CN113798731B - Amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy, and preparation method and application thereof - Google Patents
Amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy, and preparation method and application thereof Download PDFInfo
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 119
- 229910002482 Cu–Ni Inorganic materials 0.000 title claims abstract description 114
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 110
- 239000000956 alloy Substances 0.000 title claims abstract description 110
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000005219 brazing Methods 0.000 claims abstract description 250
- 238000000034 method Methods 0.000 claims abstract description 67
- 239000010936 titanium Substances 0.000 claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 claims abstract description 62
- 239000002184 metal Substances 0.000 claims abstract description 62
- 238000002844 melting Methods 0.000 claims abstract description 56
- 230000008018 melting Effects 0.000 claims abstract description 54
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 239000011888 foil Substances 0.000 claims abstract description 18
- 238000003466 welding Methods 0.000 claims abstract description 14
- 230000007704 transition Effects 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000002074 melt spinning Methods 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 61
- 230000008569 process Effects 0.000 claims description 24
- 238000007711 solidification Methods 0.000 claims description 23
- 230000008023 solidification Effects 0.000 claims description 23
- 238000004321 preservation Methods 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000010953 base metal Substances 0.000 claims description 17
- 238000010587 phase diagram Methods 0.000 claims description 15
- 238000004364 calculation method Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000002474 experimental method Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229910000905 alloy phase Inorganic materials 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000013461 design Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910017985 Cu—Zr Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 229910002059 quaternary alloy Inorganic materials 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229910004696 Ti—Cu—Ni Inorganic materials 0.000 claims description 2
- 238000013213 extrapolation Methods 0.000 claims description 2
- 238000009718 spray deposition Methods 0.000 claims description 2
- 239000000945 filler Substances 0.000 abstract description 61
- 229910001092 metal group alloy Inorganic materials 0.000 abstract description 9
- 239000012071 phase Substances 0.000 description 103
- 230000000052 comparative effect Effects 0.000 description 31
- 239000000203 mixture Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 24
- 238000004458 analytical method Methods 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 11
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 229910052729 chemical element Inorganic materials 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 229910018575 Al—Ti Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000012856 weighed raw material Substances 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
- B23K35/32—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
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
- Ceramic Products (AREA)
Abstract
The invention discloses an amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy, a preparation method and application thereof. The weight percentages of the raw materials are as follows: the Zr content is 30-70%, the Cu content is 3-14%, the Ni content is 13-35%, and the balance is Ti. The melting point of the brazing filler metal is 761-821 ℃, the beta transition temperature of the brazing filler metal is 79-139 ℃ lower than that of the SP700 titanium alloy, and the phases contained in the brazing reaction layer formed by combining the Ti-Zr-Cu-Ni brazing filler metal alloy and the SP700 titanium alloy in the brazing reaction process are as follows: niTiZr phases with an aspect ratio of 3.1 and a mass fraction of 17-47%; a Cu (Ti, zr) 2 phase having an aspect ratio of 1.9 and a mass fraction of 35 to 59%; a Bcc phase with mass fraction not more than 35% and a NiZr 2 phase with mass fraction not more than 13%; does not contain brittle phases (Cu, ni) (Ti, zr) phases. Preparing the brazing filler metal into an amorphous brazing foil tape with the thickness of 0.01-0.1 mm by adopting an amorphous melt-spinning method, lapping with SP700 titanium alloy, brazing at 850-890 ℃ and preserving heat for 60min to obtain a brazing joint. The average weld thickness of the braze welding joint is 50-100 micrometers, and the highest room temperature shear strength is 450-576MPa, so that the braze welding joint meets the use requirements of SP700 titanium alloy braze welding.
Description
Technical Field
The invention relates to a Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy and a brazing method, belonging to the field of titanium alloy smelting.
Background
The brazing parent metal SP700 titanium alloy is an important alloy applied to the aerospace field, and in recent years, the SP700 titanium alloy has been paid attention to widely due to the superplasticity exhibited by the SP700 titanium alloy at 900 ℃. However, the titanium alloy is expensive in manufacturing cost and limits further popularization and application, so that the production of the composite material, the welding of the titanium alloy and other materials to form a composite structure are effective ways for fully playing the excellent performance and popularization and application of the composite material. The SP700 titanium alloy is an (alpha+beta) titanium alloy rich in beta phase by adding beta phase stabilizing elements Mo and Fe on the basis of the component of an aviation titanium alloy-Ti-6 Al-4V (TC 4) alloy. After addition of these two elements, the SP700 titanium alloy beta phase transition temperature was 900 ℃. The brazing temperature of the current titanium-based brazing filler metal is between 900 and 940 ℃, so that the alpha phase of the close-packed hexagonal structure of the matrix is converted into the beta phase of the body-centered cubic structure, and the shearing performance of the joint is reduced. Therefore, it is urgent to design a new brazing filler metal composition for the brazing characteristics of the SP700 titanium alloy.
The titanium alloy solder comprises two parts of solder matrix elements and additive elements. Different matrix elements can cause the change of brazing conditions such as brazing temperature, brazing heat preservation time and the like; and different additive elements can generate different intermetallic compounds at the soldered joint, which affects the shearing performance at the joint. In the current brazing temperature range of the brazing filler metal, only two brazing filler metals of Ag base and Ti-Zr base meet the requirements in the expected temperature range (800-900 ℃). The prior document 1 discloses "novel amorphous solder for brazing titanium and titanium alloy" to Ningxinglong et al, and uses Ag-based and Ti-Zr-based solder to braze SP700 titanium alloy. However, the Ag-based brazing filler metal has a large composition difference from the base metal, so that the ductility at the brazing interface is poor, the Ag-based brazing filler metal cannot be fully wetted with the base metal, and the strength of the brazing joint is far lower than that of the brazing base metal; the Ti and Zr elements are completely solid-dissolved in the brazing temperature range and are relatively close to the brazing parent metal components, so that the brazing joint with the shear strength reaching 280MPa can be obtained. For the above reasons, the brazing connection method with the highest application value at present is to choose to adopt Ti-Zr based brazing filler metal to carry out SP700 titanium alloy for brazing connection.
