CN113441872A - Copper alloy composite welding material and preparation method thereof - Google Patents

Copper alloy composite welding material and preparation method thereof Download PDF

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Publication number
CN113441872A
CN113441872A CN202110777987.8A CN202110777987A CN113441872A CN 113441872 A CN113441872 A CN 113441872A CN 202110777987 A CN202110777987 A CN 202110777987A CN 113441872 A CN113441872 A CN 113441872A
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China
Prior art keywords
copper alloy
welding material
powder
brazing
alf
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CN202110777987.8A
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Chinese (zh)
Inventor
马蔷
李升国
陈永威
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Jiangsu University of Science and Technology
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Jiangsu University of Science and Technology
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Priority to CN202110777987.8A priority Critical patent/CN113441872A/en
Publication of CN113441872A publication Critical patent/CN113441872A/en
Pending legal-status Critical Current

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention relates to a copper alloy composite material welding material and a preparation method thereof, wherein the welding material is composed of 10-20% of brazing flux powder and 80-90% of copper alloy powder which are uniformly mixed, the brazing flux is composed of 90-95% of fluosilicate and 5-10% of boric anhydride, and the brazing flux and the copper alloy powder are pressed under pressure and sintered at high temperature to be processed into the copper alloy composite material welding material. The prepared composite welding material enables the mechanical property of the copper alloy welding joint to be excellent, and high-quality connection of the copper alloy is realized.

