CN113245746B - Copper-based flux-cored solder wire with easy preparation, strong wettability and high brazing seam strength - Google Patents
Copper-based flux-cored solder wire with easy preparation, strong wettability and high brazing seam strength Download PDFInfo
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- CN113245746B CN113245746B CN202110454219.9A CN202110454219A CN113245746B CN 113245746 B CN113245746 B CN 113245746B CN 202110454219 A CN202110454219 A CN 202110454219A CN 113245746 B CN113245746 B CN 113245746B
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- 238000005219 brazing Methods 0.000 title claims abstract description 104
- 239000010949 copper Substances 0.000 title claims abstract description 89
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 85
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 45
- 229910052582 BN Inorganic materials 0.000 claims abstract description 31
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 31
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 30
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000011667 zinc carbonate Substances 0.000 claims abstract description 20
- 235000004416 zinc carbonate Nutrition 0.000 claims abstract description 20
- 229910000010 zinc carbonate Inorganic materials 0.000 claims abstract description 20
- 229910021538 borax Inorganic materials 0.000 claims abstract description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004327 boric acid Substances 0.000 claims abstract description 15
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 15
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 15
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 15
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 15
- 239000006011 Zinc phosphide Substances 0.000 claims abstract description 14
- HOKBIQDJCNTWST-UHFFFAOYSA-N phosphanylidenezinc;zinc Chemical compound [Zn].[Zn]=P.[Zn]=P HOKBIQDJCNTWST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940048462 zinc phosphide Drugs 0.000 claims abstract description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052738 indium Inorganic materials 0.000 claims abstract description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 239000004332 silver Substances 0.000 claims abstract description 10
- 239000003814 drug Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 26
- 239000000945 filler Substances 0.000 abstract description 48
- 229910052751 metal Inorganic materials 0.000 abstract description 48
- 239000002184 metal Substances 0.000 abstract description 48
- 230000004907 flux Effects 0.000 abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 15
- 239000011574 phosphorus Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 10
- 238000003466 welding Methods 0.000 abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000011787 zinc oxide Substances 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000005520 cutting process Methods 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 238000005476 soldering Methods 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 16
- 229910000881 Cu alloy Inorganic materials 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 239000004115 Sodium Silicate Substances 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 229910052911 sodium silicate Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000454 talc Substances 0.000 description 8
- 229910052623 talc Inorganic materials 0.000 description 8
- 229910052787 antimony Inorganic materials 0.000 description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 241001391944 Commicarpus scandens Species 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000005641 tunneling Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000014786 phosphorus Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—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
- 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
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3601—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Nonmetallic Welding Materials (AREA)
Abstract
The invention belongs to the field of welding materials, and particularly relates to a copper-based flux-cored brazing wire which is easy to prepare, strong in wettability and high in brazing seam strength, and comprises a sheath and flux-cored powder; the drug core powder contains 5-8% of nano hexagonal boron nitride, 8-12% of nano zinc carbonate, 16-20% of zinc phosphide, 25% of borax, 18% of boric acid, 7% of potassium fluoride and the balance of tin powder; the outer skin contains 8 to 12 percent of silver, 1.2 to 2.5 percent of indium, 1.5 to 2.2 percent of stibium and the balance of copper; the mass of the flux-cored powder accounts for 25-32% of the total mass of the flux-cored solder wire. The invention has no brittle phase in the outer skin, nano hexagonal boron nitride with strong lubricity in the medicine core powder, continuous filament cutting in the drawing process and easy preparation, the wettability of the brazing filler metal can be enhanced by the existence of phosphorus and the stirring action of carbon dioxide escaping after the zinc phosphide in the medicine core powder is melted during brazing, the brazing seam strength can be effectively improved by the nano hexagonal boron nitride and the decomposed nano zinc oxide, and no brazing flux is needed during brazing.
Description
Technical Field
The invention belongs to the technical field of welding materials, and particularly relates to a copper-based flux-cored solder wire which is easy to prepare, strong in wettability and high in brazing seam strength.
Background
With the development of modern industrial technologies, especially the development of aerospace, automobile, microelectronic and other industrial technologies, the brazing technology has been widely applied with its unique advantages, becoming one of the most active and most developing potential fields, and the brazing filler metal has also been greatly demanded as a brazing welding material. The copper-based solder is widely applied to refrigeration, electromechanics, tools, automobiles, exploration, tunneling and other industries, and is used for soldering copper, copper alloy and other metal materials.
