloy complex precise structure, in the brazing process, a welded base metal and the brazing filler metal are integrally heated, the brazing temperature is higher than the melting range of the brazing filler metal and lower than the melting point of the base metal, so that the brazing filler metal is melted, and the base metal is not melted. However, the TiAl alloy and the nickel-based superalloy have great difference in physical and chemical properties, and the joint thereof is a very different material combination. The two materials have large component difference, the elements Ti and Ni are extremely different to react to form a Ti-Ni brittle compound, and the thermal expansion coefficients are different, so that cracks are easily induced in a connecting area. In addition, the existing titanium-based or nickel-based brazing filler metal is difficult to have good compatibility with the two extremely different materials, and is very difficult to realize good connection.
The high-entropy alloy is a novel material, generally can be defined as comprising five or more main elements, each element is alloyed according to equal atomic ratio or approximate equal atomic ratio, the mixed entropy of the elements is higher than the melting entropy of the alloy, and the high-entropy alloy has good comprehensive mechanical properties. According to the maximum entropy generation principle, a large entropy value can stabilize a high-entropy phase, and high mixed entropy generated by multiple elements is beneficial to forming a solid solution phase or a two-phase eutectic structure instead of an intermetallic compound by reducing Gibbs free energy.
Aiming at the technical current situation of braze welding connection of the TiAl alloy and the nickel-based high-temperature alloy, a high-entropy alloy design theory can be used for reference, the main elements in the TiAl alloy and the nickel-based high-temperature alloy are selected for design and preparation of the high-entropy alloy brazing filler metal, and the compatibility of the brazing filler metal and the base metal can be greatly enhanced due to the fact that the brazing filler metal contains more base metal elements. For example, the GH536 Ni-based superalloy has main constituent elements such as Ni, Cr, Fe and the like, and the TiAl alloy has main elements such as Ti and Al, and if the developed brazing filler metal contains more of these elements, the compatibility of the brazing filler metal and two base materials can be simultaneously improved. However, the main elements in the base material, such as Cr, Ti, Ni, Co, and Fe, have high melting points, which may cause the brazing filler metal to have high melting points, and thus the brazing temperature to increase. High welding temperatures can impair the properties of the base metal or lead to excessive erosion of the base metal during welding. Therefore, the brazing filler metal is ensured to have a proper melting interval, and the design difficulty and the key of the high-entropy alloy brazing filler metal are also the difficulties and the keys.
Disclosure of Invention
The invention provides a high-entropy alloy for brazing TiAl and nickel-based high-temperature alloy and a preparation method thereof aiming at solving the problems, and aims to provide a technical solution for the connection of two extremely dissimilar materials of the TiAl alloy and the nickel-based high-temperature alloy, so that a connection joint has heat resistance matched with a base material, and the engineering application field of the TiAl alloy is widened.
The purpose of the invention is realized by the following technical scheme:
the technical scheme of the invention provides a high-entropy alloy for brazing TiAl and nickel-based high-temperature alloy, which comprises the following chemical components in atomic percent: al: 15% -25%, Cu: 10% -20%, Co: 10-20%, Fe: 10-20%, Cr: 10% -20%, Ni: 5% -15%, Ti: 5 to 15 percent.
In one implementation, the high entropy alloy has a chemical composition and composition in atomic percent of: al: 20% -25%, Cu: 10% -15%, Co: 15% -20%, Fe: 10-15%, Cr: 15% -20%, Ni: 5% -10%, Ti: 5 to 10 percent.
The high-entropy alloy solder has high mixed entropy, and the structure and the appearance of the high-entropy alloy solder mainly adopt solid solution structures.
The technical scheme of the invention also provides a method for preparing the high-entropy alloy for brazing the TiAl and the nickel-based high-temperature alloy, which comprises the following steps:
converting the atomic percentage composition of the high-entropy alloy into mass percentage, and weighing raw materials required by smelting according to the mass percentage;
secondly, putting the prepared raw materials into a crucible, and smelting for 4-5 times to obtain a high-entropy alloy brazing filler metal ingot;
preparing the high-entropy alloy brazing filler metal ingot into a high-entropy alloy amorphous foil strip by using a vacuum quenching rapid solidification method; or preparing the high-entropy alloy brazing filler metal ingot into high-entropy alloy brazing filler metal powder by adopting a vacuum gas atomization method.
In practice, the element Al is added in the form of an Al-Ti master alloy and the element Cu is added in the form of an Al-Cu master alloy.
In the implementation, the smelting method comprises vacuum arc smelting, arc smelting under the argon protective atmosphere, vacuum induction smelting and electromagnetic suspension smelting.
