CN110666396A - Strip-shaped brazing material for titanium alloy medium-low temperature brazing, preparation method and brazing method - Google Patents
Strip-shaped brazing material for titanium alloy medium-low temperature brazing, preparation method and brazing method Download PDFInfo
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- 238000005219 brazing Methods 0.000 title claims abstract description 204
- 239000000463 material Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 49
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 106
- 229910052751 metal Inorganic materials 0.000 claims abstract description 106
- 239000002184 metal Substances 0.000 claims abstract description 105
- 239000010936 titanium Substances 0.000 claims abstract description 86
- 239000011888 foil Substances 0.000 claims abstract description 40
- 229910000679 solder Inorganic materials 0.000 claims abstract description 40
- 230000008018 melting Effects 0.000 claims abstract description 27
- 238000002844 melting Methods 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 55
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 53
- 238000003466 welding Methods 0.000 claims description 26
- 238000003723 Smelting Methods 0.000 claims description 24
- 229910004349 Ti-Al Inorganic materials 0.000 claims description 24
- 229910004692 Ti—Al Inorganic materials 0.000 claims description 24
- 238000004321 preservation Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 230000006698 induction Effects 0.000 claims description 12
- 229910000765 intermetallic Inorganic materials 0.000 claims description 10
- 238000010791 quenching Methods 0.000 claims description 10
- 230000000171 quenching effect Effects 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 229910010038 TiAl Inorganic materials 0.000 claims description 8
- 229910021330 Ti3Al Inorganic materials 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- 238000002074 melt spinning Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 14
- 229910052759 nickel Inorganic materials 0.000 abstract description 13
- 238000009792 diffusion process Methods 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 229910002482 Cu–Ni Inorganic materials 0.000 abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 39
- 239000010949 copper Substances 0.000 description 35
- 239000000956 alloy Substances 0.000 description 28
- 229910045601 alloy Inorganic materials 0.000 description 25
- 230000008569 process Effects 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 229910004356 Ti Raw Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910004353 Ti-Cu Inorganic materials 0.000 description 2
- 229910004696 Ti—Cu—Ni Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 238000007712 rapid solidification Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910017945 Cu—Ti Inorganic materials 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010381 TiNi3 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000000451 tissue damage Effects 0.000 description 1
- 231100000827 tissue damage Toxicity 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
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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
- 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
- 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)
- Ceramic Products (AREA)
Abstract
The invention provides a strip brazing material for titanium alloy medium-low temperature brazing, a preparation method and a brazing method. Wherein the brazing filler metal includes: ti element, Zr element, Cu element and Ni element. Wherein the weight percentages of the element components are as follows: ti is between 51.0 and 60.0 percent; zr is more than or equal to 15.0 percent and less than or equal to 19.0 percent; cu is more than or equal to 12.0 percent and less than or equal to 14.0 percent; ni is more than or equal to 13.0 percent and less than or equal to 16.0 percent; cu and Ni are more than or equal to 25.0 percent and less than or equal to 30.0 percent. According to the embodiment of the invention, the Ti-Zr-Cu-Ni solder is improved, the Zr element content is optimized, the total content of Cu and Ni elements is controlled, the melting point is reduced to 830-880 ℃, the diffusion capacity of the solder is improved, fewer interface compounds are used, and Ti is realized2The tensile strength level of the AlNb-TC4 heterogeneous soldered joint reaches 905MPa, the tensile strength level of the TA2 soldered joint reaches 463MPa, and the method is beneficial to forming a solder foil strip, reducing the solder cost and expanding the solder foil stripAnd applicability of the large brazing filler metal.
Description
Technical Field
The invention relates to a brazing technology, in particular to a strip brazing material for titanium alloy medium-low temperature brazing, a preparation method and a brazing method.
Background
The titanium material thin-wall component has the characteristic of light weight, for example, titanium alloy radiators and honeycomb sandwich structures manufactured by adopting a brazing technology are applied to the field of aerospace, and the structures require brazing filler metal to have better diffusion capacity so as to avoid forming intermetallic compounds at the welding interface of the thin-wall structure. Compared with the phase transition point (960 ℃ -980 ℃) of common titanium alloy materials TC4 and TC1, when the pure titanium materials are adopted, for example, the phase transition point of industrial pure titanium (TA1 and TA2) is 882 ℃ -885 ℃, the phase transition point of SP700(Ti-4.5Al-3.0V-2.0Mo-2.0Fe, weight percentage) titanium alloy suitable for manufacturing wide-width plates is about 885 ℃ -890 ℃, and the thin-wall structure of the titanium materials not only requires that the brazing filler metal has excellent diffusion capability, but also requires that the melting point of the brazing filler metal is further reduced, so as to avoid the tissue damage and performance reduction of the base materials caused by the brazing process.
