CN118204674A - Ti-Mn-Fe-Ni-Nb-Zr entropy solder for TiAl and use method thereof - Google Patents
Ti-Mn-Fe-Ni-Nb-Zr entropy solder for TiAl and use method thereof Download PDFInfo
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- CN118204674A CN118204674A CN202410513365.8A CN202410513365A CN118204674A CN 118204674 A CN118204674 A CN 118204674A CN 202410513365 A CN202410513365 A CN 202410513365A CN 118204674 A CN118204674 A CN 118204674A
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- 229910010038 TiAl Inorganic materials 0.000 title claims abstract description 55
- 229910020018 Nb Zr Inorganic materials 0.000 title claims abstract description 30
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000956 alloy Substances 0.000 claims abstract description 72
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 71
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 238000005219 brazing Methods 0.000 claims description 126
- 229910052751 metal Inorganic materials 0.000 claims description 57
- 239000000945 filler Substances 0.000 claims description 55
- 239000002184 metal Substances 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 239000010953 base metal Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910001257 Nb alloy Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000005304 joining Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005476 soldering Methods 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 230000005496 eutectics Effects 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 8
- 238000010587 phase diagram Methods 0.000 description 8
- 229910018559 Ni—Nb Inorganic materials 0.000 description 6
- 238000005728 strengthening Methods 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229910001325 element alloy Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910006281 γ-TiAl Inorganic materials 0.000 description 2
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910021325 alpha 2-Ti3Al Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- 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
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3026—Mn as the principal constituent
-
- 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
- B23K1/00—Soldering, e.g. brazing, or unsoldering
-
- 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
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3033—Ni as the principal constituent
-
- 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
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3053—Fe as the principal constituent
-
- 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
- B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
- B23K35/325—Ti as the principal constituent
-
- 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
-
- 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
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/08—Non-ferrous metals or alloys
- B23K2103/10—Aluminium or alloys thereof
-
- 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
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/08—Non-ferrous metals or alloys
- B23K2103/14—Titanium or alloys thereof
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Ceramic Products (AREA)
Abstract
The invention provides a Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy solder for TiAl and a use method thereof, wherein the solder comprises the following components in percentage by mass: 17.0 to 22.0 percent of Mn; 13.0 to 17.0 percent of Fe; ni2.0-8.0%; nb2.0-9.0%; zr 0-5.0%; the balance Ti; the content ratio of Ni to Nb is (45-50) to (55-50). The invention has the following effects: the average tensile strength of the soldering joint at room temperature obtained under the condition of (1140-1170) DEG C/(20-75) min reaches 421-457 MPa, and the high-temperature tensile strength at 700 ℃, 750 ℃ and 850 ℃ is 427-468 MPa, 435-465 MPa and 386-415 MPa.
Description
Technical Field
The invention belongs to the technical field of aviation brazing, and particularly relates to a Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy brazing filler metal for TiAl and a use method thereof.
Background
The main advantages of TiAl-based alloys include low density (3.9-4.2 g/cm), higher specific strength and specific stiffness, and good creep resistance, oxidation resistance and flame retardance at temperatures below 800 ℃. Compared with the traditional titanium alloy, the part manufactured by the TiAl-based alloy in the field of aviation can bear the working temperature of 700-850 ℃ for a long time, and compared with the titanium alloy, the part manufactured by the TiAl-based alloy can greatly improve the long-term service temperature of a component, and compared with the traditional nickel-based superalloy, the part manufactured by the TiAl-based alloy has lower density and higher specific strength. Therefore, the TiAl-based alloy has wide high-temperature application prospect in the field of aviation.
However, the TiAl-based alloy itself has a large brittleness, and room temperature plasticity of only 1 to 3%, and cracks are extremely easy to generate in the welding process. From the standpoint of high feasibility and good economy, the brazing technique is a joining technique that is well suited for welding TiAl-based alloys. At present, research on the TiAl-based alloy brazing technology focuses on improvements of a brazing method, brazing materials, a brazing process, control of a brazing process, room temperature/high temperature strength of a brazing joint and the like, however, the brazing temperature of the brazing material and the strength of the brazing joint are still not coordinated. The brazing temperature of Ag-based or Al-based brazing filler metal is low, but the high-temperature strength of the brazing joint is obviously insufficient; although room temperature strength of the Ti-based brazing filler metal braze joint is improved, high temperature strength of the braze joint is still insufficient, and brazing temperature corresponding to the Ti-based brazing filler metal is high, for example, performance damage of a base metal is easily caused when the temperature exceeds 1200 ℃. Therefore, the key point of the TiAl-based alloy brazing material is that the brazing can be realized at a lower brazing temperature (lower than 1200 ℃), and the brazing joint also has higher room temperature/high temperature (750-850 ℃) strength.