There are two types of copper-based solder wires commonly used today: one is solid solder wire and the other is flux-cored solder wire.
If a solid solder wire is adopted, a copper-based solder is generally matched with a soldering flux for use during soldering (even if the copper-phosphorus solder needs the soldering flux when a copper alloy except pure copper is soldered), the soldering flux is used for removing an oxide film on the surface of a base metal and protecting a soldered joint from oxidation, but the addition amount of the soldering flux cannot be accurately controlled, so that the problem that the soldering flux is excessively used and the soldering flux is remained much after soldering often exists. The excessive use of the brazing flux can generate a large amount of smoke dust, seriously pollute the environment, harm the health of operators and have great potential safety hazard.
If the flux-cored solder wire is adopted, the soldering flux can be added into the tubular copper-based solder according to a certain proportion to prepare the tubular copper-based flux-cored solder wire, the quantitative addition of the soldering flux is realized in the soldering process, the dosage of the soldering flux is greatly reduced, and the potential safety hazard and the environmental pollution caused by the soldering flux are reduced. However, in the drawing process of the preparation, the copper alloy is subjected to plastic deformation, the diameter of the external tubular brazing filler metal is reduced, the length of the external tubular brazing filler metal is prolonged, the powdered brazing flux filled in the core has no connection strength, the plastic deformation cannot occur during drawing and reducing, the radial and longitudinal flow is difficult, the brazing filler metal is compacted, the plastic deformation of the brazing filler metal is blocked, the flux-cored brazing filler metal is particularly easy to break, the single length of a copper-based flux-cored brazing filler metal wire is reduced, and the production efficiency is reduced.
In the process of preparing and using the copper-based solder wire, the following technical problems exist:
(1) in order to increase the wettability during brazing and dilute the molten brazing filler metal no matter a solid brazing filler metal wire or a flux-cored brazing filler metal wire is prepared, the outer skin of the solid copper-based brazing filler metal or the flux-cored copper-based brazing filler metal mostly contains phosphorus, so that the fluidity of the brazing filler metal can be enhanced after the brazing filler metal is molten, and the purpose of filling a gap to obtain a perfect brazing seam is achieved. However, the existence of phosphorus easily forms a low-melting eutectic structure Cu + Cu with a melting temperature of about 714 ℃ in the copper alloy3The brittleness phase P causes the brittleness increase of the outer skin of the solid copper-based brazing filler metal or the flux-cored copper-based brazing filler metal at room temperature, so that the toughness is reduced, the copper-based brazing filler metal wire can only be extruded or drawn in a hot state and is easy to break, the single length of the copper-based brazing filler metal wire is reduced, and the difficulty in the preparation process is increased.
(2) The sheath of the solid copper-based brazing filler metal or the flux-cored copper-based brazing filler metal without the phosphorus element has good plasticity and relatively easy preparation process, but the existence of the phosphorus element does not cause poor wettability during brazing, the molten brazing filler metal has poor fluidity, the gap between workpieces to be welded is not easy to fill, and the obtained brazing seam has low strength.
(3) When the flux-cored copper-based solder wire is prepared, even though the sheath copper alloy does not contain phosphorus element and has better plasticity, the internal flux-cored powder can not generate plastic deformation when the diameter is reduced by drawing, and the flux-cored powder is often compacted and difficult to flow in the radial direction and the longitudinal direction, so that the wire is easy to break when the wire is drawn.