Ti-Al alloy (including Ti)3Al，Ti2AlNb and TiAl alloy) has the advantages of light weight and temperature resistance, and is expected to replace part of nickel-based high-temperature alloy to be used for manufacturing parts of an aircraft engine compressor. The long-range ordered crystal structure of Ti-Al alloy results in poor room temperature plasticity of the base material compared with that of Ti alloy, and the soldered joint of the Ti-Al alloy is easy to form compound and brittle fracture.
Solder is an important material for the brazing process. According to the melting point of the brazing filler metal, titanium materials and Ti-Al alloy commonly used brazing filler metals can be divided into the following types, one type is low-temperature brazing filler metal, the using temperature range is 650-800 ℃, such as silver-based brazing filler metal (Ag-Cu or Ag-Cu-Ti brazing filler metal) and partial zirconium-based brazing filler metal (Zr-Ti-Ni-Cu, the Zr content is 50-70% by weight percent), but because the difference between the constituent elements of the brazing filler metal and the matrix elements is large, the interface structure is complicated, and the corrosion resistance of joints can be reduced due to the brazing filler metal containing a large amount of Ag element (the content is more than 30%).
The second is medium temperature brazing filler metal, the using temperature range is 870-930 ℃, such as Ti-37.5Zr-15Cu-15Ni (weight percentage) brazing filler metal which is common in titanium-based brazing filler metal, the using temperature is reported to be 875 ℃ and 930 ℃, and the like, and the brazing filler metal can be used for brazing titanium materials and Ti-Al series alloys, but intermetallic compounds such as TiNi3 are easily formed on the corresponding brazing interface.
The third is Ti-Zr-Cu-Ni-X (X ═ Fe, Be, Co, Fe, Al, Si, etc.) high temperature solder, the melting point is 940-1000 deg.C, also includes Ti-15Cu-15Ni (weight percentage) solder, the liquidus temperature range is about 900 deg.C, the using temperature range is 950-1000 deg.C, and is higher than phase change point of most titanium alloy, so that Ti-Zr-Cu-Ni-X high temperature solder and Ti-15Cu-15Ni solder are not suitable for soldering titanium alloy, also are pure titanium material.
The following table 1 shows the composition characteristics, melting point or use temperature of the publicly published Ti-Zr-Cu-Ni-X titanium-based high temperature solder. In order to achieve sufficient melting of the solder and some diffusion with the substrate, the solder is typically used at a temperature at least 10 ℃ above its melting point.
TABLE 1 ingredient, melting point or use temperature table of Ti-Zr-Cu-Ni-X Ti-based high-temperature solder of five or more elements
The applicant finds out through research that: the problems of the existing Ti-Zr-Cu-Ni-X (X ═ Fe, Be, Co, Fe, Al, Si and the like) brazing filler metal and Ti-Cu-Ni brazing filler metal are as follows:
1) when the brazing object contains a pure titanium material, the melting point of the brazing filler metal is to be further lowered. The melting point of the brazing filler metal needs to be lower than the phase transformation point (882 ℃) of pure titanium, and a certain temperature margin exists.
2) When the structure to be welded is a thin-walled structure, the diffusion capability of the brazing filler metal needs to be improved. The increase of the total of Cu and Ni elements in the brazing filler metal can lead the brazing filler metal not to be easily diffused into a matrix in the brazing process, thereby causing the corrosion and reducing the joint strength, which is particularly obvious for the brazing of thin-wall structures.
3) When the material to be welded contains a Ti — Al alloy, the problem of the complex interface structure is urgently needed to be solved. The variety of the brazing filler metal elements reaches more than 5, and most of the added elements are large in atomic radius, so that the brazing filler metal alloy is not easy to diffuse, and is enriched at a joint to form a plurality of compound phases, which is not beneficial to improving the performance of the joint. For example, trace elements such as Fe, Be, Co, Fe, Al and Si are added into the commonly used Ti-Zr-Cu-Ni solder and Ti-Cu-Ni solder so as to improve the wettability of the solder or adjust the melting point of the solder.
4) The preparation of the foil brazing filler metal.
Foil-strip solder is generally used to make it easier to control the amount of solder and to ensure assembly efficiency or production efficiency. For example, when the content of a certain element is large, the molten brazing filler metal is easy to stick on a copper roller when passing through a cooling copper roller (a cooling copper roller: a device for cooling metal melt used in the rapid solidification method), that is, a foil strip cannot be formed, or a foil strip with poor appearance quality, such as a foil strip with many holes or depressions on the surface, is obtained by cooling the copper roller and spinning. Thus, a brazing filler metal of such composition cannot be prepared into a foil strip by a rapid solidification method.
At present, the varieties of medium and low temperature brazing filler metals capable of brazing titanium materials containing pure titanium and/or Ti-Al alloy materials and/or combinations of the titanium materials and the Ti-Al alloy materials are few. The medium-temperature brazing filler metal with low melting point, low cost and good forming performance has good development and application prospects.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a titanium-based medium-low temperature brazing material, a preparation method and a brazing method, aiming at considering the melting point and the diffusion capacity of the brazing material, determining whether the brazing material can be prepared into a foil strip with uniform thickness and good appearance, controlling intermetallic compounds of a brazing interface and expanding the application range of the brazing material.