When the SP700 titanium alloy is brazed using a ti—zr-based brazing filler metal, among the choices of the added elements, the same elements as the base material elements, such as Al and V, attract considerable attention in view of rationality and joining efficiency. Prior document 2 discloses Ganjeh et Al that "Increasing Ti–6Al–4V brazedjoint strength equal to thebase metalby Ti and Zr amorphous filler alloys", uses Ti-42Al-24V brazing filler metal and Ti-6Al-4V titanium alloy to form a welded structure. However, from the brazing result, since an Al—Ti intermediate brittle phase such as Al 3Ti2 is formed at the interface between the two types of brazing, a fracture path is formed during the shearing process, and the shearing strength of the brazing joint can only reach 196MPa.
In order to avoid the formation of an Al-Ti intermediate brittle phase, a method of adding Cu and Ni elements can be adopted, so that the generation of the Al-Ti intermediate phase is effectively reduced; and the addition of Cu and Ni elements can also realize the technical effects of keeping the layered structure of a brazing reaction zone to be minimum at low temperature in the brazing process, delaying the growth of crystal grains and preventing coarse widmannstatten structures from being generated due to the growth of the crystal grains in the solidification process after the brazing is finished. In addition, in conventional document 3 (Infrared vacuum brazing of Ti-6Al-4V andNb using the Ti-15Cu-15Ni foil) Liaw et Al, an intermediate alloy phase formed between Cu, ni and Ti elements was hardly present in a brazing sample when brazing 3600s at 970 ℃ by brazing Ti-6Al-4V and Nb with a Ti-15Cu-15Ni brazing filler metal alloy by an infrared brazing method. However, according to the results of the shear test, the cracks all propagate along the Nb matrix and have typical ductile dent fracture appearance, and the Ti-6Al-4V side shear strength can only reach 230MPa.
As can be seen from the analysis of the prior art, the technical problems still existing at present are as follows:
1. The existing Ti-Zr-Cu-Ni solder has higher brazing temperature, can only meet the brazing connection of Ti-6Al-4V, and cannot be applied to SP700 titanium alloy with the beta transition temperature of 900 ℃. Specifically, the prior document 4 discloses a solder alloy for Chinese patent with a patent application number 201611094879.6: the melting point value of the Ti-Zr-Cu-Ni-Co-Fe solder is 858-899 ℃, the brazing temperature is 900-950 ℃, and the shearing strength of the brazing joint can be improved to 347MPa; the prior document 5 is Chinese patent with the patent application number 201911003215.8, and discloses a brazing alloy, wherein the melting point value is 850-880 ℃, and the brazing temperature for titanium alloy is 880-920 ℃. When the brazing filler metals are used for brazing SP700 titanium alloy at 900 ℃ or higher, phase transformation of brazing parent metal is caused, and when the brazing temperature is reduced to below 900 ℃, the brazing filler metals cannot be completely melted in the brazing process, massive brittle phases are formed in the solidification process, and the shearing strength of the brazing joint is reduced.
2. In the prior art, after Cu and Ni elements are introduced, phase transformation occurs at the braze joint to generate (Cu, ni) (Ti, zr) brittle phases. Specifically, prior document 6 discloses Infrared brazing Ti-6Al-4V and SP700 alloys using the Ti-20Zr-20Cu-20Ni braze alloy by Chang et Al, discloses a Ti-20Zr-20Cu-20Ni solder alloy, and performs a brazing experiment on the titanium alloy. When the (Cu, ni) (Ti, zr) phase occurs at the braze joint, a thin-walled structure is formed at the braze joint interface, which structure may crack due to insufficient braze temperature, resulting in a shear strength of only 391MPa.
In summary, aiming at the brazing process of the SP700 titanium alloy, the existing Ti-Zr-Cu-Ni system brazing filler metal needs to solve the following problems:
1. The brazing temperature of the melting point of the existing brazing filler metal is higher than the brazing requirement temperature of SP700 titanium alloy, the melting point of the brazing filler metal needs to be further reduced, and the optimal melting point of the brazing filler metal is lower than 800 ℃;
2. Brittle phases (Cu, ni) (Ti, zr) need to be avoided in the brazing process so as to avoid forming a thin-wall structure at the interface of a brazing joint and reduce the joint performance;
3. The brazing process includes the technological parameters of brazing temperature and brazing heat preservation time and the brazing filler metal components are not matched, so that the strength of the brazing joint cannot reach more than 400MPa, and the brazing joint with the brazing layer thickness below 100 microns cannot be obtained;
4. The cost is too high, which hinders the practical application of the product.
Therefore, according to the common requirements of the brazing melting point value and the brittle phase, a Ti-Zr-Cu-Ni solder alloy with the melting point value of 761-821 ℃ and the brazing temperature of 850-890 ℃ and avoiding the brittle phase (Cu, ni) (Ti, zr) and with the brazing joint strength of more than 400MPa and the brazing layer thickness of less than 100 microns is developed, and the Ti-Zr-Cu-Ni solder alloy has obvious application value and economic value and becomes a technical problem to be solved urgently.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art, and provides a Ti-Zr-Cu-Ni solder component and a brazing method. The brazing filler metal is suitable for brazing of SP700 titanium alloy, and has excellent properties of melting temperature lower than 800 ℃ and avoiding harmful phases (Cu, ni) (Ti, zr) during brazing.
In order to achieve the above object, the present invention adopts the following conception:
and obtaining the target Ti-Zr-Cu-Ni solder component by using a computer system and adopting a CALPHAD method and adopting a method of experimental test and phase diagram analysis. According to the common requirements of the brazing melting point value and the brittle phase, a brazing joint with the melting point value of 761-821 ℃ and the brazing temperature of 850-890 ℃ is developed, and the brittle phase (Cu, ni) (Ti, zr) is avoided, so that the strength of the brazing joint can reach more than 400 MPa.