Disclosure of Invention
In view of the above, the invention aims to provide a Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy solder for TiAl and a use method thereof, which can effectively solve the problems of overhigh soldering temperature of the solder and insufficient room temperature/high temperature (750-850 ℃) strength of soldered joints in the prior art.
The invention provides a Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy solder for TiAl, which comprises the following components in percentage by mass:
17.0 to 22.0 percent of Mn; 13.0 to 17.0 percent of Fe; ni 2.0-8.0%; nb 2.0-9.0%; zr 0-5.0%; the balance Ti;
the content ratio of Ni to Nb is (45-50) to (55-50).
Preferably, mn is 17.0-22.0%; 13.0 to 17.0 percent of Fe; ni 2.5-8.0%; nb 2.5-9.0%; zr 0-5.0%; the balance Ti; the content ratio of Ni to Nb is (45-50) to (55-50).
Preferably, the solder is used in one or more of the following shapes: a block, a crushed particle, a flake, a powder, a quenched foil, or a powder sintered body.
The invention provides a preparation method of Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy solder for TiAl, which comprises the following steps:
Proportioning according to the mass percentage of the brazing filler metal, and melting by adopting an arc melting method to obtain the Ti-Mn-Fe-Ni-Nb-Zr six-element medium-entropy alloy brazing filler metal.
The technical scheme is the application of the Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy brazing filler metal for TiAl in the connection of TiAl alloy, ti-Al-Nb alloy, ti-based composite material, tiAl-based composite material, other multi-element medium entropy or high entropy alloy matrix material containing one element of Ti, or other brazing multi-element medium entropy or high entropy alloy matrix material containing two elements of Ti and Al.
The invention provides a brazing method of TiAl alloy, which comprises the following steps:
S1, preparing a base material to be welded: preprocessing the surface of a base material and the position to be welded;
S2, assembling: adding brazing filler metal at a position to be welded of a base metal to obtain an assembled assembly; the brazing filler metal is the brazing filler metal according to the technical scheme or the brazing filler metal prepared by the preparation method according to the technical scheme;
s3, brazing: and brazing the assembled assembly.
Preferably, the brazing is vacuum brazing;
The vacuum brazing process comprises the following steps:
The vacuum degree in the furnace is better than 8X 10 -3 Pa, the temperature is raised to 600 ℃ at the speed of 10-40 ℃/min, then the temperature is raised to 900 ℃ at the speed of 10-30 ℃/min, then the temperature is raised to 1140-1170 ℃ at the speed of 10-25 ℃/min, and the temperature is kept for 20-75 min; after the heat preservation is finished, the temperature is reduced at the speed of 10-40 ℃/min, and the furnace is cooled.
Preferably, the gap between the positions to be welded of the base material is 0.03-0.07 mm.
The invention provides a Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy solder for TiAl, which comprises the following components in percentage by mass: 17.0 to 22.0 percent of Mn; 13.0 to 17.0 percent of Fe; ni 2.0-8.0%; nb 2.0-9.0%; zr 0-5.0%; the balance Ti; the content ratio of Ni to Nb is (45-50) to (55-50). The brazing filler metal provided by the invention has solid solution strengthening and fine crystal strengthening effects when being applied to brazing of TiAl alloy, and the obtained brazing joint has higher room temperature/high temperature strength. The experimental results show that: the average tensile strength of the joint at room temperature, which is obtained under the brazing condition of (1140-1170) DEG C/(20-75) min, reaches 421-457 MPa, the tensile strength at 700 ℃ is 427-4638 MPa, the tensile strength at 750 ℃ is 435-460 MPa, and the tensile strength at 850 ℃ is 386-415 MPa.
Drawings
FIG. 1 is a schematic diagram of an assembly structure in the step S2;
FIG. 2 is a front profile of a braze sample prepared in accordance with an embodiment of the present invention;
FIG. 3 is a cross-sectional microstructure of a braze joint made in accordance with an embodiment of the invention;
FIG. 4 is a ternary phase diagram of Ti-Mn-Fe;
FIG. 5 is a ternary phase diagram of Ti-Ni-Nb;
FIG. 6 is a Ni-Nb binary phase diagram;
FIG. 7 is a binary phase diagram of Ni-Zr.