In a first aspect, the invention provides a strip-shaped brazing material for low-temperature brazing of titanium alloy, and the brazing material is also suitable for a titanium material combination containing pure titanium, a Ti-Al compound combination and a titanium material and Ti-Al alloy combination (pure titanium and pure titanium, pure titanium and titanium alloy, titanium alloy and titanium alloy, TiAl and Ti3Al alloy, TiAl-Ti2AlNb alloy and Ti3Al and Ti2AlNb alloy), the braze comprising: ti element, Zr element,Cu element and Ni element, wherein the weight percentage of each element component is as follows:
51.0％≤Ti≤60.0％；
15.0％≤Zr≤19.0％；
25.0％≤Cu+Ni≤30.0％；
12％≤Cu≤14％；
13％≤Ni≤16％。
in a second aspect, the present invention provides a method for preparing a brazing filler metal, the brazing filler metal being the brazing filler metal of the first aspect, the method comprising the steps of:
material preparation: providing raw material particles of Zr element, Cu element, Ni element and Ti element according to the weight percentage of the above element components;
smelting: smelting the raw material particles by using a vacuum induction furnace, and casting into an ingot;
preparing a foil brazing filler metal: and melting the cast ingot by using a vacuum induction furnace on a vacuum rapid quenching melt spinning machine, and preparing the foil brazing filler metal.
In a third aspect, the present invention provides a method of brazing with a brazing filler metal, the method comprising the steps of:
cleaning: cleaning the surface to be brazed of a sample or part to be brazed;
positioning foil strip brazing filler metal: cutting the foil brazing filler metal according to the requirement, paving a single layer of brazing filler metal on the surface to be brazed of a sample or part to be brazed, and positioning the foil brazing filler metal on the surface to be brazed by a spot welding method;
assembling: the surface to be brazed of the other sample or part to be brazed is attached to the surface to be brazed of the sample or part to be brazed, on which the foil brazing filler metal is spread, through a clamp;
sample or part brazing step: placing the two assembled samples or parts to be welded into a vacuum brazing furnace for brazing;
and (3) cooling: and cooling to room temperature along with the furnace after brazing.
The invention optimizes Zr element content and controls the total amount of Cu and Ni elements by improving the Ti-Zr-Cu-Ni solder, thereby realizing the reduction of melting point to 830-880 ℃, improving the diffusion capability of the solder and avoiding generating interface compounds. The brazing filler metal can obtain an amorphous foil strip with the width of 25-35 mm and the thickness of 0.03-0.05 mm by a rapid quenching method, and can be used for brazing titanium material combinations containing pure titanium, Ti-Al compound combinations and titanium material and Ti-Al alloy combination components, in particular thin-wall structural members. Meanwhile, the method is favorable for manufacturing the brazing filler metal foil strip by adopting a quenching strip-spinning method, and can reduce the cost of the brazing filler metal.
The brazing filler metal of the embodiment of the invention has the following advantages and effects:
1. the brazing filler metal and a titanium material matrix have good compatibility. The brazing filler metal of the invention only contains four elements: ti, Zr, Cu and Ni elements, the solder alloy has few element types and has good compatibility with a titanium alloy base material. In contrast, other reported titanium-based solders are mostly 5-or even 7-membered alloy systems.
2. The brazing filler metal has high intrinsic strength, and the melting point of the brazing filler metal meets the use temperature requirement of pure titanium material brazing, namely the brazing temperature can be lower than the phase change point of pure titanium to-882 ℃, and a certain margin is provided.
The Zr element is increased in a certain range, so that the melting point of the brazing alloy can be reduced, and the Zr plays a role in solid solution strengthening on the brazing alloy, thereby being beneficial to improving the strength of the alloy; however, too much Zr element is not beneficial to the diffusion of the alloy at the interface, easily causes the enrichment of the brazing filler metal element, and reduces the strength of the joint. Therefore, it is one of the key problems of the present invention to optimize the Zr content, so that it can exert the strengthening effect and meet the requirement of the material to be welded on the liquidus temperature.
3. The sum of the Cu and Ni elements is controlled to avoid the formation of compounds.
The Cu element and Ti or Zr can form binary eutectic, and the reasonable Cu content is beneficial to reducing the use temperature of the solder; meanwhile, the Cu element contributes to wettability of the solder. However, referring to the Ti-Cu binary phase diagram, Cu and Ti elements can form various Ti-Cu compounds in a plurality of component ranges, which may cause brittleness of the joint. The invention controls the total content of Cu and Ni elements while reducing the Zr content as much as possible.
