CN114952078A - Preparation method of copper-based solder for brazing stainless steel and red copper and copper-based solder - Google Patents
Preparation method of copper-based solder for brazing stainless steel and red copper and copper-based solder Download PDFInfo
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- CN114952078A CN114952078A CN202210574661.XA CN202210574661A CN114952078A CN 114952078 A CN114952078 A CN 114952078A CN 202210574661 A CN202210574661 A CN 202210574661A CN 114952078 A CN114952078 A CN 114952078A
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- copper
- based solder
- stainless steel
- brazing
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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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- 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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- Mechanical Engineering (AREA)
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Abstract
The invention provides a preparation method of a copper-based solder for brazing stainless steel and red copper and the copper-based solder, wherein the copper-based solder is a Cu-Sn-Zn solder, and the mass percent of Sn is 10-15%; the Cu-Sn-Zn alloy cast ingot is obtained by carrying out hot extrusion processing on the Cu-Sn-Zn alloy cast ingot into a wire blank or a strip blank and then carrying out wire drawing or rolling. By adopting the method, the filiform or banded copper-based brazing filler metal with lower liquidus temperature can be prepared, and the method can meet the brazing temperature requirement of dissimilar metals of stainless steel and red copper; meanwhile, the wettability of the brazing filler metal is ensured, the welding seam can be completely filled, and the brazing performance between dissimilar metals is improved.
Description
Technical Field
The invention belongs to the field of brazing materials, and particularly relates to a preparation method of a copper-based brazing filler metal for brazing stainless steel and red copper and the copper-based brazing filler metal.
Background
At present, the welding mode of red copper and stainless steel is mainly brazing, and the related brazing filler metal mainly comprises silver-based brazing filler metal and nickel-based brazing filler metal. The silver-based solder has good processing performance, can be processed into wires, sheets, rings, paste and the like, has the soldering temperature of 700-; the nickel-based brazing filler metal has high brittleness and poor processability, cannot be processed into wires, sheets and the like, can only be processed into powder in an atomization mode and further processed into soldering paste, and the most common brazing filler metal for brazing red copper and stainless steel is wire-shaped or sheet-shaped, so that the application of the brazing filler metal is limited.
In recent years, some industries have tried to braze stainless steel and red copper by using silver-free copper-based brazing filler metal, and the two brands of BCu94Sn (P) and BCu88Sn (P) in the national standard GB/T6418 of the copper-based brazing filler metal are adopted, the two brands refer to Germany products, tin is added into copper to reduce the melting point of the copper, and the melting point and the performance of the brazing filler metal are determined by the amount of the added tin. Less tin is added, the melting point is high, and the forming performance is good; tin addition is high, and the melting point is lowered, but the processability is deteriorated. The solder BCu94Sn (P) has low tin content and is easy to be processed into wires or sheets, but the liquidus temperature reaches 1030 ℃, the soldering temperature is still quite high, and in the soldering process, the crystal grains of the base material copper are easy to grow up, so that the strength of the copper is reduced. The liquidus temperature of BCu88Sn (P) is lower, about 990 ℃, but the processing performance is deteriorated due to the increase of tin content, only the welding powder can be processed by an atomization method or the thin sheet can be prepared by an amorphous method, the welding wire and the welding ring can not be processed, the use range of the brazing filler metal is limited, and the cost is high.
Therefore, the development of the copper-based brazing filler metal which has lower melting point and good forming performance and is suitable for the brazing of stainless steel and red copper is particularly urgent.
Disclosure of Invention
Based on the technical problems, the invention provides a preparation method of a copper-based solder for brazing stainless steel and red copper and the copper-based solder. By adopting the brazing filler metal composition and the method, the filiform or banded copper-based brazing filler metal with lower liquidus temperature can be prepared, and the brazing filler metal can meet the brazing temperature requirement of dissimilar metals of stainless steel and red copper; meanwhile, the wettability of the brazing filler metal is ensured, the welding seam can be completely filled during brazing, and the brazing performance between dissimilar metals is improved.
The invention has the following specific scheme
The invention provides a preparation method of a copper-based solder for brazing stainless steel and red copper, wherein the copper-based solder is a Cu-Sn-Zn solder, and the mass percent of Sn is 10-15%; the Cu-Sn-Zn alloy cast ingot is obtained by carrying out hot extrusion processing on the Cu-Sn-Zn alloy cast ingot into a wire blank or a strip blank and then carrying out wire drawing or rolling.
Compared with an amorphous method, the preparation method provided by the invention is simple and easy to control, has no pollution to the environment, and the obtained brazing filler metal has stable quality, and is suitable for large-scale industrial production.
Preferably, the copper-based solder is a filiform copper-based solder or a strip copper-based solder.