Description

Copper alloy composite welding material and preparation method thereof
Technical Field
The invention relates to a welding material and a preparation method thereof, in particular to a composite welding material and a preparation method thereof.
Background
The copper alloy has excellent electrical conductivity and thermal conductivity, strong corrosion resistance and magnetic resistance, good wear resistance, processing plasticity and high fatigue limit, and is widely applied to industries such as power electronics, energy industry, transportation, mechanical metallurgy and the like. However, when the copper alloy is subjected to the brazing connection, the temperature is heated to 300 ℃ or more to start forming an oxide film to hinder the brazing connection of the copper alloy. In addition, the thermal expansion coefficient between the brazing filler metal and the copper alloy is not matched, so that large residual stress is generated in the joint, and the strength of the joint is reduced.
In the case of an oxide film formed during brazing, a scholars add a flux during flame brazing, but the amount and time of addition of the flux are difficult to control. Then, the flux core containing the flux is manufactured by the scholars, but the slit of the flux core welding wire is easy to absorb moisture and the flux of the core part and the external metal components are not uniform. In view of the above-mentioned defects, research on the integrated flux/alloy composite welding wire is receiving attention, the integrated flux/alloy composite welding wire has high material utilization rate, reduces waste treatment, enhances solder fluidity, homogenizes components, and can realize automatic welding.
At present, researchers research and discover the integrated brazing flux/alloy composite welding wire: the aluminum alloy composite welding wire containing the fluoride brazing filler metal powder has poor wettability compared with the common welding wire, and the joint filling capability is obviously better than that of the self-brazing filler metal aluminum alloy composite welding wire containing the fluoride brazing filler metal powder. The microstructure, the mechanical property and the corrosion resistance of a joint formed by the composite welding wire containing the fluoride solder powder are superior to those of the composite welding wire containing the fluoride solder powder. In addition, in order to solve the problem of oxidation of the alloy in the brazing process, researchers introduce boron into the solder, and the research finds that boron is easy to perform reduction reaction with some metal oxides, so that boron can play a role of a reducing agent. The researchers also respectively introduce a plurality of fluorides into the solder and analyze the oxidation resistance degree of the fluorides, and the research result shows that the oxidation resistance strength of the fluorides is as follows: KF > K3AlF6/KAlF4＞AlF3。
Patent 201010288311.4 discloses a new aluminum alloy welding wire containing flux and its preparation method, without adding flux before welding and cleaning after welding.
The prior art has the technical problem that how to select proper fluoride, boride and proportion can well realize that a joint formed by welding a composite material has good mechanical property and corrosion resistance.
Disclosure of Invention
The inventors of the present invention have assiduously studied and found that the following compositions and proportions of a boride-and fluoride-containing flux are selected to complete the present invention.
A copper alloy composite welding material comprises the following components: (the following contents are not particularly specified as weight percentages)
80-90% of copper alloy
10 to 20 percent of brazing flux
The brazing flux consists of the following fluosilicate and boric anhydride in percentage by weight:
90 to 95 percent of fluoride salt
5-10% of boric anhydride
The copper alloy is brass, bronze, copper, preferably brass. The fluoride salt comprises KF and AlF as essential components3The selected component is K3AlF6Or KAlF4KF and AlF are preferable3Or K3AlF6Further, KF and AlF are preferable3，The fluoride salt has equal proportion of each component.
The brazing filler metal and oxygen in the air easily react to form an oxide film, and the brazing flux reacts with the oxide film to decompose or break the oxide film, so that the brazing filler metal is oxidized, a stable alloy body cannot be formed on a welding surface, and the mechanical property of the welding surface is reduced.
A preparation method of a copper alloy composite welding material is characterized by comprising the following steps:
1. processing the prepared copper alloy into copper alloy powder, and mixing the copper alloy powder with a brazing flux;
2. and (3) applying the powder prepared in the step (1) to a pressure of 120-200 MPa, pressing for 2-10 minutes, and sintering the pressed powder blank at a temperature of 460-740 ℃ for 3-10 hours to prepare the composite welding material.
And (2) cutting the copper alloy into a thin strip shape in the step 1, grinding the thin strip copper alloy for 2-8 hours by using a vacuum ball milling device to prepare copper alloy powder with 50-500 meshes, and mixing brazing flux.
And 2, applying pressure of 120-200 MPa to the powder prepared in the step 1 by using a cold isostatic press, pressing for 2-10 minutes, sintering the pressed powder blank at the sintering temperature of 460-740 ℃ for 3-10 hours to prepare an alloy blank, and cooling to room temperature.
And further placing the composite welding material prepared in the step 2 on a hot extrusion machine to extrude a wire blank with the diameter of 5mm at the extrusion temperature of 300-500 ℃ at the extrusion speed of 1.5-2.5 m/min and the extrusion ratio of 64: 1. And (3) passing the wire blank through a welding material with the diameter reduced by 2mm for multiple times on a disc wire drawing machine at the traction speed of 3.0-4.0 m/min.
The fluosilicate is KF and AlF3Andor K3AlF6、KAlF4KF and AlF are preferable3And K3AlF6Or KAlF4Further, KF and AlF are preferable3。
And degreasing the surface of the welding material by using copper sulfate.
In order to fully mix the copper alloy powder and the brazing flux, the mixing time in the step 1 is 1-5 hours.
In the step 2, the pressure of the static pressure machine is preferably 150-200 MPa, the pressing time is preferably 2-5 minutes, the sintering temperature is preferably 460-600 ℃, further preferably 460-580 ℃, and the sintering time is preferably 5-10 hours.
The copper alloy composite welding material prepared by the invention is mainly applied to welding of copper alloy.
The invention has the beneficial effects that:
1. according to the copper alloy composite material welding material prepared by the invention, the alloy blank which is formed by fully mixing the soldering flux and the copper alloy can ensure that the soldering flux is uniformly distributed in the alloy, so that the anti-oxidation effect of the copper alloy is stable in the welding process, the shearing strength of a welding joint at room temperature generally reaches 250MPa, and finally the high-quality welding of the copper alloy is realized.
2. The copper alloy composite welding material prepared by the invention is simple, efficient, low in cost and convenient for industrial production.
The specific implementation mode is as follows:
the embodiment of the invention is a typical example applying the technical scheme of the invention, and all the technical schemes formed by adopting equivalent replacement or equivalent transformation are the protection scope of the invention. The following contents are weight percentages.
Example 1
1) The resulting brass alloy was cut into a thin strip shape on a lathe, and the thin strip-shaped brass alloy was ground for 6 hours by a vacuum ball mill to obtain 90g of 300 mesh brass alloy powder. And then mixing the brazing filler metal powder containing KF: 4.75g AlF34.75 g: boric anhydride: 0.5 g. And mechanically mixing the prepared brass alloy powder and the prepared brazing flux powder for 5 hours to prepare mixed powder.
2) And applying 150MPa pressure to the mixed powder by using a cold isostatic press, pressing for 2 minutes, sintering the pressed powder ingot in a vacuum furnace at 570 ℃ for 5 hours, and cooling to room temperature after sintering is finished, thereby preparing the brazing alloy composite casting blank containing the brazing flux.
3) And placing the casting blank on a 100-ton hot extrusion machine at a speed of 64:1, an extrusion speed of 2.0m/min and an extrusion temperature of 450 ℃ to extrude a wire blank with the diameter of 5 mm. And (3) carrying out 4 times of diameter reduction on the wire blank on a disc wire drawing machine at the traction speed of 3.0m/min to obtain a welding material with the diameter of 2mm, and then carrying out surface degreasing treatment on the welding material by using a cuso4 solution to obtain a finished welding material.
The brazing flux-containing brass alloy composite material welding material obtained in the embodiment is used for brazing of copper alloy, the brazed joint is well formed, the antioxidant effect is stable, and the shear strength of the welded joint at room temperature is 250 MPa.
Example 2
In contrast to example 1, the fluoride salt in the flux was chosen from KF and AlF3And K3AlF6，。
Example 3
Except that the mechanical mixing time in step 1 was 1.5 hours in example 1.
Example 4
Except that the pressure in step 2 was 130MPa and the pressing time was 5 minutes in example 1.
Example 5
The difference from example 1 is that the sintering temperature is 470 ℃ and the sintering time is 8 hours.
Example 5
Except that the sintering temperature was 730 ℃ and the sintering time was 5 hours as in example 1.