4. The cost is low.
The preparation of the brazing filler metal is not required to be carried out by adding intermediate alloy into a plurality of alloy elements related by the invention, and the brazing filler metal does not contain rare earth elements and noble metal elements. On the contrary, the master alloy introduces more impurity elements and has the problem of non-ideal melting uniformity.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows the welding interface structure of pure titanium TA1 (process parameters: 865 deg.C, holding time 17min, vacuum degree of 2X 10)-3Pa)；
FIG. 2 shows the welding interface structure of the brazing filler metal of the present invention corresponding to TC4 titanium alloy (process parameters: 890 deg.C, heat preservation time 18min, vacuum degree of 3X 10)-5Pa)；
FIG. 3 is a Ti-Zr binary phase diagram according to the present invention;
FIG. 4 is a welding interface structure of pure titanium TA1 corresponding to the brazing filler metal of one embodiment of the present invention (process parameters: 875 ℃ for 13min, vacuum degree 1X 10)-3Pa)；
FIG. 5 shows the structure of the welding interface of the solder corresponding to the TiAl alloy according to an embodiment of the present invention (process parameters: 900 ℃ heat preservation time 28min vacuum degree is 4X 10)-3Pa)。
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Features and illustrative embodiments of various aspects of the invention are described in detail below. In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced without some of these specific details. The following description of the embodiments is merely intended to provide a better understanding of the present invention by illustrating examples of the present invention. The present invention is in no way limited to any specific arrangement and method set forth below, but rather covers any improvements, substitutions and modifications in structure, method, and apparatus without departing from the spirit of the invention. In the drawings and the following description, well-known structures and techniques are not shown to avoid unnecessarily obscuring the present invention.
It should be noted that, in the case of conflict, the embodiments and features of the embodiments of the present invention may be combined with each other, and the respective embodiments may be mutually referred to and cited. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In some embodiments, a braze (i.e., Ti-Zr-Cu-Ni) for a titanium-containing material may include: ti element, Zr element, Cu element and Ni element. Wherein the weight percentages of the element components are as follows: ti is between 51 and 60 percent; zr is more than or equal to 15 percent and less than or equal to 19 percent; cu and Ni are more than or equal to 25 percent and less than or equal to 30 percent. Wherein Cu is more than or equal to 12% and less than or equal to 14%; ni is more than or equal to 13 percent and less than or equal to 16 percent.
The invention optimizes Zr element content by improving Ti-Zr-Cu-Ni solder, realizes the reduction of melting point to 830-880 ℃, improves the diffusion capability of the solder, avoids generating interface compounds, is beneficial to manufacturing solder foil strips by adopting a quenching strip-spinning method, and can reduce the cost of the solder.
In some embodiments, the weight percentage of each elemental composition is any one of the following (weight percentage):
table 2 example ingredient list
The brazing filler metal with the foil components of examples 1 to 10 shown in Table 2 was used, and the brazing filler metal was maintained at 870 to 880 ℃ for 10 to 20 minutes and at a vacuum degree of 1X 10-3Pa～7×10-3And (3) carrying out the brazing of the material combination of TA1-TA1, TA2-TA2 and TA1-TC4 under the Pa process condition to obtain the high-quality titanium material brazing joint. The tensile strength of the TA2-TA2 joint at room temperature is 442-463MPa, and the elongation after fracture is 0.5% -1.0%, which shows that the tensile sample containing the welded joint is not brittle and the joint has a certain level of plasticity. That is, the brazing filler metal of the present invention can be used for low and medium temperature brazing of a titanium material (particularly, a titanium material composition containing pure titanium) having a β phase transition point lower than that of a material to be brazed, and having low erosion and high strength for the material to be brazed.
The brazing filler metal with the foil components of examples 1 to 10 shown in Table 2 was used, and the heat preservation time was 10 to 20min at 880 to 920 ℃ and the vacuum degree was 1X 10-3Pa～7×10-3The brazing of TC4-TC4 and Ti2AlNb-TC4 is carried out under the Pa process condition, the pattern fracture is at the base part, but the joint part is not broken, which shows that the joint has the strength level not lower than that of the base material. The tensile strength of the joint is 895MPa-905 MPa. Namely, the brazing filler metal of the present invention can realize high-strength brazing of titanium alloys and their alloys with Ti-Al alloys.
The solder described above is suitable for, but not limited to, some application scenarios as follows: welding pure titanium materials and/or titanium alloys and/or Ti-Al compound materials of the ribbed wallboard structure; welding between pure titanium materials and/or titanium alloy and/or Ti-Al compound materials with thin-wall structures; welding pure titanium materials and/or titanium alloy and/or Ti-Al compound materials of the sandwich structure.