According to the inventive concept, the invention adopts the following technical scheme:
The amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy comprises the following components in percentage by mass: 30-70% of Zr, 3-14% of Cu, 13-35% of Ni and the balance of Ti; the obtained amorphous Ti-Zr-Cu-Ni solder alloy is in a foil shape, and the thickness is 0.01-0.1 mm; in the brazing reaction process, the brazing reaction layer formed by combining the Ti-Zr-Cu-Ni brazing alloy and the SP700 titanium alloy contains NiTiZr phases, cu (Ti, zr) 2 phases, bcc phases and NiZr 2 phases, and does not contain brittle phases (Cu, ni) (Ti, zr) phases.
Preferably, the length-diameter ratio of NiTiZr phases in the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy is 3.1, and the mass fraction of NiTiZr phases is 17-47%; the aspect ratio of the Cu (Ti, zr) 2 phase is 1.9, and the mass fraction of the Cu (Ti, zr) 2 phase is 35-59%; the mass fraction of the Bcc phase is not more than 35%, and the mass fraction of the NiZr 2 phase is not more than 13%.
Preferably, the melting point of the amorphous Ti-Zr-Cu-Ni solder alloy is 761-821 ℃, the beta transition temperature is 79-139 ℃ lower than that of the SP700 titanium alloy, and the amorphous Ti-Zr-Cu-Ni solder alloy contacts with the base metal SP700 titanium alloy in a liquid phase to increase the brazing surface area; and (3) adopting an amorphous Ti-Zr-Cu-Ni solder alloy as a solder, and welding a base metal SP700 titanium alloy to obtain the solder joint with the strength not lower than 400MPa.
The invention relates to a preparation method of an amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy, which comprises the following steps:
The mass fraction of the Ti-Zr-Cu-Ni solder alloy is as follows: the Ti-Zr-Cu-Ni solder alloy comprises the following components in percentage by mass: 30-70% of Zr, 3-14% of Cu, 13-35% of Ni and the balance of Ti; weighing pure Ti, pure Zr, pure Cu and pure Ni as raw materials; wherein the addition amount of pure Cu is 105% of the mass fraction of Cu content; then, carrying out vacuum melting on the raw materials to obtain a Ti-Zr-Cu-Ni solder alloy ingot; and preparing the Ti-Zr-Cu-Ni solder alloy ingot into the Ti-Zr-Cu-Ni solder alloy foil tape.
Preferably, the mass fraction of the Ti-Zr-Cu-Ni alloy solder alloy is obtained by adopting the following method to design the Ti-Zr-Cu-Ni alloy solder:
Calculating a phase diagram of the Ti-Zr-Cu-Ni solder alloy by using a computer system and adopting a CALPHAD method, and determining the Zr content meeting the requirement of a melting point value through melting point contour map screening according to a Ti-Zr-Cu-Ni alloy phase diagram database; and calculating the phase types and phase fractions in the solidification process through a solidification path, and obtaining the component proportion of the Ti-Zr-Cu-Ni solder alloy which does not contain brittle phases (Cu, ni) (Ti, zr) in the object phase according to the calculation result.
Preferably, the solidification paths of the Ti-Zr-Cu-Ni alloy under different Zr element addition amounts are calculated through a Ti-Zr-Cu-Ni alloy phase diagram database, the types and the phase fractions of phases in the solidification process of different solders are counted, and whether brittle phases (Cu, ni) (Ti, zr) are contained in the object phase or not is judged according to the calculation result; if the precipitated phase contains brittle phases (Cu, ni) (Ti, zr), adjusting the content proportion of elements in the alloy component, and returning to the process and recalculating; if the precipitated phase does not contain brittle phases (Cu, ni) (Ti, zr), specific solder alloy components are recorded, and the preparation and the brazing experiments are performed for verification.
Preferably, the method for establishing the Ti-Zr-Cu-Ni alloy phase diagram database comprises the following steps: and obtaining a Ti-Cu-Zr, ti-Ni-Zr and Ti-Cu-Ni ternary phase diagram through experiments by adopting a CALPHAD method, obtaining a Ti-rich angular phase relation of a Ti-Zr-Cu-Ni quaternary system through extrapolation calculation of a ternary system, obtaining thermodynamic information of melting point, beta transition temperature and phase content of the Ti-Zr-Cu-Ni system solder, and obtaining a relation between component-melting point-phase composition-phase content.
Preferably, the method for determining the Zr content meeting the requirement of the melting point value through melting point contour map screening is a secondary screening method, and the method comprises the following steps:
Firstly, calculating Ti-Zr-Cu-Ni alloy liquid phase projection pictures under different Zr element addition amounts through a Ti-Zr-Cu-Ni alloy phase diagram database, and calculating corresponding melting point contour diagrams according to the projection pictures; then screening for the first time, wherein the specific method comprises the following steps:
Carrying out first screening according to the requirement that the melting point value is lower than 800 ℃ by using a gradient with the adding amount of Zr element of 10%; then carrying out secondary screening, and the specific method comprises the following steps:
and carrying out secondary screening according to the requirement that the melting point value is lower than 800 ℃ by using a gradient of 1% of Zr element.
Preferably, the method of vacuum melting is as follows:
and (3) adopting a vacuum arc melting furnace, vacuumizing to a vacuum degree not lower than 5 multiplied by 10 -3 Pa, filling argon, repeatedly melting for 3-5 times by adopting an arc heating mode to ensure that the alloy components are uniform, and cooling along with the furnace to obtain the Ti-Zr-Cu-Ni solder alloy ingot.
Preferably, the preparation method of the Ti-Zr-Cu-Ni solder alloy foil belt comprises the following steps:
Crushing a Ti-Zr-Cu-Ni solder alloy ingot, heating the Ti-Zr-Cu-Ni solder alloy by adopting an induction heating mode, and then adopting an amorphous melt-spinning method to carry out spray casting under the conditions that the copper wheel rotating speed is 2000-2500r/s and the spray pressure is 0.02-0.05MPa, so as to obtain the continuous Ti-Zr-Cu-Ni solder alloy foil belt.