Claims (10)

1. A copper alloy composite welding material comprises the following copper alloy and brazing flux in percentage by weight, wherein
80-90% of copper alloy
10 to 20 percent of brazing flux
The brazing flux consists of the following fluosilicate and boric anhydride in percentage by weight:
fluoride salt: 90 to 95 percent
5-10% of boric anhydride
The fluosilicate is KF and AlF3Or K3AlF6、KAlF4One of them.
2. The copper alloy composite material welding material according to claim 1, wherein the copper alloy is brass.
3. The brazing material for copper alloy composite material according to claim 1, wherein said fluoride salt is KF and AlF3Or K3AlF6。
4. The brazing material for copper alloy composite material according to claim 3, wherein said fluoride salt is KF and AlF3。
5. The method for preparing a brazing material of copper alloy composite material as set forth in claim 1, comprising the steps of:
1) processing the prepared copper alloy into copper alloy powder, and mixing the copper alloy powder with a brazing flux;
2) and (3) applying the powder prepared in the step (1) to a pressure of 120-200 MPa, pressing for 2-10 minutes, and sintering the pressed powder blank at a temperature of 460-740 ℃ for 3-10 hours to prepare the composite welding material.
6. The method of claim 5, wherein: and 1) mixing the copper alloy and the brazing flux for 1-5 hours.
7. The method according to claim 5, wherein the pressure applied in step 2) is 150 to 200MPa, and the pressing time is 2 to 5 minutes.
8. The preparation method of claim 5, wherein the sintering temperature of the powder blank in the step 2) is 460 to 600 ℃, and the sintering time is 5 to 10 hours.
9. The preparation method of claim 8, wherein the sintering temperature of the powder blank in the step 2) is 460 to 580 ℃ and the sintering time is 5 to 10 hours.
10. The method of claim 5, wherein: the composite material welding material is further processed into a welding material with the thickness of 2mm, and then the surface of the welding material is degreased to obtain a finished product welding material.
CN202110777987.8A 2021-07-09 2021-07-09 Copper alloy composite welding material and preparation method thereof Pending CN113441872A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001276998A (en) * 2000-01-28 2001-10-09 Mazda Motor Corp Brazing flux
CN101947702A (en) * 2010-09-21 2011-01-19 北京工业大学 Novel brazing flux-containing aluminum alloy soldering wire and preparation method thereof
CN104759781A (en) * 2015-04-17 2015-07-08 郑州机械研究所 Silver substitute copper phosphorus tin coating brazing alloy ring and preparation method thereof
CN104907722A (en) * 2015-05-25 2015-09-16 郑州机械研究所 Brass flux-cored brazing filler metal with reducing agents and flow aids and preparation method thereof
CN104907728A (en) * 2015-05-25 2015-09-16 郑州机械研究所 Environment-friendly coated copper brazing filler metal
CN105618961A (en) * 2016-03-15 2016-06-01 南京理工大学 Cesium and rubidium brazing flux containing zinc tetrafluoroborate hydrate
CN112621019A (en) * 2020-12-25 2021-04-09 中机智能装备创新研究院(宁波)有限公司 Flux-cored copper brazing filler metal and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001276998A (en) * 2000-01-28 2001-10-09 Mazda Motor Corp Brazing flux
CN101947702A (en) * 2010-09-21 2011-01-19 北京工业大学 Novel brazing flux-containing aluminum alloy soldering wire and preparation method thereof
CN104759781A (en) * 2015-04-17 2015-07-08 郑州机械研究所 Silver substitute copper phosphorus tin coating brazing alloy ring and preparation method thereof
CN104907722A (en) * 2015-05-25 2015-09-16 郑州机械研究所 Brass flux-cored brazing filler metal with reducing agents and flow aids and preparation method thereof
CN104907728A (en) * 2015-05-25 2015-09-16 郑州机械研究所 Environment-friendly coated copper brazing filler metal
CN105618961A (en) * 2016-03-15 2016-06-01 南京理工大学 Cesium and rubidium brazing flux containing zinc tetrafluoroborate hydrate
CN112621019A (en) * 2020-12-25 2021-04-09 中机智能装备创新研究院(宁波)有限公司 Flux-cored copper brazing filler metal and preparation method thereof

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