The copper-based brazing filler metal directly obtained by the method is filamentous or banded, and can be further processed into rings by a ring making machine or sheets by a punch press on the basis.
Preferably, the copper-based brazing filler metal comprises the following components in percentage by mass: 10-12% of Sn, 4-6% of Zn and the balance of Cu.
Preferably, the copper-based brazing filler metal comprises the following components in percentage by mass: 12% of Sn, 5% of Zn and the balance of Cu.
The Cu-Sn-Zn solder can control the liquidus temperature of the solder to be below 995 ℃ by regulating and controlling the proportion of each element so as to meet the requirement of the brazing temperature of dissimilar metals of stainless steel and red copper, avoid the damage to the red copper base material caused by overhigh brazing temperature and improve the processing performance of the copper base solder.
Preferably, when the wire blank is processed by hot extrusion, the preheating temperature of the Cu-Sn-Zn alloy cast ingot is 650-700 ℃, and the wire outlet speed is 2-2.5 m/min; when the strip billet is processed by hot extrusion, the preheating temperature of the Cu-Sn-Zn alloy cast ingot is 650-700 ℃, and the strip billet discharging speed is 1.0-1.2 m/min.
Preferably, the wire drawing has a working rate of 45-65% per pass.
Preferably, the reduction rate is 45-65% per pass during rolling.
The processing rate of each pass in the invention is calculated according to the sectional area.
Preferably, during drawing or rolling, after each pass, vacuum annealing treatment is carried out, wherein the annealing temperature is 600-650 ℃.
Preferably, the Cu-Sn-Zn alloy cast ingot is obtained by smelting and casting a red copper plate, a tin ingot and a zinc ingot which are used as raw materials.
The invention also provides a copper-based solder for brazing stainless steel and red copper, which is prepared by any one of the methods.
Compared with the prior art, the invention has the beneficial effects that:
the invention obtains a copper-based solder by matching the solder composition and the preparation process, controls the copper-based solder to have lower liquidus temperature so as to meet the requirement of the soldering temperature of dissimilar metals of stainless steel and red copper, overcomes the technical defect that the conventional BCu88Sn (P) can only be processed into welding powder by an atomization method or be prepared into sheets by an amorphous method and can not obtain welding wires and welding rings, provides a filiform/strip-shaped copper-based solder, enlarges the application range of the solder, improves the performance of welding joints and improves the strength of the welding joints.
Drawings
FIG. 1 is a DSC curve of the filamentous copper-based brazing filler metal obtained in example 1.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
In the following examples and comparative examples, Cu-Sn-Zn alloy ingots were prepared as follows: weighing red copper plate, tin ingot and zinc ingot according to mass percent, placing the red copper plate, the tin ingot and the zinc ingot into a medium-frequency induction furnace in sequence from low melting point to high melting point, wherein the vacuum degree is 1 multiplied by 10 -3 Smelting under the condition of argon under the MPa, wherein the smelting power is 100KW, and smelting for 60 min; and then vacuumizing and refining for 10min, and casting the molten metal into a water-cooling copper mold for cooling to obtain the Cu-Sn-Zn alloy cast ingot.
When the liquidus temperature of the copper-based solder is tested, a DSC curve of the copper-based solder is analyzed by a NETZSCH protein thermal analysis system.
The following wettability refers to the wettability of the copper-based solder on stainless steel and is obtained by adopting a test of SJ/T11390-2009 lead-free solder test method.
Example 1
The copper-based brazing filler metal for brazing the stainless steel and the red copper is a Cu-Sn-Zn brazing filler metal and comprises the following components in percentage by mass: 12% of Sn, 5% of Zn and the balance of Cu; the copper-based brazing filler metal is a filiform copper-based brazing filler metal obtained by carrying out hot extrusion processing on a Cu-Sn-Zn alloy cast ingot to form a wire blank and then carrying out wire drawing. The preparation method comprises the following steps:
(1) hot extrusion: heating the Cu-Sn-Zn alloy cast ingot to 650 ℃ by adopting a resistance furnace, extruding the Cu-Sn-Zn alloy cast ingot into a wire blank with the diameter of 6mm by a 300-ton extruder, wherein the wire outlet speed is 2 m/min;
(2) drawing: reducing the diameter of the wire blank by a wire drawing machine step by step according to the diameter of 6 mm-3.6 mm-2.4-1.5 mm in each pass, processing the wire blank into a wire shape, and annealing in vacuum at 620 ℃ after wire drawing in each pass to obtain the wire-shaped copper-based brazing filler metal.
The wire-like copper-based brazing filler metal obtained in this example was examined:
(1) the DSC curve is shown in figure 1 by analyzing with a NETZSCH protein thermal analysis system, and the peak temperature of the curve corresponds to the liquidus temperature of 982.2 ℃;
(2) the wettability of the filiform copper-based brazing filler metal on stainless steel is 91%, and the requirement of brazing the stainless steel and the red copper dissimilar metal can be met.