Example 1
1. Preparing materials: the composition 7 in Table 2 is adopted, and the chemical compositions of the strip solder in percentage by weight are as follows: zr: 18 percent; cu: 12 percent; ni: 15 percent; ti: and 55 percent. Weighing required Zr, Cu, Ni and Ti raw material powder according to a proportion, wherein the purity of the raw material is not less than 99.9 percent, and the granularity of the raw material is not less than 40 meshes;
2. vacuum smelting: smelting the raw material powder by using a vacuum induction furnace, wherein the smelting temperature is 1700 ℃, the heat preservation time is 0.5h, then casting into an ingot, and air cooling to room temperature; repeatedly smelting for 5 times;
3. preparing a band-shaped brazing filler metal: melting the ingot by a vacuum induction furnace on a vacuum rapid quenching melt spinning machine at 1700 ℃, and then preparing amorphous ribbon solder with the thickness delta of 0.046 mm.
Pure titanium TA1 foil (thickness 0.1mm) brazing was performed using a brazing tape as described above, characterized in that the brazing steps were as follows:
1. cleaning the surface to be brazed of the foil to be welded;
2. positioning the band-shaped brazing filler metal: a layer of strip-shaped brazing filler metal is laid on the surface to be brazed of a part to be brazed, and the strip-shaped brazing filler metal is positioned on the surface to be brazed by a spot welding method;
3. assembling parts: the surface to be brazed of the other part to be brazed is attached to the surface to be brazed of the part to be brazed with the spread ribbon-shaped brazing filler metal through a clamp, and the gap between the two surfaces to be brazed is 0.07 mm;
4. brazing parts: putting the two assembled parts to be welded into a vacuum brazing furnace, wherein the brazing process comprises the following steps: 865 deg.C, holding for 17min, and vacuum degree of 2 × 10-3Pa；
5. And (3) cooling: cooling to room temperature along with the furnace after brazing;
6. the braze welding joint is prepared into a metallographic model, the pure titanium TA1 material does not have phase transformation, the grain size is close to the grain size before welding, the base part is not corroded by the brazing filler metal, no intermetallic compound is formed on the interface, and the interface structure is shown in figure 1.
Example 2
1. Preparing materials: the component 2 in the table 2 is adopted, and the chemical components of the strip solder are as follows by weight percent: zr: 16 percent; cu: 12 percent; ni: 13 percent; ti: 59 percent. Weighing required Zr, Cu, Ni and Ti raw material powder according to a proportion, wherein the purity of the raw material is not less than 99.9 percent, and the granularity of the raw material is not less than 40 meshes;
2. vacuum smelting: smelting the raw material powder by using a vacuum induction furnace, wherein the smelting temperature is 1800 ℃, the heat preservation time is 0.5h, then casting into an ingot, and air cooling to room temperature; repeatedly smelting for 4 times;
3. preparing a band-shaped brazing filler metal: melting the ingot by a vacuum induction furnace on a vacuum rapid quenching melt spinning machine at 1750 ℃ to prepare amorphous state strip solder with the thickness of 0.035 mm.
Brazing of TC4 titanium alloy sheets (thickness 0.6mm) using a brazing ribbon as described above, characterised in that the brazing steps are as follows:
1. cleaning the surface to be brazed of the part to be brazed;
2. positioning the band-shaped brazing filler metal: a layer of strip-shaped brazing filler metal is laid on the surface to be brazed of a part to be brazed, and the strip-shaped brazing filler metal is positioned on the surface to be brazed by a spot welding method;
3. assembling parts: the surface to be brazed of the other part to be brazed is attached to the surface to be brazed of the part to be brazed with the spread strip-shaped brazing filler metal through a clamp, and the gap between the two surfaces to be brazed is 0.06 mm;
4. brazing parts: placing the two assembled parts to be welded into a vacuum brazing furnace for brazing, wherein the brazing process comprises the following steps: 890 deg.C, heat preservation for 18min, and vacuum degree of 3 × 10-5Pa；
5. And (3) cooling: and cooling to room temperature along with the furnace after brazing.
6. The brazed joint is prepared into a metallographic structure, the TC4 material has no phase transformation, the grain size is close to the grain size before welding, no intermetallic compound is formed at the interface, and the interface structure is shown in FIG. 2.
Example 3
1. Preparing materials: the strap-shaped brazing filler metal comprises the following chemical components in percentage by weight: zr: 19.0 percent; cu: 13.5 percent; ni: 16 percent; ti: 51.5 percent. Weighing required Zr, Cu, Ni and Ti raw material powder according to a proportion, wherein the purity of the raw material is not less than 99.9 percent, and the granularity of the raw material is not less than 40 meshes;
2. vacuum smelting: smelting the raw material powder by using a vacuum induction furnace, wherein the smelting temperature is 1700 ℃, the heat preservation time is 0.5, then casting into an ingot, and air cooling to room temperature; repeatedly smelting for 5 times;
3. preparing a band-shaped brazing filler metal: melting the ingot by a vacuum induction furnace on a vacuum rapid quenching melt spinning machine at 1800 ℃ to prepare the amorphous ribbon solder with the thickness of 0.035 mm.
