CN111496417A - Ti-Ni-Nb-Zr brazing material of Nb-Si-based ultrahigh-temperature structural material and brazing connection process - Google Patents
Ti-Ni-Nb-Zr brazing material of Nb-Si-based ultrahigh-temperature structural material and brazing connection process Download PDFInfo
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- CN111496417A CN111496417A CN202010392447.3A CN202010392447A CN111496417A CN 111496417 A CN111496417 A CN 111496417A CN 202010392447 A CN202010392447 A CN 202010392447A CN 111496417 A CN111496417 A CN 111496417A
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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
- B23K35/32—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
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/008—Soldering within a furnace
-
- 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
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
- B23K1/206—Cleaning
Abstract
The invention belongs to the technical field of welding, and particularly relates to a Ti-Ni-Nb-Zr brazing material of an Nb-Si-based ultrahigh-temperature structural material and a brazing connection process. At present, a special brazing material for connecting Nb-Si based ultra-high temperature structural materials is lacked, the content of brittle phases in the joint can be reduced, and the brazed joint with higher strength is obtained. The Ti-Ni-Nb-Zr brazing solder of the Nb-Si based ultrahigh temperature structural material comprises the following chemical components in percentage by weight: ni: 15.0-20.0, Nb: 12.0 to 18.0, Zr: 18.0 to 25.0, and the balance Ti. The brazing solder has good spreading performance, can be well wetted and spread on the Nb-Si base surface, has good plasticity, can be processed into different brazing solder forms, and is beneficial to adding and assembling the brazing solder before welding.
Description
Technical Field
The invention belongs to the technical field of welding, and particularly relates to a Ti-Ni-Nb-Zr brazing material of an Nb-Si-based ultrahigh-temperature structural material and a brazing connection process.
Background
Advanced aircraft engines have higher turbine temperatures, which require higher temperature capability of the blade material. At present, the temperature bearing capacity of the fifth generation nickel-based single crystal superalloy, which is the most advanced blade material, still does not exceed 1150 ℃, and reaches more than 80% of the melting point of the fifth generation nickel-based single crystal superalloy, and the fifth generation nickel-based single crystal superalloy approaches the limit use temperature of the fifth generation nickel-based single crystal superalloy, so that the use requirement of a future high-performance engine is difficult to meet.
The Nb-Si based ultra-high temperature structural material mainly consists of a solid solution of Nb (Nb)SS) And an intermetallic compound Nb5Si3Two-phase composition of NbSSHas good room temperature toughness and intermetallic compound phase Nb5Si3The high-temperature-resistant material has excellent high-temperature strength, large unit cell lattice constant, difficulty in dislocation and creep, good creep resistance and thermodynamic stability at 1600-1800 ℃. The Nb-Si based ultra-high temperature structural material with a tough/brittle two-phase structure is formed by NbSSProviding room temperature ductility of the material, Nb5Si3The high-temperature strength is provided, the excellent high-temperature strength is ensured, and meanwhile, the high-temperature strength has certain room temperature plasticity, and is expected to become a next-generation advanced aeroengine blade material. Generally speaking, the service temperature can be as high as 1200-1400 ℃.
The Nb-Si based ultra-high temperature structural material has high melting point, high rigidity, low density and excellent high temperature strength, has great potential to replace the existing Ni based high temperature alloy and is applied to the aerospace field. Soldering/joining is one of the indispensable key manufacturing techniques to achieve its engineering applications. At present, few relevant documents are reported about the connection of the materials. The connection of Nb-Si-based ultrahigh-temperature structural materials can be realized by adopting traditional Ni-based brazing materials BNi-2(Ni-7Cr-5Si-3B-3Fe, mass percent), BNi-5(Ni-19Cr-10Si, mass percent) and the like, but the excessively high Ni content in the brazing materials enables a large amount of Ni-Nb and Ni-B brittle intermetallic compound phases to be generated in a joint, so that the defects of microcracks, unwelded joints and the like are generated in the joint, and the joint strength is low.