Chinese patent CN112195055A discloses a drawing lubricant for a flux-cored copper-based solder wire, a drawing lubrication method, the flux-cored copper-based solder wire and application thereof (the application date is 2020, 9, 30 days), the drawing lubricant composed of specific components and proportions is placed in a die box where a seamed flux-cored copper solder precursor and a drawing die are located and covers the surface of the flux-cored copper solder precursor, the drawing lubricant and the flux-cored copper solder wire enter the drawing die together, the drawing lubricant plays a drawing lubrication role between the drawing die and the solder, the drawing lubrication method does not break the wire, and the drawing efficiency can be improved. And a trace amount of lubricant remained on the surface of the flux-cored copper brazing filler metal or entering the core part of the flux-cored brazing filler metal after drawing is finished can form a glassy state slag shell to float on the surface of a brazing seam during welding, so that the brazing seam is protected. However, the technical scheme has the following defects: firstly, although the lubricating effect of the brazing filler metal during drawing is enhanced by using the lubricant, the problem that the radial and longitudinal flowing of the flux-cored powder is difficult to change is solved, so that the drawing and reducing of the flux-cored brazing filler metal wire are still difficult, and although the wire breakage problem does not occur in the embodiment of the patent, the wire breakage phenomenon still exists in the practical production application; the copper-based brazing filler metal comprises at least one of BCu54Zn, BCu58ZnMn and BCu60Zn (Si), which is the mark of the copper-zinc brazing filler metal in GB/T6418-2008 copper-based brazing filler metal, and the alloy components do not contain phosphorus elements, so that the fluidity and wettability of the molten brazing filler metal during brazing are poor, and gaps among workpieces to be brazed are not easy to fill; thirdly, after the drawing is finished, a lubricant remained on the surface of the flux-cored copper brazing filler metal or entering the core part of the flux-cored brazing filler metal forms a glassy slag shell during welding, and the fluidity and wettability of the molten brazing filler metal can be hindered in the floating process without the action of external force; and fourthly, although the glassy slag shell floats on the surface of the brazing seam to protect the brazing seam, the effect is limited, the strength of the brazing seam is not obviously improved, and the test result of the strength of the brazing seam is not given in the patent text, but the test value in industrial application is about 260MPa, and the use requirement cannot be completely met.
How to solve the above problems is a critical need for the technicians in this field to work.
Disclosure of Invention
The invention aims to provide a copper-based flux-cored solder wire which is easy to prepare, strong in wettability and high in brazing seam strength, and solves the following technical problems: firstly, how to achieve strong plasticity of a sheath material of the copper-based flux-cored solder wire and good fluidity in the drawing process of the flux-cored powder, and the whole copper-based flux-cored solder wire is not broken in the drawing process and is easy to prepare; secondly, how to achieve good fluidity and strong wettability when the copper-based flux-cored solder wire is brazed; enhancing the strength of the drill seam; fourthly, no brazing flux is needed to be used additionally during brazing.
In order to solve the technical problems, the invention adopts the following technical scheme:
the copper-based flux-cored brazing wire with high wettability and brazing seam strength, which is easy to prepare, comprises a sheath and flux-cored powder, wherein the sheath is in a shape of a seamed/seamless circular tube, and the flux-cored powder is filled in the sheath.
The chemical components of the medicine core powder are as follows by mass percent: 5-8% of nano hexagonal boron nitride, 8-12% of nano zinc carbonate, 16-20% of zinc phosphide, 25% of borax, 18% of boric acid, 7% of potassium fluoride and the balance of tin powder.
The outer skin comprises the following chemical components in percentage by mass: 8 to 12 percent of silver, 1.2 to 2.5 percent of indium, 1.5 to 2.2 percent of stibium and the balance of copper.
The mass of the flux-cored powder accounts for 25-32% of the total mass of the flux-cored solder wire. By accurately controlling the content of the flux core powder, the content of the soldering flux (borax + boric acid + potassium fluoride) can be accurately controlled, and the problem of excessive residual soldering flux after soldering is solved.
Further, the particle size of the nanometer hexagonal boron nitride is 30nm-50 nm.
Furthermore, the particle size of the nano zinc carbonate is 30nm-50 nm.
Further, the particle size of the zinc phosphide is 200-300 meshes.
Further, the particle size of the borax is 200-300 meshes, the particle size of the boric acid is 200-300 meshes, and the particle size of the potassium fluoride is 100-200 meshes.
Furthermore, the particle size of the tin powder is 5-10 μm. Tin is easy to melt during brazing, and the fluidity and wettability of the molten solder can be effectively promoted.
The diameter of the flux-cored solder wire is 2.0mm-3.0mm, preferably 2.2mm-2.8 mm.
The invention has the following beneficial technical effects:
1. the copper-based flux-cored solder wire is not broken in the drawing process and is easy to prepare. Because the sheath does not contain phosphorus element, the low-melting eutectic structure Cu + Cu can not be generated3The P brittle phase is matched with elements such as silver, indium, antimony and the like which are beneficial to enhancing the toughness of the copper alloy, so that the plasticity of the copper alloy sheath is effectively enhanced, and the processing processes such as drawing and the like are facilitated; the hexagonal boron nitride in the flux-cored powder is a two-dimensional structure crystal similar to graphene, nitrogen and boron form a hexagonal net-shaped layer surface, and the two-dimensional structure crystal is overlapped with each other, the two-dimensional structure crystal has excellent lubricity, and in addition, the nano hexagonal boron nitride also has the quantum size effect and the macroscopic tunneling effect of nano particles, so that the flux-cored powder has better fluidity in the drawing process of the brazing filler metal, the radial and longitudinal fluidity of the flux-cored powder in the outer skin of the brazing filler metal is good, the whole copper-based flux-cored brazing filler metal wire is not broken in the drawing process, and the copper-based flux-cored brazing filler metal wire is easy to prepare.