The brazing of SP700 titanium alloy sheets (thickness 0.5mm-0.6mm) was carried out using a brazing ribbon as described above, characterized in that the brazing steps were as follows:
1. cleaning the surface to be brazed of the part to be brazed;
2. positioning the band-shaped brazing filler metal: a layer of strip-shaped brazing filler metal is laid on the surface to be brazed of a part to be brazed, and the strip-shaped brazing filler metal is positioned on the surface to be brazed by a spot welding method;
3. assembling parts: the surface to be brazed of the other part to be brazed is attached to the surface to be brazed of the part to be brazed with the spread strip-shaped brazing filler metal through a clamp, and the gap between the two surfaces to be brazed is 0.06 mm;
4. brazing parts: putting the two assembled parts to be welded into a vacuum brazing furnace, wherein the heating temperature during brazing the SP700 titanium alloy is as follows: 875 deg.C, holding for 16min, and vacuum degree of 3 × 10-4Pa；
5. And (3) cooling: after brazing, the material is cooled to room temperature.
FIG. 4 shows the welding interface structure of another pure titanium TA1 (process parameters: 875 deg.C, heat preservation time 13min, vacuum degree of 1X 10) corresponding to the brazing filler metal of the embodiment of the present invention-3Pa); FIG. 5 shows the structure of the welding interface of the solder corresponding to the TiAl alloy according to one embodiment of the present invention (process parameters: 900 deg.C, holding time 28min, vacuum degree 4X 10)-3Pa) is added. Fig. 4 and fig. 5 also prove that the lower thin-wall structure of the brazing filler metal has no corrosion, no compound at the interface and uniform interface structure, namely the brazing filler metal has the advantage of better diffusion.
In some embodiments, a medium and low temperature ribbon braze for titanium alloys comprises: ti element, Zr element, Cu element and Ni element, wherein the weight percentage of each element component is as follows: ti is between 51 and 60 percent; zr is more than or equal to 15 percent and less than or equal to 19 percent; cu and Ni are more than or equal to 25 percent and less than or equal to 30 percent; cu is more than or equal to 12 percent and less than or equal to 14 percent; ni is more than or equal to 13 percent and less than or equal to 16 percent.
In some embodiments, the weight percentage of each element component is any one of the following:
60.0% of Ti, 15.0% of Zr, 13.0% of Ni and 12.0% of Cu; 25.0% of Cu + Ni;
59.0% of Ti, 16.0% of Zr, 13.0% of Ni and 12.0% of Cu; 25.0% of Cu + Ni;
58.0% of Ti, 15.0% of Zr, 14.0% of Ni and 13.0% of Cu; cu + Ni 27.0%;
57.0% of Ti, 17.0% of Zr, 13.5% of Ni and 12.5% of Cu; cu + Ni 26.0%;
56.0% of Ti, 16.0% of Zr, 14.5% of Ni and 13.5% of Cu; cu + Ni 28.0%;
55.0% of Ti, 18.0% of Zr, 15.0% of Ni and 12.0% of Cu; cu + Ni 27.0%;
54.0% of Ti, 17.0% of Zr, 15.0% of Ni and 14.0% of Cu; cu + Ni 29.0%;
53.0% of Ti, 18.0% of Zr, 15.5% of Ni and 13.5% of Cu; cu + Ni 29.0%;
52.0% of Ti, 19.0% of Zr, 15.5% of Ni and 13.5% of Cu; cu + Ni 29.0%;
51.5% of Ti, 19.0% of Zr, 16.0% of Ni and 13.5% of Cu; cu + Ni 29.5%.
In some embodiments, the brazing filler metal is suitable for, but not limited to, some application scenarios as follows: welding pure titanium materials and/or titanium alloys and/or Ti-Al compound materials of the ribbed wallboard structure; welding between pure titanium materials and/or titanium alloy and/or Ti-Al compound materials with thin-wall structures; welding pure titanium materials and/or titanium alloy and/or Ti-Al compound materials of the sandwich structure.
In some embodiments, a method of making a braze can include the steps of:
material preparation: providing raw material particles of Zr element, Cu element, Ni element and Ti element in a weight percentage of each element component according to any one of claims 1 to 4;
smelting: smelting the raw material particles by using a vacuum induction furnace, and casting into an ingot;
preparing a foil brazing filler metal: and melting the cast ingot by using a vacuum induction furnace on a vacuum rapid quenching melt spinning machine, and preparing the foil brazing filler metal.
In some embodiments, the smelting step comprises: the smelting temperature is 1700 ℃ to 2000 ℃, the heat preservation time is 0.5h to 1h, and the vacuum degree is 1 multiplied by 10-3Pa～7×10-3Pa, repeatedly smelting for 3-5 times.