Therefore, the special brazing material for connecting Nb-Si based ultra-high temperature structural materials is lacked, the content of brittle phases in the joint can be reduced, and the brazed joint with higher strength is obtained.
Disclosure of Invention
The invention aims to specially design a Ti-Ni-Nb-Zr brazing material of an Nb-Si-based ultrahigh-temperature structural material and a brazing connection process aiming at the technical defects, so that the effective brazing connection of the Nb-Si-based ultrahigh-temperature structural material is realized, and a brazed joint with excellent room temperature and high temperature strength is obtained.
The purpose of the invention is realized by the following technical scheme:
a Ti-Ni-Nb-Zr brazing solder of an Nb-Si based ultrahigh temperature structure material comprises the following chemical components in percentage by weight: ni: 15.0-20.0, Nb: 12.0 to 18.0, Zr: 18.0 to 25.0, and the balance Ti.
Optionally, the brazing material comprises the following chemical components in percentage by weight: ni: 15.0 to 17.0, Nb: 12.0 to 18.0, Zr: 18.0 to 25.0, and the balance Ti.
Optionally, the brazing material comprises the following chemical components in percentage by weight: ni: 17.0 to 20.0, Nb: 12.0 to 18.0, Zr: 18.0 to 25.0, and the balance Ti.
Optionally, the brazing material comprises the following chemical components in percentage by weight: ni: 16.0, Nb: 12.0 to 18.0, Zr: 18.0 to 25.0, and the balance Ti.
Optionally, the brazing material comprises the following chemical components in percentage by weight: ni: 15.0-20.0, Nb: 14.0 to 18.0, Zr: 18.0 to 25.0, and the balance Ti.
Optionally, the brazing material comprises the following chemical components in percentage by weight: ni: 15.0-20.0, Nb: 12.0 to 18.0, Zr: 20.0, and the balance being Ti.
The brazing connection process of the Nb-Si based ultrahigh-temperature structural material adopts the Ti-Ni-Nb-Zr brazing material and comprises the following steps:
cleaning the surfaces of a first Nb-Si-based ultrahigh-temperature structure material and a second Nb-Si-based ultrahigh-temperature structure material to be brazed, and assembling, wherein the fit clearance of the first Nb-Si-based ultrahigh-temperature structure material and the second Nb-Si-based ultrahigh-temperature structure material is 0.02-0.09 mm;
fixing the brazing solder at the fitting angle of the first Nb-Si base ultra-high temperature structure material and the second Nb-Si base ultra-high temperature structure material to be welded or between the first Nb-Si base ultra-high temperature structure material and the second Nb-Si base ultra-high temperature structure material to be welded, and ensuring close fitting;
step three, uniformly coating aluminum oxide flow resisting agents on the top and the bottom of a welding seam, and then placing a combination of the first Nb-Si-based ultrahigh-temperature structural material and the second Nb-Si-based ultrahigh-temperature structural material to be welded and the brazing material in a vacuum heating furnace for brazing;
step four, adjusting the vacuum degree in the furnace to be better than 8 × 10-3And when Pa is needed, heating, wherein the heating speed is not more than 15 ℃/min, the brazing connection temperature is 1250-1290 ℃, the heat preservation time is 50-100 min, and furnace cooling is carried out after the heat preservation is finished.
Optionally, the braze is in the form of a block, a strip, a wire, or an alloy powder.
Optionally, the first Nb-Si-based ultra-high temperature structural material and the second Nb-Si-based ultra-high temperature structural material are assembled and combined by adopting a butt joint or splicing method.
Alternatively, the braze joint temperature is 1270 ℃.