Detailed Description
The invention provides a Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy solder for TiAl, which comprises the following components in percentage by mass:
17.0 to 22.0 percent of Mn; 13.0 to 17.0 percent of Fe; ni 2.0-8.0%; nb 2.0-9.0%; zr 0-5.0%; the balance Ti;
the content ratio of Ni to Nb is (45-50) to (55-50).
The medium entropy alloy brazing filler metal provided by the invention comprises 7.0-22.0% of Mn, and preferably 17.0-21.0%.
The medium entropy alloy brazing filler metal provided by the invention comprises 13.0-17.0% of Fe, and preferably 13.0-16.0%.
The medium entropy alloy brazing filler metal provided by the invention comprises 2.0-8.0% of Ni, preferably 2.5-8.0%, and more preferably 3.0-7.8%.
The medium entropy alloy brazing filler metal provided by the invention comprises 2.0-9.0% of Nb, preferably 2.5-9.0%, and more preferably 3.5-9.0%.
The medium entropy alloy solder provided by the invention comprises 0-5.0% of Zr. The medium entropy alloy brazing filler metal provided by the invention comprises the balance Ti.
In the specific embodiment of the invention, the Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy solder for TiAl comprises the following components in percentage by mass:
Ti 57.63％、Fe 15.52％、Mn 20.35％、Ni 3.00％、Nb 3.50％；
Or Ti 55.17%, fe 14.85%, mn 19.48%, ni 5.00%, nb 5.50%;
or Ti 51.16%, fe 13.77%, mn 18.07%, ni 7.00%, nb 7.50%;
Or Ti 53.63%, fe 14.43%, mn 18.94%, ni 5.00%, nb 5.50%, zr 2.50%;
or 48.18% of Ti, 13.00% of Fe, 17.02% of Mn, 7.80% of Ni, 9.00% of Nb and 5.00% of Zr.
The interface reaction between the brazing filler metal and the welded TiAl base metal is greatly reduced: comprehensively considering the metallurgical actions of the elements and providing the component range of the Ti-Mn-Fe-Ni-Nb-Zr alloy solder for TiAl; through thermodynamic calculation, the mixing entropy of the Ti-Mn-Fe-Ni-Nb-Zr alloy solder is between 8.84 and 11.16 J.mol -1·K-1, and the key parameters of the multi-principal element alloy, namely between 1.0R and 1.5R, are met, and the alloy solder belongs to the medium-entropy alloy solder. The multi-element alloy solder does not have a severe chemical reaction with the welded TiAl parent metal, and is favorable for obtaining good metallurgical connection.
The solidus temperature of the brazing filler metal is 1000.3-1083.5 ℃, the liquidus temperature of the brazing filler metal is 1062.0-1106.7 ℃, and lower-temperature brazing (T b =1140-1170 ℃) can be realized. Conversely, if the liquidus temperature T L of the brazing filler metal is too high, the natural brazing temperature T b is also higher, so that the energy consumption is too high in the brazing production process, the environment is not protected, the tissue of a near-seam area is influenced by too high T b, and the performance of a base metal is greatly damaged.
The solder provided by the invention has wide preparation forms, and Ti-Mn-Fe-Ni-Nb-Zr alloy for TiAl can be prepared into various use forms, and various use forms exist during soldering. After smelting the Ti-Mn-Fe-Ni-Nb-Zr alloy, adopting different preparation methods to prepare corresponding use forms, wherein the use forms of the brazing filler metal are one or more of the following shapes: a block, a crushed particle, a flake, a powder, a quenched foil, or a powder sintered body.
The brazing filler metal provided by the invention does not contain precious metals: ti, fe, ni, mn are all conventional metal elements, and refractory metal elements Nb and Zr have low content and do not contain noble metals, so that the method has great price advantage in the aspect of economy.
The invention provides a preparation method of Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy solder for TiAl, which comprises the following steps:
Proportioning according to the mass percentage of the brazing filler metal, and melting by adopting an arc melting method to obtain the Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy brazing filler metal for TiAl.
The application provides the application of the Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy solder for TiAl in the connection of TiAl alloy, ti-Al-Nb alloy, ti-based composite material, tiAl-based composite material, other multi-element medium entropy or high entropy alloy matrix material containing one element of Ti, or other braze welding multi-element medium entropy or high entropy alloy matrix material containing two elements of Ti and Al.