In some embodiments, in the step of preparing a foil brazing filler metal: the melting temperature is 1700-1800 deg.C, and the vacuum degree is 1X 10-3Pa～7×10-3Pa, and then preparing foil brazing filler metal, wherein the thickness of the foil brazing filler metal is controllable and ranges from 0.03mm to 0.05 mm.
In some embodiments, a method of brazing with a braze, the method comprising the steps of:
cleaning: cleaning the surface to be brazed of a sample or part to be brazed;
positioning foil strip brazing filler metal: cutting the foil brazing filler metal according to the requirement, paving a single layer of brazing filler metal on the surface to be brazed of a sample or part to be brazed, and positioning the foil brazing filler metal on the surface to be brazed by a spot welding method;
assembling: the surface to be brazed of the other sample or part to be brazed is attached to the surface to be brazed of the sample or part to be brazed, on which the foil brazing filler metal is spread, through a clamp;
sample or part brazing step: placing the two assembled samples or parts to be welded into a vacuum brazing furnace for brazing;
and (3) cooling: and cooling to room temperature along with the furnace after brazing.
In some embodiments, in the assembling step: the gap between the two surfaces to be brazed is 0-0.1 mm.
In some embodiments, in the sample or part brazing step: for pure titanium materials, the heating temperature during brazing is as follows: 870-880 ℃, the heat preservation time is 10-20 min, and the vacuum degree is 1 multiplied by 10-3Pa～7×10-3Pa; for titanium alloys, the heating temperature during brazing is as follows: at 880-920 ℃, the heat preservation time is 10-20 min, and the vacuum degree is 1 multiplied by 10-3Pa～7×10-3Pa; for the combination of pure titanium material and titanium alloy, the heating temperature during brazing is as follows: 870-880 ℃, the heat preservation time is 10-20 min, and the vacuum degree is 1 multiplied by 10-3Pa～7×10-3Pa; for the material combination of the titanium alloy and the Ti-Al compound, the heating temperature during brazing is as follows: 920 to 960 ℃, the heat preservation time is 20 to 40min, and the vacuum degree is 1 multiplied by 10-3Pa～7×10-3Pa; for the combination of TiAl and Ti3Al intermetallic compound materials, the heating temperature during brazing is as follows: 920 to 960 ℃, the heat preservation time is 20 to 40min, and the vacuum degree is 1 multiplied by 10-3Pa～7×10-3Pa; for the combination of TiAl and Ti2AlNb intermetallic compound materials, the heating temperature during brazing is as follows: 920 to 960 ℃, the heat preservation time is 20 to 40min, and the vacuum degree is 1 multiplied by 10-3Pa～7×10-3Pa; for the combination of Ti3Al and Ti2AlNb intermetallic material, the heating temperature during brazing is: 920 to 960 ℃, the heat preservation time is 20 to 40min, and the vacuum degree is 1 multiplied by 10-3Pa～7×10-3Pa。
As can be seen from fig. 1 to 5, the embodiment of the present invention can be implemented as follows: the melting point and the diffusion capacity of the brazing filler metal are considered, and the brazing filler metal can be prepared into a foil tape with uniform thickness and good appearance and an interface intermetallic compound. In addition, through a large number of experiments, the technical scheme of the invention has better effect in the technical field of aviation welding.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive various equivalent modifications or substitutions within the technical scope of the present invention, and these modifications or substitutions should be covered within the scope of the present invention.
Claims (10)
1. A strip brazing material for titanium alloy medium and low temperature brazing is characterized by comprising the following components:
ti element, Zr element, Cu element and Ni element, wherein the weight percentage of each element component is as follows:
51.0％≤Ti≤60.0％；
15.0％≤Zr≤19.0％；
25.0％≤Cu+Ni≤30.0％。
2. the solder according to claim 1, wherein:
12.0％≤Cu≤14.0％；
13.0％≤Ni≤16.0％。
3. a brazing filler metal according to claim 1 or 2, wherein the weight percentage of each element component is any one of the following:
60.0% of Ti, 15.0% of Zr, 13.0% of Ni and 12.0% of Cu; 25.0% of Cu + Ni;
59.0% of Ti, 16.0% of Zr, 13.0% of Ni and 12.0% of Cu; 25.0% of Cu + Ni;
58.0% of Ti, 15.0% of Zr, 14.0% of Ni and 13.0% of Cu; cu + Ni 27.0%;
57.0% of Ti, 17.0% of Zr, 13.5% of Ni and 12.5% of Cu; cu + Ni 26.0%;
56.0% of Ti, 16.0% of Zr, 14.5% of Ni and 13.5% of Cu; cu + Ni 28.0%;
55.0% of Ti, 18.0% of Zr, 15.0% of Ni and 12.0% of Cu; cu + Ni 27.0%;
54.0% of Ti, 17.0% of Zr, 15.0% of Ni and 14.0% of Cu; cu + Ni 29.0%;
53.0% of Ti, 18.0% of Zr, 15.5% of Ni and 13.5% of Cu; cu + Ni 29.0%;
52.0% of Ti, 19.0% of Zr, 15.5% of Ni and 13.5% of Cu; cu + Ni 29.0%;
51.5% of Ti, 19.0% of Zr, 16.0% of Ni and 13.5% of Cu; cu + Ni 29.5%.