The technical scheme of the invention has the advantages and beneficial effects that:
1. the solder has good spreading performance, can be well wetted and spread on the surface of the Nb-Si-based alloy, has good plasticity, can be processed into different solder forms such as blocks, strips, wires or alloy powder, and is beneficial to adding and assembling the solder before welding;
2. in the invention, a certain content of Ni is added for reducing the melting point of the brazing solder, but the content of the Ni element in the brazing solder is controlled to be not more than 20 percent by mass, so that the generation tendency and the content of Ni-Nb and Ni-Ti brittle compound phases in the joint can be reduced; the other elements Nb and Ti in the brazing material are constituent elements of Nb-Si alloy base metal, and the element Zr and Nb are completely mutually soluble, so that the brazing material has good compatibility with the welded Nb-Si base metal, and the joint performance is improved;
3. the brazing filler metal disclosed by the invention is combined with related binary alloy phase diagram theoretical calculation and repeated test optimization to obtain brazing filler metal components with reasonable Ti-Ni-Nb-Zr component distribution ratio, the melting temperature range is 1194-1223 ℃, the connection can be carried out within the brazing temperature range of 1230-1300 ℃, the recommended brazing connection temperature is 1250-1290 ℃, the heat treatment temperature is lower than that of Nb-Si base metal (1450-1500 ℃), and the performance of the base metal is not damaged; moreover, under the condition that the brazing connection temperature is 1250-1290 ℃, and the fit clearance of the materials to be welded is 0.02-0.09 mm, the welding seam can be welded at one time without repair welding, and the defects of corrosion, fusion, microcrack and the like in the brazing seam can be ensured;
4. the brazing filler metal and the joint obtained under the process condition have high performance, the joint structure obtained by interdiffusion of the brazing filler metal and the base metal is close to the base metal, and the joint mainly comprises (Nb, Ti) solid solution phase and Nb5Si3Phase composition, and Ti, Zr and Ni elements in the brazing filler metal are dissolved in (Nb, Ti)SSAnd (Nb, Ti, Zr)5Si3In the phase, the connecting joint does not have residual brazing filler metal with the melting temperature of 1194-1223 ℃ or brittle intermetallic compound phases such as Ni-Nb, Ni-Ti and the like. When the Ni-based brazing filler metal is adopted, a large amount of brittle intermetallic compound phases such as Nb-Ni, Ni-Si, Ni-B and the like are generated in a joint due to high elements such as Si, B and the like, so that the joint strength is low, and even microcracks occur in the joint. The room-temperature bending strength of the connection joint obtained by the brazing material reaches 330-363 MPa, reaches 60-66% of the room-temperature bending strength (550MPa) of a base material, and is 40-45% higher than that of a Ni-based brazing filler metal joint. Due to the main phase (Nb, Ti) in the soldered jointSSAnd (Nb, Ti, Zr)5Si3The melting temperature of the phase is up to more than 2000 ℃, so that the connecting joint has satisfactory high-temperature strength, the high-temperature bending strength of the joint reaches 152-168 MPa at 1200 ℃, 54-60% of the high-temperature bending strength (280MPa) of the base material is reached, and the performance of the connecting joint exceeds that of other conventional brazing materials;
5. the brazing material is green and environment-friendly, does not contain toxic elements, and does not contain noble metal elements such as Ag, Au, Pd, Pt and the like.
Drawings
FIG. 1 is a schematic view of a weld configuration of an embodiment of a butt joint;
fig. 2 is a schematic view of a welding structure of an embodiment of the plug connector.
In the figure: 1 is a first Nb-Si based ultra-high temperature structural material to be brazed, 2 is a second Nb-Si based ultra-high temperature structural material to be brazed, and 3 is brazing solder.
Detailed Description
The technical scheme of the invention is further detailed in the following by combining the drawings and the embodiment:
referring to fig. 1 for the butt-joint brazing position and fig. 2 for the splicing brazing position, the brazing material 3 is fixed at the fitting angle of the first and second Nb-Si based ultra-high temperature structural materials 1 and 2 to be welded or is arranged between the two materials, and close fitting is ensured.