The application also provides an application of the Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy solder for TiAl in the TiAl alloy brazing connection.
The invention provides a brazing method of TiAl alloy, which comprises the following steps:
S1, preparing a base material to be welded: preprocessing the surface of a base material and the position to be welded;
S2, assembling: adding brazing filler metal at a position to be welded of a base metal to obtain an assembled assembly; the brazing filler metal is the brazing filler metal according to the technical scheme or the brazing filler metal prepared by the preparation method according to the technical scheme;
s3, brazing: and brazing the assembled assembly.
The application applies the design concept of multi-element medium-high entropy alloy, more than five alloy elements are added into the solder, the solid solution strengthening of different elements is comprehensively utilized, and the refining strengthening effect improves the strength of the soldered joint. The Fe and Mn elements in the medium entropy alloy material provided by the application can refine grains and strengthen solid solution, so that the room temperature and high temperature mechanical properties of the TiAl joint are improved. When the content of Ni element in the joint is 0.25-2.0 at%, dynamic recrystallization can be promoted, the work hardening rate is stabilized, the softening rate and degree are reduced, and the thermal processing plasticity of the TiAl joint is improved. Nb element is advantageous for improving room temperature toughness and room temperature/high temperature strength of TiAl joints. When the content of Zr element in the joint is 0.5-3.0 at%, the yield strength of the TiAl joint can be obviously improved, and the toughness and the breaking behavior can be improved.
The invention pretreats the surface of the base material and the position to be welded, in particular to remove greasy dirt and impurities on the surface of the base material and remove oxides on the position to be welded.
According to the invention, brazing filler metal is added at the position to be welded of the base metal, so that an assembled assembly is obtained. The invention controls the brazing gap between the base materials to be welded to be 0.03-0.07 mm through machining or a fixture of a tool. See fig. 1.
The brazing temperature in the invention is 1140-1170 ℃.
The brazing of the invention preferably adopts vacuum brazing; the vacuum brazing process comprises the following steps:
The vacuum degree in the furnace is better than 8X 10 -3 Pa, the temperature is raised to 600 ℃ at the speed of 10-40 ℃/min, then the temperature is raised to 900 ℃ at the speed of 10-30 ℃/min, then the temperature is raised to 1140-1170 ℃ at the speed of 10-25 ℃/min, and the temperature is kept for 20-75 min; after the heat preservation is finished, the temperature is reduced at the speed of 10-40 ℃/min, and the furnace is cooled.
The invention performs brazing under verified brazing conditions, preferably under (1140-1170) DEG C/(20-75) min conditions; in specific embodiments, the brazing conditions are (1160-1170) DEG C/45 min, (1150-1160) DEG C/60 min, (1140-1150) DEG C/60 min or (1140-1150) DEG C/75 min.
FIG. 2 is a front topography of a braze sample prepared according to an embodiment of the invention. Figure 3 is a cross-sectional microstructure of a braze joint made in accordance with an embodiment of the invention.
In some embodiments of the invention, the brazing alloy is used for brazing at the temperature of (1140-1170) DEGC/(20-75) min, the structure of the brazing joint is mainly gamma-TiAl and alpha 2-Ti3 Al, and alloy elements in the brazing alloy are diffused to a welded TiAl alloy matrix in the brazing process, so that the content of the alloy elements in the brazing joint reaches the following level: fe is more than or equal to 0.5% and less than or equal to 4.0%, mn is more than or equal to 0.5% and less than or equal to 4.0%, ni is more than or equal to 0.25% and less than or equal to 2.0%, nb is more than or equal to 1.0% and Zr is more than or equal to 0.5% and less than or equal to 3.0% (at.%), which play a role in strengthening a small amount or trace of alloying elements for gamma-TiAl phase in the soldered joint.
The high-temperature strength of the TiAl/TiAl braze joint obtained by the brazing filler metal in the invention in the wide temperature range of 700-850 ℃ is obviously superior to that of braze joints corresponding to simple ternary and quaternary brazing filler metal alloys such as Ti-Fe-Mn or Ti-Zr-Ni-Cu or Ti-Ni-Nb or Ti-Zr-Ni-Nb.