The application of the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy adopts the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy as solder, and welds the base metal SP700 titanium alloy, comprising the following steps:
(1) Preparing and pre-treating brazing materials:
Placing the amorphous Ti-Zr-Cu-Ni solder alloy in acetone at the temperature of not lower than 50 ℃ for ultrasonic cleaning; simultaneously, grinding, polishing and ultrasonically cleaning the surface of the brazing parent metal in acetone;
(2) The brazing treatment process comprises the following steps:
Overlapping the amorphous Ti-Zr-Cu-Ni solder alloy with a brazing base metal by using a fixture, and attaching the amorphous Ti-Zr-Cu-Ni solder alloy to the surface of the brazing base metal; then, carrying out brazing under the conditions that the vacuum degree is not higher than 5 multiplied by 10 -3 Pa, the heating rate is 10-15 ℃/min, the brazing temperature is 850-890 ℃ and the brazing heat preservation time is not more than 60min, and cooling along with a furnace after the brazing is finished to obtain a brazing joint; the average weld thickness of the resulting braze joint is 50-100 microns and the shear strength is 450-576MPa.
Preferably, in the step (1), an amorphous Ti-Zr-Cu-Ni solder alloy foil tape for SP700 titanium alloy is used for cutting an amorphous Ti-Zr-Cu-Ni solder alloy sample with the thickness of 10 multiplied by 1mm, and the cut solder alloy sample is placed in acetone with the temperature of 50 ℃ for 20min; and cutting 2 samples with the length of 50 mm or 10 mm from the brazing parent metal, and carrying out surface grinding, polishing and ultrasonic cleaning in acetone.
Preferably, the amorphous Ti-Zr-Cu-Ni solder alloy has a melting point value of 761-821 ℃ which is 79-139 ℃ below the beta transition temperature of the SP700 titanium alloy. In the brazing reaction process, a brazing reaction layer formed by combining amorphous Ti-Zr-Cu-Ni brazing alloy and SP700 titanium alloy comprises the following phases: niTiZr, cu (Ti, zr) 2, bcc and NiZr 2 phase, avoiding (Cu, ni) (Ti, zr) harmful phase, which is superior to the prior art.
Compared with the prior art, the invention has the following obvious prominent substantive features and obvious advantages:
1. The amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy does not contain brittle phases (Cu, ni) (Ti, zr), the amorphous solder is prepared into an amorphous brazing foil strip with the thickness of 0.01-0.1 mm by adopting an amorphous melt-spinning method, and the amorphous brazing foil strip is brazed at the temperature of 850-890 ℃ and is insulated for 60min after being lapped with the SP700 titanium alloy to obtain a brazed joint; the average weld thickness of the braze welding joint is 50-100 micrometers, the highest room temperature shear strength is 450-576MPa, and the braze welding joint meets the use requirements of SP700 titanium alloy braze welding; the invention utilizes a computer system and adopts a CALPHAD method, thereby improving the efficiency of designing and developing the amorphous Ti-Zr-Cu-Ni solder alloy;
2. The brazing temperature of the melting point of the amorphous Ti-Zr-Cu-Ni brazing alloy for the SP700 titanium alloy is lower than the brazing requirement temperature of the SP700 titanium alloy, the phase transition of a brazing parent metal is not induced, a large brittle phase is not formed, the brazing joint can be ensured to have higher shearing strength, and the welding quality and the joint performance are ensured;
3. The brazing process comprises the steps of matching the brazing temperature and the brazing heat preservation time with the brazing filler metal components well, wherein the strength of a brazing joint reaches more than 400MPa, the brazing joint with the brazing layer thickness of less than 100 microns can be obtained, and the welding process level is improved;
4. the invention does not adopt noble metal raw materials, has low cost and is beneficial to actual popularization and application of solder products.
Drawings
FIG. 1 shows the calculation results of melting point and solidification path of the brazing filler metal according to example 1 of the present invention.
FIG. 2 shows the calculation results of melting point and solidification path of the brazing filler metal according to example 2 of the present invention.
FIG. 3 shows the calculation results of melting point and solidification path of the brazing filler metal according to example 3 of the present invention.
FIG. 4 shows the calculation results of melting point and solidification path of the brazing filler metal of comparative example 5 of the present invention.
Figure 5 is a SEM photograph of the shear fracture morphology of a braze joint of example 1 of the present invention.
FIG. 6 shows DSC test results of solder of examples 1-3 of the present invention.
FIG. 7 is a photomicrograph of the braze joint morphology of example 1 of the invention.
FIG. 8 is a graph of the shear strength versus the braze joint of examples 1-3, comparative example 5, and comparative example 6 of the present invention.
FIG. 9 is a plot of braze soak time versus diffusion layer thickness square root fit for example 1, comparative examples 1-4 of the present invention.
FIG. 10 is an SEM photograph of the phase composition of a brazing reaction layer according to example 1 of the present invention.