The technical scheme of the invention has the following characteristics and beneficial technical effects:
(1) compatibility of the brazing filler metal and the base metal: as mentioned above, the compatibility between the existing solder and the existing solder is poor due to the difference of the physical and chemical properties between the TiAl alloy and the nickel-based superalloy. The invention provides a thought for designing a novel high-entropy brazing filler metal by selecting main elements in two welded base metals based on a high-entropy alloy theory, namely designing the high-entropy alloy brazing filler metal of an AlCuCoCrFeNiTi system. Ni, Cr and Fe in the brazing filler metal are main constituent elements of the nickel-based high-temperature alloy (such as GH536), and Cu, Ni, Co and Ni are infinitely mutually soluble, so that a continuous solid solution can be formed, namely the brazing filler metal has very good compatibility. Meanwhile, Al and Ti elements in the brazing filler metal are main constituent elements of the TiAl alloy. Therefore, the composition design can maintain good wettability of the brazing filler metal with two extremely different base materials.
(2) Controlling the melting point of the brazing filler metal: as described above, in the brazing process, the brazing temperature is higher than the melting range of the brazing filler metal and lower than the melting point of the base metal, so that the brazing filler metal is melted, and the base metal is not melted. Therefore, when developing a novel brazing filler metal, it is important to ensure that the brazing filler metal has a proper melting point. For the AlCuCoCrFeNiTi high-entropy alloy solder, the melting points of the elements Al and Cu are 660 ℃ and 1083 ℃ respectively, which is beneficial to controlling the melting points of the solder. In addition, the element Ti can perform eutectic reaction with elements such as Cu, Ni, Co and the like, and the melting point of the brazing filler metal can be effectively reduced. The AlCuCoCrFeNiTi high-entropy alloy solder can complete the soldering of TiAl alloy and nickel-based high-temperature alloy at the temperature of 1100 ℃.
(3) Compared with Ag-based and Ti-based solders, the solder disclosed by the invention has the advantages that the raw material cost is obviously reduced, the production cost of the solder is effectively reduced, but the heat resistance of a connecting joint is greatly improved, and the high-entropy alloy solder provided by the invention can meet the requirement that the connecting joint made of the TiAl alloy and the nickel-based high-temperature alloy dissimilar materials works at the high temperature of 750 ℃. Specifically, the room-temperature shear strength of the brazing joint corresponding to the TiAl alloy and the nickel-based high-temperature alloy reaches 250-300 MPa, and the 750-DEG C shear strength reaches 240-260 MPa.
(4) The high-entropy alloy solder can be used for directly carrying out the soldering connection of the TiAl alloy and the nickel-based high-temperature alloy dissimilar materials, does not need to apply pressure in the soldering process, has simple and easily controlled process compared with some contact reaction soldering and pressure diffusion soldering, and has the advantage of soldering a plurality of welding lines simultaneously.
Detailed Description
Example one
The method for preparing the high-entropy alloy for brazing the TiAl and the nickel-based high-temperature alloy comprises the following steps:
step one, mixing Al in atomic percent of the high-entropy alloy solder: 25%, Cu: 12.5%, Co: 12.5%, Fe: 12.5%, Cr: 12.5%, Ni: 12.5%, Ti: converting 12.5 percent into mass percent, weighing simple substances of aluminum, copper, cobalt, iron, chromium, nickel and titanium according to the mass percent, and mixing to obtain the proportioned raw materials
And step two, putting the prepared raw materials into a crucible, smelting by adopting a vacuum arc smelting method, and repeatedly smelting for 4 times to obtain the high-entropy alloy brazing filler metal ingot.
And thirdly, preparing the brazing ingot into a high-entropy alloy amorphous foil strip by using a vacuum quenching rapid solidification technology, and brazing the TiAl alloy and the nickel-based high-temperature alloy under a vacuum condition.
Example two
The difference between the present embodiment and the first embodiment is: in the first step, the high-entropy alloy solder comprises the following components in atomic percentage: 25%, Cu: 12.5%, Co: 19%, Fe: 12.5%, Cr: 19%, Ni: 6%, Ti: 6 percent; in the second step, the used smelting method is arc smelting under the argon protective atmosphere. The rest is the same as the first embodiment.
EXAMPLE III
The difference between the present embodiment and the first embodiment is: in the first step, the simple substance Al may be added in the form of an Al-10Ti (wt.%) intermediate alloy, that is, the amount of the Al-10Ti (wt.%) intermediate alloy is determined according to the amount of the simple substance Al, and the amount of the simple substance Ti to be added is calculated, and then the raw materials after proportioning are respectively weighed and obtained; in the second step, the smelting method is vacuum induction smelting. The rest is the same as the first embodiment.