According to a Ti-Mn-Fe ternary phase diagram, the Ti element, the Mn and the Fe element have good compatibility, and ternary eutectic components Ti- (19-24) Mn- (14-19) Fe (wt.%) exist, and the eutectic temperature is about 1126 ℃. Meanwhile, according to a Ni-Nb binary phase diagram, a binary eutectic component Ni- (50-55) Nb (wt.%) exists, and the eutectic temperature is 1175 ℃. Furthermore, according to the ternary phase diagram of Ti-Ni-Nb, there is ternary eutectic composition Ti- (32-37) Ni- (14-19) Nb (wt.%) and the eutectic temperature is 900.3 ℃. In addition, according to the Ni-Zr binary phase diagram, binary eutectic components Ni- (45-50) Zr (wt.%) exist, and the eutectic temperature is 1061-1070 ℃. The Ni-Zr eutectic composition can further lower the alloy melting point. See fig. 4-7. Ti, zr and Nb elements are infinitely dissolved in a pair mode, and the compatibility is good.
In order to further illustrate the present invention, the following examples are provided to describe the Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy brazing filler metal for TiAl and the method of use thereof in detail, but they should not be construed as limiting the scope of protection of the present invention.
Examples 1 to 3
Preparing the materials of the brazing filler metals according to the mass percentages of the raw materials of the brazing filler metals shown in the table 1, and melting the materials by adopting an arc melting method to obtain alloy ingots;
TABLE 1
| Examples | Ti | Fe | Mn | Ni | Nb | Zr |
| 1 | 57.63 | 15.52 | 20.35 | 3.00 | 3.50 | 0 |
| 2 | 55.17 | 14.85 | 19.48 | 5.00 | 5.50 | 0 |
| 3 | 51.16 | 13.77 | 18.07 | 7.00 | 7.50 | 0 |
The alloy ingot is prepared into brazing filler metals with different shapes by adopting different manufacturing processes, wherein the brazing filler metals comprise blocks, powder sintered bodies and quenched foil strips.
The TiAl-based alloy matrix material is adopted, and the nominal component is Ti-46Al- (3-4) Nb- (2-3) (Cr, ta, B) (at%). Cutting a pure Ti foil strip with the thickness of 0.03-0.07 mm into narrow strips with the width of 0.5-1 mm, spot-welding the narrow strips on one side of a surface to be welded of a base material by using a spot welder, clamping the base materials on two sides by using a tool, and controlling the brazing gap to be 0.03-0.07 mm; then, prefabricating solder powder at a position to be welded of a base metal to form an assembly component;
And (3) putting the assembled assembly into a vacuum furnace for brazing, wherein the vacuum degree in the furnace is 5.0X10 -3 Pa, and the brazing temperature is 1140-1170 ℃ to obtain the brazing joint.
The invention performs performance tests on braze joints, the results are shown in Table 2:
TABLE 2
The brazing temperature of the brazing filler metal is 1140-1170 ℃; under proper brazing specifications, the braze joint has high room temperature/high temperature tensile strength.
Examples 4 to 5
Proportioning the raw materials of the brazing filler metals according to the mass percentages in the table 3, and melting the brazing filler metals by an arc melting method to obtain alloy ingots;
TABLE 3 Table 3
| Examples | Ti | Fe | Mn | Ni | Nb | Zr |
| 4 | 53.63 | 14.43 | 18.94 | 5.00 | 5.50 | 2.50 |
| 5 | 48.18 | 13.00 | 17.02 | 7.80 | 9.00 | 5.00 |
The alloy ingot is prepared into brazing filler metals with different shapes by adopting different manufacturing processes, wherein the brazing filler metals comprise blocks, powder and quenched foil strips.
The base material is TiAl-based alloy, and the nominal composition is Ti-46Al- (3-4) Nb- (2-3) (Cr, ta, B) (at%). Cutting a pure Ti foil strip with the thickness of 0.03-0.07 mm into narrow strips with the width of 0.5-1 mm, spot-welding the narrow strips on one side of a surface to be welded of a base material by using a spot welder, clamping the base materials on two sides by using a tool, and controlling the brazing gap to be 0.03-0.07 mm; then, the brazing filler metal powder is prefabricated at the position to be welded of the base metal to form the assembly component.
And (3) putting the assembled assembly into a vacuum furnace for brazing, wherein the vacuum degree in the furnace is 5.0X10 -3 Pa, and the brazing temperature is 1140-1170 ℃ to obtain the brazing joint.