Detailed Description
The foregoing aspects are further described in conjunction with specific embodiments, and the following detailed description of preferred embodiments of the present invention is provided:
example 1:
the chemical element composition and mass percentage are that Zr content is 60%, cu content is 10%, ni content is 14%, the preparation method of the amorphous Ti-Zr-Cu-Ni solder alloy with the balance of Ti comprises the following steps:
Step 1, calculating a phase diagram of the Ti-Zr-Cu-Ni solder alloy by using a computer system and adopting a CALPHAD method, wherein the steps are as follows:
firstly, thermodynamic parameters of Ti-Zr-Cu-Ni system phases are measured through experiments to serve as calculation bases, and then corresponding thermodynamic models are established according to crystal structures of the phases;
Then, using a computer system, adopting a CALPHAD method, and establishing thermodynamic data of four ternary systems of Ti-Cu-Zr, ti-Ni-Zr, ti-Cu-Ni and Cu-Ni-Zr according to a thermodynamic principle and a phase equilibrium law and phase diagram calculation software; establishing a high-element system through a low-element system to obtain a Ti-Zr-Cu-Ni alloy phase diagram database of a quaternary system;
then according to a Ti-Zr-Cu-Ni alloy phase diagram database, determining that the Zr content meeting the requirement of a melting point value is 60% through melting point contour diagram screening; calculating the types and the phase fractions of phases in the solidification process through a solidification path, wherein the calculation result is shown in figure 1, and obtaining the element composition and the mass percentage of the Ti-Zr-Cu-Ni solder alloy which does not contain brittle phases (Cu, ni) (Ti, zr) in the object phase according to the calculation result, wherein the element composition and the mass percentage of the Ti-Zr-Cu-Ni solder alloy are 60 percent of Zr content, 10 percent of Cu content, 14 percent of Ni content and the balance of Ti;
Step 2, preparing Ti-Zr-Cu-Ni solder alloy:
Weighing pure Ti, pure Zr, pure Cu and pure Ni serving as raw materials according to the component proportion of the Ti-Zr-Cu-Ni solder alloy obtained in the step 1, wherein the addition amount of the pure Cu is 105% of the mass fraction of the Cu content; putting the weighed raw materials into a vacuum arc melting furnace, and filling argon when the vacuum degree in the furnace is below 5X 10 -3 Pa; repeatedly smelting for 5 times by adopting an electric arc heating mode to ensure that alloy components are uniform, cooling along with a furnace, and taking out a brazing alloy ingot; crushing the obtained brazing alloy ingot, and heating the Ti-Zr-Cu-Ni brazing alloy by adopting an induction heating mode;
and then after the alloy is completely melted and the liquid level fluctuates, adopting an amorphous melt-spinning method to spray the molten alloy onto a copper wheel rotating at a high speed by utilizing air pressure difference under the condition that the copper wheel rotating speed is 2500r/s and the spraying pressure is 0.05MPa, so as to obtain a continuous Ti-Zr-Cu-Ni solder alloy foil belt with the thickness of 0.1 millimeter.
The brazing method of the Ti-Zr-Cu-Ni brazing alloy prepared by adopting the embodiment is as follows:
Firstly, cutting an amorphous solder foil into a10 x 1 mm sample, and placing the cut sample in acetone at 50 ℃ for cleaning for 20min; simultaneously, cutting 2 samples with the length of 50 mm and the length of 10 mm from the brazing parent metal, and carrying out surface grinding, polishing and ultrasonic cleaning in acetone;
Overlapping the amorphous sample and the brazing parent metal by using a clamp, and attaching the brazing filler metal sample to the surface of the brazing parent metal; subsequently, heating the sample in a brazing reaction furnace to be molten at a vacuum degree of less than 5X 10 -3 Pa and a heating rate of 10 ℃/min; after the brazing filler metal is completely melted, brazing is carried out according to the brazing temperature of 890 ℃ and the brazing heat preservation time of 60min, and the brazing is carried out along with the furnace cooling condition after brazing, so that the brazed joint can be obtained.
Experimental test analysis:
To test the actual melting point value of the solder, the design solder was subjected to DSC test, and the test results are shown in fig. 6. Compared with the calculated result, the actual melting point of the brazing filler metal is 775 ℃, and the brazing filler metal can be completely melted by selecting the brazing experiment at 890 ℃. The shear performance of the obtained soldered joint was evaluated, and the average value of the room temperature shear strength of the soldered joint was 576MPa, and the fracture morphology was as shown in FIG. 5. In order to observe microstructure and phase composition of the braze joint, a scanning electron microscope is adopted to analyze the microstructure morphology of the braze joint obtained in the embodiment, and the main phase composition is as follows: niTiZr and Cu (Ti, zr) 2 phases, the inclusion phase is NiTiZr with an aspect ratio of 3.1 and 47% by mass, the aspect ratio is 1.9 and Cu (Ti, zr) 2 with an aspect ratio of 53% by mass, and the brazing reaction layer phase composition is shown in FIG. 10. Fine needle-like Wittig structures are generated in the solidification process of the brazing filler metal, the brazing layer thickness reaches 66 microns, and the joint morphology is shown in figure 7.
The Ti-Zr-Cu-Ni solder foil prepared by the embodiment has the advantages of bright surface, neat edge, good toughness and 775 ℃ of melting temperature of the solder. The brazing filler metal prepared by the embodiment is used for carrying out vacuum brazing connection on SP700 titanium alloy under the conditions of brazing temperature 890 ℃ and heat preservation for 60min, and the average value of room temperature shear strength of a brazing joint is 576MPa.
In the brazing process, the change of the brazing heat preservation time can influence the diffusion degree of elements, and the change of the diffusion rate is mainly reflected. And the diffusion rate of the element cannot be directly measured, so that the analysis is performed by adopting a method for representing the thickness of the diffusion layer. The relation between the thickness of the diffusion layer and the brazing heat preservation time is calculated by adopting a dynamic model, and the selected model is a solid phase reaction dynamic model. According to the model, under the interface solid-liquid phase reaction condition of diffusion control, the square of the thickness (x) of the reaction layer is in direct proportion to the brazing heat preservation time (t) within 30-180 min. Thus, comparative examples 1,2, 3,4 are provided below for comparative experiments of the effect of different holding times on the thickness of the braze layer to seek corresponding braze reaction layer thicknesses at different holding times:
Comparative example 1
The procedure not specifically described for the Ti-Zr-Cu-Ni amorphous filler metal alloy used in the SP700 titanium alloy was the same as in example 1, except that:
The brazing heat preservation time was 30min, and the brazing alloy composition was the same as in example 1.
Experimental test analysis
In order to obtain the brazing layer thickness of comparative example 1, the braze joint obtained in this example was analyzed by scanning electron microscopy, and its phase composition was mainly the (Ti, zr) phase that was not completely melted in the braze, and the interface position of the braze and the base material was not completely reacted, and no intermediate structure was formed during solidification. The braze layer thickness of comparative example 1 was 167 microns. The average value of the room temperature shear strength of the soldered joint is 261MPa.
