CN110193682B - Brazing filler metal and preparation method thereof - Google Patents
Brazing filler metal and preparation method thereof Download PDFInfo
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- CN110193682B CN110193682B CN201910467956.5A CN201910467956A CN110193682B CN 110193682 B CN110193682 B CN 110193682B CN 201910467956 A CN201910467956 A CN 201910467956A CN 110193682 B CN110193682 B CN 110193682B
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- filler metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/008—Soldering within a furnace
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/302—Cu as the principal constituent
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- Arc Welding In General (AREA)
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Abstract
The invention discloses a brazing filler metal and a preparation method thereof, wherein the brazing filler metal comprises the following components in percentage by weight: 15 to 30 percent of Mn, 4 to 10 percent of Ni, 0.1 to 3 percent of Fe, 0.01 to 0.3 percent of Al, 0.01 to 0.3 percent of Mg and the balance of Cu.
Description
Technical Field
The embodiment of the invention relates to the technical field of welding, in particular to brazing filler metal and a preparation method thereof.
Background
The brazing device made of the kovar alloy and the TZM alloy material is widely applied to the fields of nuclear industry, aerospace, electric power and the like. In the prior art, kovar alloys are typically welded to TZM alloys using silver-based solders (e.g., silver-based solders containing 40-70 wt% silver, 15-30 wt% palladium, and 15-30 wt% copper).
However, the vapor pressure of the silver-based solder is high, and silver-containing vapor is often deposited at a relatively low temperature portion (such as the inner wall of a soldering furnace, other portions of a soldered device, etc.) during soldering, thereby causing contamination, and particularly, when a precision device is developed, the problem of contamination is difficult to solve, thereby affecting the overall performance of the device. On the other hand, the neutron absorption cross section of silver is large, so that the strength and the air tightness of a welding seam can be seriously influenced when the welding seam runs for a long time in a neutron irradiation environment, and great trouble is caused to the application of a brazing device in the field of nuclear industry. In addition, silver and palladium are precious metal elements, and the use of silver-based solders can result in higher welding costs.
Therefore, there is a need to develop a solder which can replace silver-based solder with stable and reliable performance and economical usage.
Disclosure of Invention
The present invention is directed to a brazing filler metal and a method for preparing the same, which solves at least one of the above problems.
According to one aspect of the present invention, a brazing filler metal is provided, which comprises, by weight: 15 to 30 percent of Mn, 4 to 10 percent of Ni, 0.1 to 3 percent of Fe, 0.01 to 0.3 percent of Al, 0.01 to 0.3 percent of Mg and the balance of Cu.
According to some embodiments, the brazing filler metal comprises, in weight percent: 22 to 27 percent of Mn, 4.2 to 7.2 percent of Ni, 0.5 to 1.5 percent of Fe, 0.01 to 0.05 percent of Al, 0.01 to 0.05 percent of Mg and the balance of Cu.
According to some embodiments, the brazing filler metal has a thickness of 0.1 to 1 mm.
According to another aspect of the present invention, there is provided a method of preparing a brazing filler metal, the method comprising the steps of: step 1, preparing 15-30% of Mn, 4-10% of Ni, 0.1-3% of Fe, 0.01-0.3% of Al, 0.01-0.3% of Mg and the balance of Cu according to the weight percentage of the total formula, and placing the mixture in a heating furnace to be smelted at 1010-1310 ℃ to obtain liquid alloy; step 2, casting the liquid alloy to obtain a cast ingot; and step 3, rolling the cast ingot to prepare the brazing filler metal with the required thickness.
According to some embodiments, before step 2, further comprising: and preserving the heat of the liquid alloy for 5-25 min at the temperature of 950-1010 ℃.
According to some embodiments, step 3 comprises: step 31, carrying out hot rolling on the cast ingot at 350-550 ℃ to obtain a hot rolled strip; and step 32, cold rolling the hot rolled strip to prepare the brazing filler metal with the required thickness.
According to some embodiments, the purity of each metallic material is greater than 99.9%.