Table 1 shows the components and weight percentage compositions of the Ti-Ni-Nb-Zr brazing material for the Nb-Si based ultra high temperature structural material according to the technical solution of the present invention, and lists examples of 16 Ti-Ni-Nb-Zr brazing materials.
TABLE 1 compositions and weight percentages of brazing materials in examples of the invention
The following 11 components (all atomic ratios) Nb-Si based ultra-high temperature structural materials are brazed and connected by adopting the brazing materials with the compositions of examples 1 to 16 shown in Table 1 and respectively used as blocks, strips, wires or alloy powder at the brazing temperature of 1250-1290 ℃ for the heat preservation time of 50-100 min:
(1)Nb-17Si-23Ti；
(2)Nb-18Si-24Ti-2Cr-2Al-2Hf；
(3)Nb-16Si-22Ti-3Cr-2Al-2Hf；
(4)NB-17Si-20Ti-8Zr-2Al-2Hf；
(5)Nb-18Si-20Ti-12Zr-3Mo-2Al；
(6)Nb-26Si-22Ti-6Cr-3Al-2Hf；
(7)Nb-16Si-22Ti-3Cr-3Al-2Hf；
(8)Nb-12Si-24Ti-4Cr-4Al-2Hf；
(9)Nb-20Si-24Ti-2Cr-2Al；
(10)Nb-16Si-10Ti-10Zr-3Cr-3Al-2Hf；
(11)Nb-16Si-20Ti-4V-3Cr-3Al-2Hf。
verification of connection effect of each embodiment: the joint structure obtained by interdiffusion of the brazing filler metal and the base metal is close to the base metal and mainly comprises (Nb, Ti) solid solution phase and Nb5Si3Phase composition, and Ti, Zr and Ni elements in the brazing filler metal are dissolved in (Nb, Ti)SSAnd (Nb, Ti, Zr)5Si3In the phase, the connecting joint does not have residual brazing filler metal with the melting temperature of 1194-1223 ℃ or brittle intermetallic compound phases such as Ni-Nb, Ni-Ti and the like. The room-temperature bending strength of the connection joint obtained by the brazing material reaches 330-363 MPa, reaches 60-66% of the room-temperature bending strength (550MPa) of a base material, and is 40-45% higher than that of a Ni-based brazing filler metal joint. Due to the main phase (Nb, Ti) in the soldered jointSSAnd (Nb, Ti, Zr)5Si3The melting temperature of the phase is up to more than 2000 ℃, so that the connecting joint has satisfactory high-temperature strength, the high-temperature bending strength of the joint reaches 152-168 MPa at 1200 ℃, 54-60% of the high-temperature bending strength (280MPa) of the base material is reached, and the performance of the connecting joint exceeds that of other conventional brazing materials.
It should be noted that, in the embodiments described in the present invention, the formula of the brazing material, the name of the process, the name and specific components of the material to be brazed, etc. may be different. All equivalent or simple changes of the structure, the characteristics and the principle based on the patent conception of the invention are included in the protection scope of the invention.
Claims (10)
1. A Ti-Ni-Nb-Zr brazing solder of an Nb-Si based ultrahigh temperature structure material is characterized in that: the brazing material comprises the following chemical components in percentage by weight: ni: 15.0-20.0, Nb: 12.0 to 18.0, Zr: 18.0 to 25.0, and the balance Ti.
2. The Ti-Ni-Nb-Zr brazing material according to claim 1, characterized in that: the brazing material comprises the following chemical components in percentage by weight: ni: 15.0 to 17.0, Nb: 12.0 to 18.0, Zr: 18.0 to 25.0, and the balance Ti.
3. The Ti-Ni-Nb-Zr brazing material according to claim 1, characterized in that: the brazing material comprises the following chemical components in percentage by weight: ni: 17.0 to 20.0, Nb: 12.0 to 18.0, Zr: 18.0 to 25.0, and the balance Ti.