Example 2
The copper-based brazing filler metal for brazing the stainless steel and the red copper is a Cu-Sn-Zn brazing filler metal and comprises the following components in percentage by mass: 12% of Sn, 5% of Zn and the balance of Cu; the strip copper-based brazing filler metal is obtained by performing hot extrusion on a Cu-Sn-Zn alloy cast ingot to obtain a strip blank and then rolling the strip blank. The preparation method comprises the following steps:
(1) hot extrusion: heating a Cu-Sn-Zn alloy cast ingot to 700 ℃ by adopting a resistance furnace, extruding the Cu-Sn-Zn alloy cast ingot into a strip blank with the thickness of 80mm multiplied by 2mm in a 300 ton extruding machine, wherein the strip blank discharging speed is 1.2 m/min;
(2) rolling: and (3) gradually rolling and thinning the strip blank by using a four-roller machine in each pass of 2.0 mm-phi 1.2 mm-phi 0.8-phi 0.5mm, processing the strip blank into a strip coil, and annealing in vacuum at 620 ℃ after each pass of rolling to obtain the strip-shaped copper-based brazing filler metal.
And further processing the obtained banded copper-based brazing filler metal by using a punch press to obtain the flaky copper-based brazing filler metal.
The sheet-like copper-based brazing filler metal obtained in this example was examined:
(1) measuring to obtain a liquidus temperature of 985 ℃;
(2) the wettability of the flaky copper-based brazing filler metal on stainless steel is 90%, and the brazing requirement of the stainless steel and red copper can be met.
Example 3
The copper-based brazing filler metal for brazing the stainless steel and the red copper is a Cu-Sn-Zn brazing filler metal and comprises the following components in percentage by mass: 10% of Sn, 6% of Zn and the balance of Cu; the copper-based brazing filler metal is obtained by carrying out hot extrusion processing on a Cu-Sn-Zn alloy cast ingot to form a wire blank and then carrying out wire drawing. The preparation method comprises the following steps:
(1) hot extrusion treatment: heating the Cu-Sn-Zn alloy cast ingot to 680 ℃ by adopting a resistance furnace, extruding the Cu-Sn-Zn alloy cast ingot into a wire blank with the diameter of 6mm by a 300-ton extruder, wherein the wire outlet speed is 2.5 m/min;
(2) drawing: and gradually reducing the diameter of each pass by a wire drawing machine according to the diameter between 6mm and 3.6mm to 2.4 to 1.5mm, processing the wire blank into wires, and performing vacuum annealing at the temperature of 620 ℃ after each pass of wire drawing to obtain the wire-shaped copper-based brazing filler metal.
The wire-like copper-based brazing filler metal obtained in this example was examined:
(1) the liquidus temperature was measured to be 995 deg.C;
(2) the wettability of the filamentous copper-based brazing filler metal on stainless steel is 86%, and the brazing requirement of the stainless steel and red copper can be met.
Comparative example 1
A copper-based solder for brazing stainless steel and red copper is disclosed, which is BCu88Sn (P). The same method as that used in example 1 was used for processing, and the alloy ingot was difficult to extrude due to its high yield strength, and the wire was easily brittle during wire drawing, so that it was impossible to mass-produce the brazing filler metal.
Therefore, the comparative example is directed to the solder being processed into solder powder by atomization and further into a solder paste.
The solder paste obtained in this comparative example was tested:
(1) the liquidus temperature of the product is measured to be 996 ℃;
(2) the wetting property of the solder paste on stainless steel was 85%.
The copper-based brazing filler metal described in examples 1 to 3 and comparative example 1 was used to braze-join stainless steel and red copper to obtain a welded joint, and the strength of the obtained welded joint was measured according to GB/T228.1-2010 part 1 of tensile test for metallic materials: Room temperature test method, with the results shown in Table 1 below:
TABLE 1 stainless steel and red copper weld joint strength
| Tensile strength/MPa | |
| Example 1 | 225 |
| Example 2 | 222 |
| Example 3 | 220 |
| Comparative example 1 | 183 |
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (10)
1. A preparation method of a copper-based solder for brazing stainless steel and red copper is characterized in that the copper-based solder is a Cu-Sn-Zn solder, wherein the mass percent of Sn is 10-15%; the Cu-Sn-Zn alloy cast ingot is obtained by carrying out hot extrusion processing on the Cu-Sn-Zn alloy cast ingot into a wire blank or a strip blank and then carrying out wire drawing or rolling.
2. The method for preparing the copper-based solder for brazing stainless steel and red copper according to claim 1, wherein the copper-based solder is a filiform copper-based solder or a ribbon copper-based solder.