According to another aspect of the invention, a method for welding by using the brazing filler metal is provided, and the method comprises the following steps of placing the brazing filler metal at a position to be welded of a first material and a second material to obtain a part to be welded, and placing the part to be welded at a vacuum degree of more than 1.0 × 10-3And (3) keeping the temperature of the soldering furnace of Pa at 940-970 ℃ for 1-5 min, and then cooling to room temperature to obtain a welding piece of the first material and the second material.
In the brazing filler metal according to the embodiment of the invention, Mn, Cu, Ni and Fe are selected as main elements, a small amount of Al and Mg are added for adjustment, and the content of each element is controlled within a proper range, so that compared with the existing silver-based brazing filler metal, the brazing filler metal has the characteristics of low welding cost, relatively smaller neutron absorption cross section and low vapor pressure, the formed welding seam can be ensured to have strong irradiation resistance and stable and reliable performance, and the problem of pollution caused by welding can be avoided to influence the overall performance of a device.
Drawings
Other objects and advantages of the present invention will become apparent from the following description of the invention which refers to the accompanying drawings, and may assist in a comprehensive understanding of the invention.
Fig. 1 shows a schematic view of a weld joint when a brazing filler metal according to an exemplary embodiment of the present invention is used for welding a first material and a second material; and
fig. 2 shows a flowchart of a method of preparing a filler metal according to an exemplary embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments and the accompanying drawings. It should be noted that while examples of parameters including particular values may be provided herein, it should be appreciated that the parameters need not be exactly equal to the corresponding values, but may be approximated to the corresponding values within acceptable error tolerances or design constraints.
Fig. 1 shows a schematic view of a welded joint when a filler metal 3 according to an exemplary embodiment of the present invention is used to weld a first material 1 and a second material 2, and as shown in fig. 1, the filler metal 3 of the present invention may be used to weld the first material 1 and the second material 2. The first material and the second material may be the same material or different materials. In a preferred embodiment, the first material may be a kovar alloy and the second material may be a TZM alloy, but of course, the brazing filler metal of the invention may be used for welding any suitable material, depending on the actual situation.
KOVAR (KOVAR) alloy, also known as KOVAR, material designation 4J29, is a hard glass iron-based sealing alloy containing 29 wt% nickel and 17 wt% cobalt. The alloy has a linear expansion coefficient close to that of hard glass within the range of 20-450 ℃, and can be effectively sealed and matched with corresponding hard glass. Kovar alloys are widely used in the vacuum electronics, power electronics, and other industries, such as in the fabrication of electric vacuum components, emitter tubes, picture tubes, switch tubes, transistors, and hermetic plugs and relay housings.
The TZM alloy, also called molybdenum-zirconium-titanium alloy and titanium-zirconium-molybdenum alloy, is a molybdenum-based alloy containing 0.50 wt% of titanium, 0.08 wt% of zirconium and 0.02 wt% of carbon. The TZM alloy has the characteristics of high melting point, high strength, high elastic modulus, small linear expansion coefficient, low steam pressure, good electric and thermal conductivity, strong corrosion resistance, good high-temperature mechanical property and the like, and can be widely applied to the fields of military industry, electronic and electrical industry, nuclear industry and the like.
The filler metal is filler added in or beside the gap of the filler metal to realize the combination of two materials (or parts), namely the filler material used for forming the welding seam. The melting point of the brazing filler metal is lower than that of the base metal, the brazing filler metal and the base metal are heated together during welding, and under the condition that the base metal is not melted, the liquid brazing filler metal fills gaps between the connected base metals under the capillary action through the melting of the brazing filler metal and the wetting of the base metal, so that welding seams are formed.
The brazing filler metal of the embodiment of the invention comprises the following components in percentage by weight: 15 to 30 percent of Mn, 4 to 10 percent of Ni, 0.1 to 3 percent of Fe, 0.01 to 0.3 percent of Al, 0.01 to 0.3 percent of Mg and the balance of Cu. In the brazing filler metal according to the embodiment of the invention, Mn, Cu, Ni and Fe are selected as main elements, a small amount of Al and Mg are added for adjustment, and the content of each element is controlled within a proper range, so that compared with the existing silver-based brazing filler metal, the brazing filler metal has the characteristics of low welding cost, relatively smaller neutron absorption cross section and low vapor pressure, the formed welding seam can be ensured to have strong irradiation resistance and stable and reliable performance, and the problem of pollution caused by welding can be avoided to influence the overall performance of a device. The brazing filler metal of the present invention enhances brazeability to refractory alloys, kovar alloys, and the like, in terms of improvements in wettability, spreadability, and interface reversal effects, and the like.