4. The Ti-Ni-Nb-Zr brazing material according to claim 1, characterized in that: the brazing material comprises the following chemical components in percentage by weight: ni: 16.0, Nb: 12.0 to 18.0, Zr: 18.0 to 25.0, and the balance Ti.
5. The Ti-Ni-Nb-Zr brazing material according to claim 1, characterized in that: the brazing material comprises the following chemical components in percentage by weight: ni: 15.0-20.0, Nb: 14.0 to 18.0, Zr: 18.0 to 25.0, and the balance Ti.
6. The Ti-Ni-Nb-Zr brazing material according to claim 1, characterized in that: the brazing material comprises the following chemical components in percentage by weight: ni: 15.0-20.0, Nb: 12.0 to 18.0, Zr: 20.0, and the balance being Ti.
7. A brazing connection process of an Nb-Si based ultrahigh-temperature structural material is characterized by comprising the following steps: a Ti-Ni-Nb-Zr brazing material according to any one of claims 1 to 6 is used and comprises the steps of:
cleaning the surfaces of a first Nb-Si-based ultrahigh-temperature structural material (1) and a second Nb-Si-based ultrahigh-temperature structural material (2) to be brazed, and assembling, wherein the fit clearance of the first Nb-Si-based ultrahigh-temperature structural material and the second Nb-Si-based ultrahigh-temperature structural material is 0.02-0.09 mm;
fixing the brazing solder (3) at the matching angle of the first Nb-Si base ultra-high temperature structure material (1) and the second Nb-Si base ultra-high temperature structure material (2) to be welded or between the first Nb-Si base ultra-high temperature structure material and the second Nb-Si base ultra-high temperature structure material to be welded, and ensuring close fitting;
step three, uniformly coating an alumina flow inhibitor on the top and the bottom of a welding seam, and then placing a combination of the first Nb-Si-based ultrahigh-temperature structural material (1) and the second Nb-Si-based ultrahigh-temperature structural material (2) to be welded and the brazing solder (3) in a vacuum heating furnace for brazing;
step four, adjusting the vacuum degree in the furnace to be better than 8 × 10-3At Pa, the temperature starts to riseThe speed is not more than 15 ℃/min, the brazing connection temperature is 1250-1290 ℃, the heat preservation time is 50-100 min, and furnace cooling is carried out after the heat preservation is finished.
8. The process for braze joining of Nb-Si based ultra high temperature structural materials as claimed in claim 7, wherein: the brazing material (3) is in the form of a block, a strip, a wire or an alloy powder.
9. The process for braze joining of Nb-Si based ultra high temperature structural materials as claimed in claim 7, wherein: and assembling and combining the first Nb-Si based ultra-high temperature structural material (1) and the second Nb-Si based ultra-high temperature structural material (2) by adopting a butt joint or splicing method.
10. The process for braze joining of Nb-Si based ultra high temperature structural materials as claimed in claim 7, wherein: the braze joint temperature was 1270 ℃.
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| CN110605498A (en) * | 2019-05-14 | 2019-12-24 | 中国航发北京航空材料研究院 | TiNiNbZr high-temperature brazing filler metal for TiAl alloy, preparation method and brazing method thereof |
| CN110666395A (en) * | 2019-10-21 | 2020-01-10 | 中国航发北京航空材料研究院 | Brazing filler metal for brazing titanium-containing material, preparation method and brazing method |
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| JPS63317276A (en) * | 1987-06-18 | 1988-12-26 | Tanaka Kikinzoku Kogyo Kk | Gold alloy filler metal for brazing |
| JPH06228714A (en) * | 1993-02-05 | 1994-08-16 | Hitachi Metals Ltd | Low thermal expansion superalloy excellent in oxidation resistance |
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| JPH042354B2 (en) |
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