Comparative example 2
The procedure not specifically described for the Ti-Zr-Cu-Ni amorphous filler metal alloy used in the SP700 titanium alloy was the same as in example 1, except that:
The brazing heat preservation time was 120min, and the brazing alloy composition was the same as in example 1.
Experimental test analysis
In order to obtain the brazing layer thickness of comparative example 2, the braze joint obtained in this example was analyzed by scanning electron microscopy, and its phase composition was mainly NiTiZr and Cu (Ti, zr) 2 phases, and its solidification structure was needle-like widmannstatten structure. The braze layer of comparative example 2 had a thickness of 357 microns. The average value of room temperature shear strength of the soldered joint is 191MPa.
Comparative example 3
The procedure not specifically described for the Ti-Zr-Cu-Ni amorphous filler metal alloy used in the SP700 titanium alloy was the same as in example 1, except that:
The brazing holding time was 150min, and the brazing alloy composition was the same as in example 1.
Experimental test analysis
In order to obtain the brazing layer thickness of comparative example 3, the braze joint obtained in this example was analyzed by scanning electron microscopy, and its phase composition was mainly Cu (Ti, zr) 2 phase, and its solidification structure was Wittig structure. The braze layer thickness of comparative example 3 was 667 microns. The average value of the room temperature shear strength of the soldered joint is 147MPa.
Comparative example 4
The procedure not specifically described for the Ti-Zr-Cu-Ni amorphous filler metal alloy used in the SP700 titanium alloy was the same as in example 1, except that:
the brazing heat preservation time is 180min, and the brazing alloy has the same components as in the example 1.
Experimental test analysis
In order to obtain the brazing layer thickness of comparative example 4, the brazing joint obtained in this example was analyzed by a scanning electron microscope, and its phase composition was mainly Cu (Ti, zr) 2 phase, and its solidification structure was coarse basket structure. The braze layer thickness of comparative example 4 was 714 microns. The average value of room temperature shear strength of the soldered joint is 144MPa.
According to a solid phase reaction dynamics model, combined with the Fick first law and experimental results, under the interface solid-liquid phase reaction condition of diffusion control, the thickness x of the reaction layer and the 1/2 th power of the brazing heat preservation time t can be fitted, a fitting schematic diagram is shown in fig. 9, and the fitting result is:
x＝120t1/2-884.7
Compared to example 1, the braze layer thickness of comparative example 1 increased to 167 microns, but the shear strength of the braze joint decreased to 261MPa; the method is mainly characterized in that the heat preservation time of the comparative example 1 is short, the element diffusion of the brazing reaction layer is incomplete, obvious layering phenomenon occurs at the brazing joint, and the brazing filler metal is not completely combined with the base metal; and as the brazing heat preservation time is prolonged to 180min from 60min, the thickness of the brazing reaction layers of the comparative examples 2,3 and 4 shows a trend of gradually rising, the phase of the brazing reaction layers is gradually changed into Cu (Ti, zr) 2 phase, the brazing reaction layers are changed into coarse basket structures from fine needle-shaped Wittig structures, and the shearing strength of the brazing joint is gradually reduced to 144MPa.
The preferred brazing reaction layer thickness range is thus set as: the thickness of the brazing filler metal is less than 1/2 that of the brazing reaction layer, namely, the thickness of the brazing reaction layer is less than 50 micrometers and less than 100 micrometers. In this region, the brazing filler metal element can be sufficiently diffused into the brazing base material, and the formation of intermediate phases in the brazing reaction layer can be reduced, thereby reducing the adverse effect on the structure of the braze joint.
The following conclusions can be drawn from example 1, comparative example 2, comparative example 3 and comparative example 4:
under the interface solid-liquid phase reaction condition of diffusion control:
1. The brazing interface reaction is incomplete due to the reduction of the brazing heat preservation time, and an intermediate structure cannot be generated between the brazing filler metal and the base metal;
2. The brazing heat preservation time is prolonged, the thickness of the brazing layer can be effectively increased, and the element diffusion degree of the brazing filler metal is increased;
3. the brazing heat preservation time is prolonged, the Cu (Ti, zr) 2 phase content is increased, and the structure morphology of the brazing joint is changed.
In order to demonstrate the effect of the different element contents of the Ti-Zr-Cu-Ni solder alloys, cases of example 2, example 3, comparative example 5 and comparative example 6 were provided.
Example 2:
This embodiment is substantially the same as embodiment 1, except that:
the procedure not specifically described for the Ti-Zr-Cu-Ni amorphous solder alloy for SP700 titanium alloy was the same as in example 1, except that the chemical element composition and mass percent were as follows:
The Zr content is 70%, the Cu content is 3%, the Ni content is 16%, and the balance is Ti. The brazing temperature is set to 850 ℃, and the mass percentages of phases contained in the brazing material are as follows: the NiTiZr phase content was 41% and the Cu (Ti, zr) 2 phase content was 59%, the calculated results are shown in FIG. 2.
Experimental test analysis:
To test the actual melting point value of the solder, the design solder was subjected to DSC test, and the test results are shown in fig. 6. Compared with the calculated result, the actual melting point of the brazing filler metal is 761 ℃, so that the brazing filler metal can be completely melted by selecting a brazing experiment at 850 ℃. The main phase composition of the material is as follows: niTiZr and Cu (Ti, zr) 2 phases, and fine needle-like widmannstatten structures are generated in the solidification process of the brazing filler metal. The shear properties of the resulting braze joints were evaluated and the average room temperature shear strength of the braze joints was 488MPa.
Example 3:
This embodiment is substantially the same as the above embodiment, and is characterized in that:
the procedure not specifically described for the Ti-Zr-Cu-Ni amorphous solder alloy for SP700 titanium alloy was the same as in example 1, except that the chemical element composition and mass percent were as follows:
The Zr content is 30%, the Cu content is 4%, the Ni content is 35%, and the balance is Ti. The mass percentages of the phases are as follows: the Bcc phase content was 35%, the NiZr 2 phase content was 13%, the NiTiZr phase content was 17%, and the Cu (Ti, zr) 2 phase content was 35%, the calculation results are shown in fig. 3.