3. The method for preparing the copper-based solder for brazing stainless steel and red copper according to claim 1 or 2, wherein the copper-based solder comprises the following components in percentage by mass: 10-12% of Sn, 4-6% of Zn and the balance of Cu.
4. A method for preparing a copper-based solder for brazing stainless steel and red copper according to any one of claims 1 to 3, wherein the copper-based solder comprises the following components in percentage by mass: 12% of Sn, 5% of Zn and the balance of Cu.
5. The method for preparing the copper-based solder for brazing stainless steel and red copper according to any one of claims 1 to 4, wherein the preheating temperature of the Cu-Sn-Zn alloy ingot is 650-; when the strip billet is processed by hot extrusion, the preheating temperature of the Cu-Sn-Zn alloy cast ingot is 650-700 ℃, and the strip billet discharging speed is 1.0-1.2 m/min.
6. A method of producing a copper based solder for brazing stainless steel to red copper according to any one of claims 1 to 5, characterised in that the wire drawing is performed at a work rate of 45 to 65% per pass.
7. A method for preparing a copper-based solder for brazing stainless steel to red copper according to any one of claims 1 to 6, characterized in that the reduction rate is 45-65% per pass during rolling.
8. The method for preparing the copper-based solder for brazing stainless steel and red copper according to claim 6 or 7, wherein the vacuum annealing treatment is performed after each pass during the wire drawing or rolling, and the annealing temperature is 600-650 ℃.
9. The method for preparing the copper-based solder for brazing stainless steel and red copper according to any one of claims 1 to 8, wherein the Cu-Sn-Zn alloy ingot is obtained by melting and casting a red copper plate, a tin ingot and a zinc ingot.
10. A copper-based solder for brazing stainless steel and red copper, characterized in that the copper-based solder is prepared by the method of any one of claims 1 to 9.
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Citations (10)
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|---|---|---|---|---|
| FR2256959A1 (en) * | 1974-01-04 | 1975-08-01 | Masatoshi Tsuda | Copper-base soldering or brazing alloy - contg. zinc manganese and titanium for brazing cutting tools |
| US4522331A (en) * | 1983-06-03 | 1985-06-11 | Allied Corporation | Method of brazing with low melting point copper-tin foils |
| US4587097A (en) * | 1984-06-22 | 1986-05-06 | Allied Corporation | Homogeneous low melting temperature brazing filler metal for joining ferrous and non-ferrous alloys |
| CN1039986A (en) * | 1989-04-08 | 1990-02-28 | 浙江大学材料制造厂 | A kind of copper-based polybasic alloy soldering materials |
| JP2010131698A (en) * | 2008-12-04 | 2010-06-17 | Akita Univ | Saw wire and method of manufacturing the same |
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| CN109570823A (en) * | 2017-09-29 | 2019-04-05 | 河南智联寰宇知识产权运营有限公司 | Copper alloy ultrahigh-temperature wear-resistant coating cored solder wire and preparation method thereof |
| CN111151916A (en) * | 2019-12-26 | 2020-05-15 | 浙江大学 | Foil brazing filler metal for brazing sintered neodymium-iron-boron permanent magnet material and preparation method |
-
2022
- 2022-05-25 CN CN202210574661.XA patent/CN114952078A/en active Pending
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| FR2256959A1 (en) * | 1974-01-04 | 1975-08-01 | Masatoshi Tsuda | Copper-base soldering or brazing alloy - contg. zinc manganese and titanium for brazing cutting tools |
| US4522331A (en) * | 1983-06-03 | 1985-06-11 | Allied Corporation | Method of brazing with low melting point copper-tin foils |
| US4587097A (en) * | 1984-06-22 | 1986-05-06 | Allied Corporation | Homogeneous low melting temperature brazing filler metal for joining ferrous and non-ferrous alloys |
| CN1039986A (en) * | 1989-04-08 | 1990-02-28 | 浙江大学材料制造厂 | A kind of copper-based polybasic alloy soldering materials |
| JP2010131698A (en) * | 2008-12-04 | 2010-06-17 | Akita Univ | Saw wire and method of manufacturing the same |
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| CN106238962A (en) * | 2016-08-30 | 2016-12-21 | 郑州机械研究所 | A kind of active solder alloy |
| CN109570823A (en) * | 2017-09-29 | 2019-04-05 | 河南智联寰宇知识产权运营有限公司 | Copper alloy ultrahigh-temperature wear-resistant coating cored solder wire and preparation method thereof |
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| CN111151916A (en) * | 2019-12-26 | 2020-05-15 | 浙江大学 | Foil brazing filler metal for brazing sintered neodymium-iron-boron permanent magnet material and preparation method |
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