The brazing filler metal of the embodiment of the invention is particularly suitable for vacuum brazing. When used, the fluidity of the solder can be adjusted by adjusting the contents of the respective components within the above-mentioned composition ranges according to actual welding conditions. The brazing filler metal is suitable for welding parts with high requirements on cleanliness, conductivity and radiation resistance, such as conductive joints, pipe joints and power generation devices of reactors and aerospace devices.
Silver-based solders used to weld kovar alloys and TZM alloys include silver (Ag), palladium (Pd), and copper (Cu), and solders of embodiments of the present invention include copper (Cu), manganese (Mn), nickel (Ni), aluminum (Al), iron (Fe), and magnesium (Mg). Table 1 shows the thermal neutron absorption cross section reference data of the above several metal elements.
TABLE 1 reference data of thermal neutron absorption cross-sections of several metal elements
As shown in table 1, the neutron absorption cross section of the constituent elements of the brazing filler metal in the embodiment of the present invention is significantly smaller than that of silver, so that the performance influence after neutron irradiation is small, and the strength and the airtightness of the weld joint can be maintained well for a long time.
In the examples of the present invention, Mn, Cu, Ni, Fe are main elements of the silver-free solder, which have a large influence on the workability and weldability of the solder. By controlling the content of each element within the range, the requirements of the brazing filler metal on the processing performance can be met on one hand, and the melting point of the brazing filler metal can be ensured to be 900-1000 ℃ on the other hand.
Mn and Cu are two elements with the largest content in the brazing filler metal, and a certain solid solution is formed under the proportion, so that the welding temperature of the brazing filler metal can be controlled between 950 ℃ and 1010 ℃, and is basically the same as that of the existing silver-copper-palladium brazing filler metal. According to table 1, Mn and Cu have a smaller neutron absorption cross section than silver and are more resistant to irradiation. The other element with relatively high content is Ni, the Ni can increase the wetting capacity of the brazing filler metal, improve the surface characteristics of the liquid brazing filler metal and the surface quality of a welding seam, and simultaneously improve the corrosion resistance of the brazing filler metal, and the content of the Ni is preferably 4.0-10.0 wt%.
The addition of a small amount of Fe element can increase the spreadability of the brazing filler metal on the first material (such as Kovar alloy) and the second material (such as TZM alloy), but the addition amount is not too large, otherwise an iron independent phase is formed, the corrosion resistance of the brazing filler metal is reduced, and the content of the Fe element is preferably 0.1-3.0 wt%. The addition of trace Al and Mg can increase the extensibility of the brazing filler metal and adjust the melting point temperature of the brazing filler metal, but the addition amount is not too much, otherwise, the overall performance of the brazing filler metal is affected, and the content of the Al and Mg is controlled to be 0.01-0.30 wt%.
In some embodiments, the brazing filler metal may include, in weight percent: 22 to 27 percent of Mn, 4.2 to 7.2 percent of Ni, 0.5 to 1.5 percent of Fe, 0.01 to 0.05 percent of Al, 0.01 to 0.05 percent of Mg and the balance of Cu.
The thickness of the brazing filler metal in the embodiment of the invention can be 0.1-1 mm, such as 0.2mm, 0.3mm or 0.5 mm. The brazing filler metal can be formed into strips, wires and other specifications with different shapes.
Fig. 2 illustrates a flowchart of a method of preparing a filler metal according to an exemplary embodiment of the present invention, which may include the steps of, as shown in fig. 2:
and 3, rolling the cast ingot to prepare the brazing filler metal with the required thickness.
In some embodiments, before step 2, further comprising: and preserving the heat of the liquid alloy for 5-25 min at the temperature of 950-1010 ℃. Therefore, the smelting process can be ensured to achieve a sufficient metallurgical bonding effect.
In some embodiments, step 3 may further comprise:
step 31, carrying out hot rolling on the cast ingot at 350-550 ℃ to obtain a hot rolled strip; and
and step 32, cold rolling the hot rolled strip to prepare the brazing filler metal with the required thickness.