Example four
The difference between the present embodiment and the first embodiment is: in the first step, the simple substance Cu can be added in the form of Al-40Cu (wt.%) intermediate alloy, that is, the amount of the required Al-40Cu (wt.%) intermediate alloy is determined according to the amount of the required simple substance Cu, the amount of the simple substance Al which needs to be added in addition is calculated, and then the raw materials after proportioning are respectively weighed and obtained; in the second step, the smelting method is electromagnetic suspension smelting; and in the third step, the brazing filler metal ingot is prepared into high-entropy alloy brazing filler metal powder by adopting a vacuum gas atomization technology. The rest is the same as the first embodiment.
Claims (8)
1. The high-entropy alloy for brazing the TiAl and the nickel-based high-temperature alloy is characterized by comprising the following chemical components in atomic percent: al: 15% -25%, Cu: 10% -20%, Co: 10-20%, Fe: 10-20%, Cr: 10% -20%, Ni: 5% -15%, Ti: 5 to 15 percent.
2. The high-entropy alloy for brazing TiAl and nickel-based superalloy according to claim 1, wherein the high-entropy alloy comprises the following chemical components in atomic percent: al: 20% -25%, Cu: 10% -15%, Co: 15% -20%, Fe: 10-15%, Cr: 15% -20%, Ni: 5% -10%, Ti: 5 to 10 percent.
3. The high-entropy alloy for brazing TiAl and nickel-based superalloy according to claim 1, wherein the high-entropy alloy comprises the following chemical components in atomic percent: al: 25%, Cu: 12.5%, Co: 12.5%, Fe: 12.5%, Cr: 12.5%, Ni: 12.5%, Ti: 12.5 percent.
4. The high-entropy alloy for brazing TiAl and nickel-based superalloy according to claim 1, wherein the high-entropy alloy comprises the following chemical components in atomic percent: al: 25%, Cu: 12.5%, Co: 19%, Fe: 12.5%, Cr: 19%, Ni: 6%, Ti: 6 percent.
5. A method for preparing the high-entropy alloy for brazing TiAl and nickel-based superalloy as claimed in claim 1, wherein the method comprises the steps of:
converting the atomic percentage composition of the high-entropy alloy into mass percentage, and weighing raw materials required by smelting according to the mass percentage;
secondly, putting the prepared raw materials into a crucible, and smelting for 4-5 times to obtain a high-entropy alloy brazing filler metal ingot;
preparing the high-entropy alloy brazing filler metal ingot into a high-entropy alloy amorphous foil strip by using a vacuum quenching rapid solidification method; or preparing the high-entropy alloy brazing filler metal ingot into high-entropy alloy brazing filler metal powder by adopting a vacuum gas atomization method.
6. A method for producing a high entropy alloy for brazing TiAl with nickel based superalloy according to claim 5, wherein the element Al is added in the form of an Al-Ti master alloy.
7. A method for producing a high entropy alloy for brazing TiAl with nickel based superalloy according to claim 5, wherein the element Cu is added in the form of an Al-Cu master alloy.
8. The method for preparing the high-entropy alloy for brazing TiAl and the nickel-based superalloy according to claim 5, wherein the smelting method is vacuum arc smelting, arc smelting under an argon protective atmosphere, vacuum induction smelting or electromagnetic suspension smelting.
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Cited By (7)
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| CN113122764A (en) * | 2021-03-19 | 2021-07-16 | 西安理工大学 | Preparation method of CuCrFeCoNixTi high-entropy alloy thin strip |
| CN113182632A (en) * | 2021-05-07 | 2021-07-30 | 浙江工业大学 | Method for connecting C/C composite material by adopting high-entropy alloy brazing |
| CN113245747A (en) * | 2021-05-26 | 2021-08-13 | 临沂大学 | High-entropy alloy high-temperature brazing filler metal |
| CN113564493A (en) * | 2021-08-10 | 2021-10-29 | 成都大学 | High-entropy alloy reinforced FeCrAl alloy cladding material and preparation process thereof |
| CN113814604A (en) * | 2021-10-12 | 2021-12-21 | 大连理工大学 | Eutectic high-entropy alloy solder for brazing titanium, titanium alloy and stainless steel and preparation method thereof |
| CN113814606A (en) * | 2021-08-20 | 2021-12-21 | 西安理工大学 | Ni-Cr-Al-Ti-Co welding wire, method and groove form |
| CN114310037A (en) * | 2022-01-27 | 2022-04-12 | 哈尔滨工业大学 | NiCrFeCuZrHf brazing filler metal and preparation method thereof |
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| CN114310037A (en) * | 2022-01-27 | 2022-04-12 | 哈尔滨工业大学 | NiCrFeCuZrHf brazing filler metal and preparation method thereof |
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