Experimental test analysis:
To test the actual melting point value of the solder, the design solder was subjected to DSC test, and the test results are shown in fig. 6. Compared with the calculated result, the actual melting point of the brazing filler metal is 821 ℃, and the brazing filler metal can be completely melted by selecting the brazing experiment at 890 ℃. The microstructure morphology of the braze joint obtained in this example was analyzed by scanning electron microscopy, and the main phase composition was: the Bcc phase, niTiZr and Cu (Ti, zr) 2 phase, and needle-shaped Wittig structures are generated in the solidification process of the brazing filler metal. The shear properties of the resulting braze joints were evaluated and the average room temperature shear strength of the braze joints was 450MPa.
Comparative example 5:
The procedure not specifically described for the Ti-Zr-Cu-Ni amorphous filler metal alloy used in the SP700 titanium alloy was the same as in example 1, except that: the chemical element composition and mass percentage thereof were 40% of Zr content, 4% of Cu content, 29% of Ni content, and the balance of Ti, and the calculation results are shown in fig. 4.
Experimental test analysis
In order to test the actual melting point value of the solder, the design solder was subjected to DSC test, and the actual melting point of the solder was 958 ℃ compared with the calculated result, so that the solder could not be completely melted by the choice of the soldering experiment at 890 ℃. The phase mainly comprises (Ti, zr) phases which are not completely melted in the brazing filler metal, the brazing filler metal and the base metal do not have interface reaction, and an intermediate structure is not formed in the solidification process. The shear properties of the resulting soldered joints were evaluated, and the average of the room temperature shear strengths of the soldered joints was 163MPa.
Comparative example 6:
The procedure not specifically described for the Ti-Zr-Cu-Ni amorphous filler metal alloy for SP700 titanium alloy was the same as in comparative example 5, except that: since the brazing test was chosen to be performed at 890 c and the brazing filler metal was not completely melted, the brazing test was chosen to be performed at 970 c. The main phase composition of the material is as follows: (Cu, ni) (Ti, zr) phase, and Wittig structure is generated during solidification of the solder. The shear properties of the resulting braze joints were evaluated and the average room temperature shear strength of the braze joints was 342MPa.
Comparative analysis of the data obtained for examples 1-3, comparative example 5, comparative example 6, as shown in FIG. 8, the following conclusions can be drawn:
(1) The thickness of the brazing joint reaction layer shows a change trend of firstly decreasing and then rising along with the increase of the brazing heat preservation time, wherein the thickness of the brazing reaction layer reaches a minimum value of 66 microns when the heat preservation is carried out for 60 min; the structure at the soldered joint shows a change trend of firstly refining and then coarsening, wherein the structure at the joint is a fine needle-shaped Wittig structure when the heat is preserved for 60 min.
(2) With the increase of Zr element in the solder, the melting point of the solder shows a gradually reduced change trend, wherein when the Zr content reaches 60% -70%, the melting point of the solder can reach below 800 ℃, and when the Zr content reaches 30% -50%, the melting point of the solder can reach below 850 ℃.
(3) When the chemical element composition and the mass percentage of the brazing filler metal are that the Zr content is 60%, the Cu content is 10%, the Ni content is 14%, and the balance is Ti, the actual melting point of the brazing filler metal is 775 ℃, and after the brazing experiment is carried out at 890 ℃ and the brazing filler metal is kept for 60min, the main phase composition of the brazing joint part is as follows: niTiZr and Cu (Ti, zr) 2 phases, and the average room temperature shear strength of the soldered joint can reach 576MPa.
In summary, the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy of the embodiment and the preparation method and the application thereof are provided. The weight percentage of each raw material is 30-60% of Zr, 3-14% of Cu, 14-35% of Ni and the balance of Ti. The melting point value of the brazing filler metal is 761-821 ℃, the beta transition temperature of the brazing filler metal is 79-139 ℃ lower than that of the SP700 titanium alloy, and a brazing reaction layer formed by combining the Ti-Zr-Cu-Ni brazing filler metal alloy and the SP700 titanium alloy in the brazing reaction process comprises NiTiZr phases with the length-diameter ratio of 3.1 and the mass fraction of 17-47%; a Cu (Ti, zr) 2 phase having an aspect ratio of 1.9 and a mass fraction of 35 to 59%; a Bcc phase of not more than 35% by mass and a NiZr 2 phase of not more than 13% by mass; does not contain brittle phases (Cu, ni) (Ti, zr) phases. The brazing filler metal is prepared into an amorphous brazing foil tape with the thickness of 0.01-0.1 mm by adopting an amorphous melt-spinning method, and the amorphous brazing foil tape is lapped with SP700 titanium alloy, then brazed at 850-890 ℃ and kept for 60min to obtain a brazed joint. The average welding seam thickness of the braze welding joint of the embodiment of the invention is 50-100 micrometers, and the highest room temperature shear strength is 450-576MPa, thereby meeting the use requirements of SP700 titanium alloy braze welding.
The embodiment of the present invention has been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes, modifications, substitutions, combinations or simplifications made under the spirit and principles of the technical scheme of the present invention should be equivalent substitution, so long as the technical principles and the inventive concept of the Ti-Zr-Cu-Ni solder and the brazing method for the SP700 titanium alloy of the present invention are not deviated, and the present invention is within the scope of protection.