When the ingot is hot-rolled, rolling may be performed a predetermined number of times, and heat treatment may be performed between the respective passes. The hot rolled strip may be pickled before being cold rolled, and may be thereafter cold rolled a predetermined number of times. The resulting braze may be annealed after cold rolling to eliminate cold rolling work hardening. Besides rolling, the brazing filler metal can be processed into brazing filler metal with required shape and specification by processing methods such as extrusion, wire drawing and the like.
The invention also provides a method for welding by using the brazing filler metal, which comprises the following steps:
placing the brazing filler metal at a position to be welded of the first material and the second material to obtain a part to be welded; wherein, the base material and the brazing filler metal can be fixed together by adopting a clamp; and
placing the workpiece to be welded in a vacuum degree of more than 1.0 × 10-3And (3) keeping the temperature of the soldering furnace of Pa at 940-970 ℃ for 1-5 min, and then cooling to room temperature to obtain a welding piece of the first material and the second material.
According to the above description, the brazing filler metal of the embodiment of the invention has at least the following beneficial effects:
(1) the brazing filler metal does not contain noble metal elements such as Ag and Pd, and the cost is lower;
(2) the melting point of the brazing filler metal is moderate, the solidus temperature of the brazing filler metal is 920-940 ℃, the liquidus temperature of the brazing filler metal is 940-970 ℃, the minimum brazing temperature is 950-1010 ℃, and the brazing filler metal is suitable for welding Kovar alloy and TZM alloy;
(3) the processing performance of the brazing filler metal is good, and the brazing filler metal can be processed into brazing filler metals with different shapes and specifications such as strips or wires by processing methods such as proportioning, smelting, casting, rolling or extruding, wire drawing and the like;
(4) the brazing filler metal has good wettability to the kovar alloy and the TZM alloy, the weld joint is well formed, and the brazing process is easy to operate.
The following is a description of specific examples.
Example 1
1. Preparing a brazing filler metal for welding a kovar alloy with a TZM alloy, comprising the steps of:
(1) smelting: preparing 24.5% of Mn, 5.7% of Ni, 1.0% of Fe, 0.01% of Al, 0.01% of Mg and the balance of Cu according to the weight percentage of the total formula, wherein the purity of each metal material is more than 99.9%, putting the metal materials into a heating furnace to be heated to 1250 ℃, cooling to 980 ℃ after complete melting and full stirring, preserving heat for 10min, and then casting to obtain an ingot;
(2) hot rolling: heating the cast ingot obtained in the step (1) to 400 ℃ for hot rolling to obtain a hot rolled strip with the specification of 2.0 mm;
(3) cold rolling: and (3) cold-rolling the hot-rolled strip obtained in the step (2) into brazing filler metal with the required thickness of 0.5mm, 0.3mm and 0.2 mm.
2. The kovar alloy and the TZM alloy are welded by using the brazing filler metal, and the method comprises the following specific steps:
placing the obtained brazing filler metal at a to-be-welded position of the TZM alloy and the kovar alloy device to obtain a to-be-welded part;
placing the workpiece to be welded in a vacuum degree of more than 1.0 × 10-3And (3) keeping the temperature of the high-temperature brazing furnace with Pa at 955 ℃ for 2min, and then cooling the high-temperature brazing furnace to room temperature to finish welding.
3. Performance detection
The welding section of the device is observed by SEM to find that the wetting and spreading effect of the brazing filler metal in the welding line is good, and the helium mass spectrometer leak detector is adopted to test the welding piece to obtain the leakage rate of less than 1.0 × 10-10Pa·m3And/s, the welding seam has good air tightness.
Although the present invention has been described in connection with the accompanying drawings, the embodiments disclosed in the drawings are intended to be illustrative of embodiments of the invention and should not be construed as limiting the invention.
It would be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the general inventive concept, the scope of which is defined in the claims and their equivalents.
Claims (8)
1. The brazing filler metal is characterized by comprising the following components in percentage by weight:
15 to 30 percent of Mn, 4 to 10 percent of Ni, 0.1 to 3 percent of Fe, 0.01 to 0.3 percent of Al, 0.01 to 0.3 percent of Mg and the balance of Cu;
the brazing filler metal is a strip material or a wire material.