The invention performs performance tests on braze joints, and the results are shown in Table 4:
TABLE 4 Table 4
The brazing temperature of the brazing filler metal is 1140-1170 ℃; under proper brazing specifications, the braze joint has high room temperature/high temperature tensile strength.
The invention provides a Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy solder for TiAl, which comprises the following components in percentage by mass: 17.0 to 22.0 percent of Mn; 13.0 to 17.0 percent of Fe; ni2.0-8.0%; nb2.0-9.0%; zr 0-5.0%; the balance Ti; the content ratio of Ni to Nb is (45-50) to (55-50). The brazing filler metal controls the content of each component by introducing Ni, nb and Zr into the Ti-Mn-Fe matrix alloy, and when the brazing filler metal is applied to the brazing of TiAl alloy, the obtained brazing joint has lower brazing temperature and higher room temperature/high temperature tensile strength.
As is clear from the above examples, the joints obtained using the brazing filler metal of the present invention under brazing conditions of (1140-1150) °c/(50-75) min had room temperature average tensile strengths of 421-428 MPa, and at high temperatures of 700 ℃, 750 ℃ and 850 ℃ average tensile strengths of 438MPa, 447MPa and 399MPa, respectively. The room temperature tensile strength of the joint obtained under the conditions of 1150-1160 ℃ and/(40-60) min reaches 426-440 MPa, and the average tensile strength at the high temperature of 700 ℃, 750 ℃ and 850 ℃ is 445MPa, 453MPa and 404MPa respectively. The room temperature tensile strength of the joint obtained under the condition of (1160-1170) DEG C/(20-50) min reaches 434-457 MPa, and the average tensile strength at the high temperature of 700 ℃, 750 ℃ and 850 ℃ is 456MPa, 459MPa and 411MPa respectively.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy solder for TiAl is characterized by comprising the following components in percentage by mass:
17.0 to 22.0 percent of Mn; 13.0 to 17.0 percent of Fe; ni 2.0-8.0%; nb 2.0-9.0%; zr 0-5.0%; the balance Ti;
the content ratio of Ni to Nb is (45-50) to (55-50).
2. The Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy filler metal for TiAl according to claim 1, wherein Mn is 17.0 to 22.0%; 13.0 to 17.0 percent of Fe; ni2.5-8.0%; nb 2.5-9.0%; zr 0-5.0%; the balance Ti; the content ratio of Ni to Nb is (45-50) to (55-50).
3. The Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy solder for TiAl according to claim 1, wherein the solder is used in one or more of the following shapes: a block, a crushed particle, a flake, a powder, a quenched foil, or a powder sintered body.
4. A method for preparing the Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy solder for TiAl according to any one of claims 1 to 3, comprising the steps of:
Proportioning according to the mass percentage of the brazing filler metal, and melting by adopting an arc melting method to obtain the Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy brazing filler metal for TiAl.
5. Use of the Ti-Mn-Fe-Ni-Nb-Zr medium entropy alloy filler metal for TiAl according to any one of claims 1 to 3 in joining of a TiAl alloy, a Ti-Al-Nb alloy, a Ti-based composite, a TiAl-based composite, a matrix material of other multi-elements comprising Ti one element or a matrix material of other braze-ing multi-elements comprising Ti and Al.
6. A method of brazing a TiAl alloy comprising the steps of:
S1, preparing a base material to be welded: preprocessing the surface of a base material and the position to be welded;
s2, assembling: adding brazing filler metal at a position to be welded of a base metal to obtain an assembled assembly; the brazing filler metal is the brazing filler metal according to any one of claims 1 to 3 or the brazing filler metal prepared by the preparation method according to claim 4;
s3, brazing: and brazing the assembled assembly.
7. The brazing method according to claim 6, wherein the brazing is vacuum brazing;
The vacuum brazing process comprises the following steps:
The vacuum degree in the furnace is better than 8X 10 -3 Pa, the temperature is raised to 600 ℃ at the speed of 10-40 ℃/min, then the temperature is raised to 900 ℃ at the speed of 10-30 ℃/min, then the temperature is raised to 1140-1170 ℃ at the speed of 10-25 ℃/min, and the temperature is kept for 20-75 min; after the heat preservation is finished, the temperature is reduced at the speed of 10-40 ℃/min, and the furnace is cooled.
8. The brazing method according to claim 6, wherein the gap between the positions to be welded of the base material is 0.03 to 0.07mm.
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