4. A brazing filler metal according to any one of claims 1 to 3, wherein the brazing filler metal is adapted to:
the brazing method is suitable for brazing of titanium materials containing pure titanium, Ti-Al compounds and titanium alloys;
welding pure titanium materials and/or titanium alloys and/or Ti-Al compound materials of the ribbed wallboard structure;
welding between pure titanium materials and/or titanium alloy and/or Ti-Al compound materials with thin-wall structures;
welding pure titanium materials and/or titanium alloy and/or Ti-Al compound materials of the sandwich structure.
5. A method for preparing a brazing filler metal, said brazing filler metal being as defined in any one of claims 1 to 4, characterized in that said method comprises the steps of:
material preparation: providing raw material particles of Zr element, Cu element, Ni element and Ti element in a weight percentage of each element component according to any one of claims 1 to 4;
smelting: smelting the raw material particles by using a vacuum induction furnace, and casting into an ingot;
preparing a foil brazing filler metal: and melting the cast ingot by using a vacuum induction furnace on a vacuum rapid quenching melt spinning machine, and preparing the foil brazing filler metal.
6. The method according to claim 5, characterized in that in the smelting step:
the smelting temperature is 1700 ℃ to 2000 ℃, the heat preservation time is 0.5h to 1h, and the vacuum degree is 1 multiplied by 10-3Pa-7×10-3Pa, repeatedly smelting for 3-5 times.
7. The method according to claim 5, wherein in the step of preparing foil solder:
the melting temperature is 1700-1800 deg.C, and the vacuum degree is 1X 10-3Pa-7×10-3Pa, and then preparing the foil strip by adopting a vacuum rapid quenching melt-spun machine, wherein the thickness of the foil strip is controllable, and the thickness range is 0.03 mm-0.05 mm.
8. A method of brazing using a brazing filler metal according to any one of claims 1 to 4, characterized in that the method comprises the steps of:
cleaning: cleaning the surface to be brazed of a sample or part to be brazed;
positioning foil strip brazing filler metal: cutting the foil brazing filler metal according to the requirement, paving a single layer of brazing filler metal on the surface to be brazed of a sample or part to be brazed, and positioning the foil brazing filler metal on the surface to be brazed by a spot welding method;
assembling: the surface to be brazed of the other sample or part to be brazed is attached to the surface to be brazed of the sample or part to be brazed, on which the foil brazing filler metal is spread, through a clamp;
sample or part brazing step: placing the two assembled samples or parts to be welded into a vacuum brazing furnace for brazing;
and (3) cooling: and cooling to room temperature along with the furnace after brazing.
9. The method of claim 8, wherein in the assembling step:
the gap between the two surfaces to be brazed is 0-0.1 mm.
10. The method according to claim 8, wherein in the sample or part brazing step:
for pure titanium materials, the heating temperature during brazing is as follows: 870-880 ℃, the heat preservation time is 10-20 min, and the vacuum degree is 1 multiplied by 10-3Pa～7×10-3Pa; or,
for titanium alloys, the heating temperature during brazing is as follows: at 880-920 ℃, the heat preservation time is 10-20 min, and the vacuum degree is 1 multiplied by 10-3Pa～7×10-3Pa; or,
for the combination of pure titanium material and titanium alloy, the heating temperature during brazing is as follows: 870-880 ℃, the heat preservation time is 10-20 min, and the vacuum degree is 1 multiplied by 10-3Pa～7×10-3Pa; or,
for the material combination of the titanium alloy and the Ti-Al compound, the heating temperature during brazing is as follows: 920 to 960 ℃, the heat preservation time is 20 to 40min, and the vacuum degree is 1 multiplied by 10-3Pa～7×10-3Pa; or,
for the combination of TiAl and Ti3Al intermetallic compound materials, the heating temperature during brazing is as follows: 920 to 960 ℃, the heat preservation time is 20 to 40min, and the vacuum degree is 1 multiplied by 10-3Pa～7×10-3Pa; or,
brazing for TiAl and Ti2AlNb intermetallic compound material combinationThe heating temperature is as follows: 920 to 960 ℃, the heat preservation time is 20 to 40min, and the vacuum degree is 1 multiplied by 10-3Pa～7×10-3Pa; or,
for the combination of Ti3Al and Ti2AlNb intermetallic material, the heating temperature during brazing is: 920 to 960 ℃, the heat preservation time is 20 to 40min, and the vacuum degree is 1 multiplied by 10-3Pa～7×10-3Pa。
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Application publication date: 20200110 |