2. Brazing filler metal according to claim 1, comprising, in weight percent:
22 to 27 percent of Mn, 4.2 to 7.2 percent of Ni, 0.5 to 1.5 percent of Fe, 0.01 to 0.05 percent of Al, 0.01 to 0.05 percent of Mg and the balance of Cu.
3. The brazing filler metal according to claim 1, wherein the brazing filler metal has a thickness of 0.1 to 1 mm.
4. The preparation method of the brazing filler metal is characterized by comprising the following steps:
step 1, preparing 15-30% of Mn, 4-10% of Ni, 0.1-3% of Fe, 0.01-0.3% of Al, 0.01-0.3% of Mg and the balance of Cu according to the weight percentage of the total formula, and placing the mixture in a heating furnace to be smelted at 1010-1310 ℃ to obtain liquid alloy;
step 2, casting the liquid alloy to obtain a cast ingot; and
and 3, rolling the cast ingot to prepare the brazing filler metal with the required thickness.
5. The method of claim 4, further comprising, prior to step 2:
and preserving the heat of the liquid alloy for 5-25 min at the temperature of 950-1010 ℃.
6. The method of claim 4, wherein step 3 comprises:
step 31, carrying out hot rolling on the cast ingot at 350-550 ℃ to obtain a hot rolled strip; and
and step 32, cold rolling the hot rolled strip to prepare the brazing filler metal with the required thickness.
7. The method of claim 4, wherein each metallic material has a purity greater than 99.9%.
8. A method of welding using the brazing filler metal according to any one of claims 1 to 3, comprising the steps of:
placing the brazing filler metal at a position to be welded of the first material and the second material to obtain a part to be welded; and
placing the workpiece to be welded in a vacuum degree of more than 1.0 × 10-3And (3) keeping the temperature of the soldering furnace of Pa at 940-970 ℃ for 1-5 min, and then cooling to room temperature to obtain a welding piece of the first material and the second material.
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| DE2712994A1 (en) * | 1977-02-09 | 1978-08-10 | Peter Sixt | Copper-manganese alloy filler rod - for MIG welding ferrous and non-ferrous metals (OE 15.1.78) |
| US4133473A (en) * | 1975-02-10 | 1979-01-09 | Tabelev Vladislav D | Method for brazing ferromagnetic materials |
| CN1799760A (en) * | 2005-01-05 | 2006-07-12 | 罗成林 | Copper based brazing alloy |
| CN101890588A (en) * | 2009-05-19 | 2010-11-24 | 天津市三条石有色金属铸造有限公司 | Novel copper-based dip brazing alloy for drilling bit |
| CN103358051A (en) * | 2013-07-23 | 2013-10-23 | 华南理工大学 | Copper-based solder and preparation method thereof |
| CN109514128A (en) * | 2019-01-10 | 2019-03-26 | 新利得（天津）焊接材料有限公司 | A kind of formula and processing technology of complexity Mn-Al-Ni bronze welding wire |
-
2019
- 2019-05-31 CN CN201910467956.5A patent/CN110193682B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4133473A (en) * | 1975-02-10 | 1979-01-09 | Tabelev Vladislav D | Method for brazing ferromagnetic materials |
| DE2712994A1 (en) * | 1977-02-09 | 1978-08-10 | Peter Sixt | Copper-manganese alloy filler rod - for MIG welding ferrous and non-ferrous metals (OE 15.1.78) |
| CN1799760A (en) * | 2005-01-05 | 2006-07-12 | 罗成林 | Copper based brazing alloy |
| CN101890588A (en) * | 2009-05-19 | 2010-11-24 | 天津市三条石有色金属铸造有限公司 | Novel copper-based dip brazing alloy for drilling bit |
| CN103358051A (en) * | 2013-07-23 | 2013-10-23 | 华南理工大学 | Copper-based solder and preparation method thereof |
| CN109514128A (en) * | 2019-01-10 | 2019-03-26 | 新利得（天津）焊接材料有限公司 | A kind of formula and processing technology of complexity Mn-Al-Ni bronze welding wire |
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