Claims (7)
1. A braze joint of an amorphous Ti-Zr-Cu-Ni solder alloy for an SP700 titanium alloy is characterized in that the mass fraction of the Ti-Zr-Cu-Ni solder alloy is as follows: zr content is 60%, cu content is 10%, ni content is 14%, and the rest is Ti; the amorphous Ti-Zr-Cu-Ni solder alloy is in a foil shape, and the thickness is 0.1 millimeter; the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy is used as solder, and the base metal SP700 titanium alloy is welded to obtain a soldered joint, and the preparation method of the soldered joint comprises the following steps:
(1) Preparing and pre-treating brazing materials:
Placing the amorphous Ti-Zr-Cu-Ni solder alloy in acetone at 50 ℃ for ultrasonic cleaning for 20min; simultaneously, grinding, polishing and ultrasonically cleaning the surface of the brazing parent metal in acetone;
(2) The brazing treatment process comprises the following steps:
Overlapping the amorphous Ti-Zr-Cu-Ni solder alloy with a brazing base metal by using a fixture, and attaching the amorphous Ti-Zr-Cu-Ni solder alloy to the surface of the brazing base metal; then, adopting the conditions that the vacuum degree is lower than 5 multiplied by 10 -3 Pa, the heating rate is 10 ℃/min, the brazing temperature is 890 ℃, the brazing heat preservation time is 60min for brazing, and cooling along with a furnace after the brazing is finished to obtain a brazing joint; the thickness of the brazing layer is 66 microns, and the shearing strength is 576MPa; in the brazing treatment process, the brazing reaction layer formed by combining the Ti-Zr-Cu-Ni brazing alloy and the SP700 titanium alloy contains NiTiZr phases and Cu (Ti, zr) 2 phases, and does not contain brittle phases (Cu, ni) (Ti, zr) phases.
2. The braze joint of amorphous Ti-Zr-Cu-Ni braze alloy for SP700 titanium alloy according to claim 1 wherein: wherein the length-diameter ratio of the NiTiZr phases is 3.1, and the mass fraction of the NiTiZr phase is 47%; the aspect ratio of the Cu (Ti, zr) 2 phase was 1.9, and the mass fraction of the Cu (Ti, zr) 2 phase was 53%.
3. A method for producing an amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy in a soldered joint according to claim 1, comprising the steps of:
The mass fraction of the Ti-Zr-Cu-Ni solder alloy is as follows: zr content is 60%, cu content is 10%, ni content is 14%, and the rest is Ti; weighing pure Ti, pure Zr, pure Cu and pure Ni as raw materials; wherein the addition amount of pure Cu is 105% of the mass fraction of Cu content; then, carrying out vacuum melting on the raw materials to obtain a Ti-Zr-Cu-Ni solder alloy ingot; preparing a Ti-Zr-Cu-Ni solder alloy foil tape from the Ti-Zr-Cu-Ni solder alloy ingot;
The mass fraction of the Ti-Zr-Cu-Ni alloy solder alloy is obtained by adopting the following method to design the Ti-Zr-Cu-Ni alloy solder:
Calculating a phase diagram of the Ti-Zr-Cu-Ni solder alloy by using a computer system and adopting a CALPHAD method, and determining the Zr content meeting the requirement of a melting point value through melting point contour map screening according to a Ti-Zr-Cu-Ni alloy phase diagram database; and calculating the phase types and phase fractions in the solidification process through a solidification path, and obtaining the component proportion of the Ti-Zr-Cu-Ni solder alloy which does not contain brittle phases (Cu, ni) (Ti, zr) in the object phase according to the calculation result.
4. The method for producing an amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy in a soldered joint according to claim 3, wherein: the method for establishing the Ti-Zr-Cu-Ni alloy phase diagram database comprises the following steps: and obtaining a Ti-Cu-Zr, ti-Ni-Zr and Ti-Cu-Ni ternary phase diagram through experiments by adopting a CALPHAD method, obtaining a Ti-rich angular phase relation of a Ti-Zr-Cu-Ni quaternary system through extrapolation calculation of a ternary system, obtaining thermodynamic information of melting point, beta transition temperature and phase content of the Ti-Zr-Cu-Ni system solder, and obtaining a relation between component-melting point-phase composition-phase content.
5. A method for producing an amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy in a soldered joint according to claim 3, characterized by the method of vacuum melting:
And (3) adopting a vacuum arc melting furnace, vacuumizing to reach a vacuum degree lower than a value of 5 multiplied by 10 -3 Pa, filling argon, repeatedly melting for 5 times by adopting an arc heating mode to ensure that the alloy components are uniform, and cooling along with the furnace to obtain the Ti-Zr-Cu-Ni solder alloy ingot.
6. The method for producing an amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy in a soldered joint according to claim 3, wherein the method for producing a foil strip of Ti-Zr-Cu-Ni solder alloy is:
Crushing a Ti-Zr-Cu-Ni solder alloy ingot, heating the Ti-Zr-Cu-Ni solder alloy by adopting an induction heating mode, and then carrying out spray casting under the conditions that the copper wheel rotating speed is 2500 r/s and the spray pressure is 0.05 MPa by adopting an amorphous melt-spinning method to obtain a continuous Ti-Zr-Cu-Ni solder alloy foil belt.
7. The application of the amorphous Ti-Zr-Cu-Ni solder alloy for the SP700 titanium alloy is characterized in that: adopting amorphous Ti-Zr-Cu-Ni solder alloy for SP700 titanium alloy as solder, and welding base metal SP700 titanium alloy to obtain the braze joint of claim 1, comprising the following steps:
(1) Preparing and pre-treating brazing materials:
Placing the amorphous Ti-Zr-Cu-Ni solder alloy in acetone at 50 ℃ for ultrasonic cleaning for 20min; simultaneously, grinding, polishing and ultrasonically cleaning the surface of the brazing parent metal in acetone;
(2) The brazing treatment process comprises the following steps:
Overlapping the amorphous Ti-Zr-Cu-Ni solder alloy with a brazing base metal by using a fixture, and attaching the amorphous Ti-Zr-Cu-Ni solder alloy to the surface of the brazing base metal; then, adopting the conditions that the vacuum degree is lower than 5 multiplied by 10 -3 Pa, the heating rate is 10 ℃/min, the brazing temperature is 890 ℃, and the brazing heat preservation time is 60min to braze, and cooling along with a furnace after the brazing is finished to obtain a brazing joint; the braze layer had a thickness of 66 microns and a shear strength of 576MPa.
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