2. The copper-based flux-cored solder wire has good fluidity and strong wettability during brazing. During brazing, zinc phosphide is decomposed into zinc and phosphorus, and the existence of phosphorus element effectively promotes the fluidity of the brazing filler metal; the zinc carbonate is decomposed into zinc oxide and carbon dioxide, and the molten brazing filler metal is stirred by the escape of the carbon dioxide gas, so that the fluidity of the brazing filler metal is effectively increased; the silver, indium and antimony elements in the sheath reduce the melting point of the brazing filler metal and enhance the fluidity of the molten brazing filler metal. The comprehensive effect of the three effectively enhances the wettability of the brazing filler metal, so that the gap between the workpieces to be welded is easily filled with the molten brazing filler metal.
3. The strength of the brazing seam is high. The melting point of hexagonal boron nitride is about 3100 ℃, the melting point of zinc oxide decomposed by heating zinc carbonate is about 1300 ℃, the temperature range during brazing is 600-1000 ℃, the hexagonal boron nitride and the zinc oxide are not melted during brazing, but the particle size of the zinc oxide decomposed by the zinc carbonate is nano-grade because the hexagonal boron nitride and the zinc carbonate are nano-grade, the nano-grade particles are uniformly distributed in the molten brazing filler metal, and when the brazing filler metal is cooled to form a brazing seam, the particles can be used as non-self-forming nuclear particles, so that the crystal grains of the brazing seam are effectively refined, and the strength of the brazing seam is improved. Experiments show that: when the copper-based flux-cored solder wire prepared by the method is used for brazing copper alloy, the tensile strength of a brazing joint reaches more than 362MPa, and is more than 1.2 times of the tensile strength (generally not more than 300MPa) of the joint brazed by common copper-based solder.
4. The brazing filler metal is phosphorus, borax, boric acid and potassium fluoride, and no brazing flux is needed during brazing no matter pure copper or copper alloy is brazed.
Detailed Description
The invention is further illustrated by the following examples, without restricting its scope to the specific embodiments.
Example 1:
the copper-based flux-cored solder wire which is easy to prepare, strong in wettability and high in brazing seam strength comprises a sheath and flux-cored powder, wherein the sheath is in a shape of a seamed round tube, and the flux-cored powder is filled in the sheath.
The chemical components of the medicine core powder are as follows by mass percent: 5% of nano hexagonal boron nitride, 8% of nano zinc carbonate, 16% of zinc phosphide, 25% of borax, 18% of boric acid, 7% of potassium fluoride and the balance of tin powder.
The outer skin comprises the following chemical components in percentage by mass: 8% of silver, 1.2% of indium, 1.5% of antimony and the balance of copper.
The mass of the flux-cored powder accounts for 25 percent of the total mass of the flux-cored solder wire.
The grain size of the nanometer hexagonal boron nitride is 30nm-50 nm.
The particle size of the nano zinc carbonate is 30nm-50 nm.
The grain diameter of the zinc phosphide is 200-300 meshes.
The particle size of borax is 200-300 meshes, the particle size of boric acid is 200-300 meshes, and the particle size of potassium fluoride is 100-200 meshes.
The particle size of the tin powder is 5-10 μm.
The diameter of the flux-cored solder wire is 2.0 mm.
Drawing according to the conventional technology.
Example 2:
the copper-based flux-cored solder wire which is easy to prepare, strong in wettability and high in brazing seam strength comprises a sheath and flux-cored powder, wherein the sheath is in a shape of a seamed round tube, and the flux-cored powder is filled in the sheath.
The chemical components of the medicine core powder are as follows by mass percent: 6.5 percent of nano hexagonal boron nitride, 10 percent of nano zinc carbonate, 18 percent of zinc phosphide, 25 percent of borax, 18 percent of boric acid, 7 percent of potassium fluoride and the balance of tin powder.
The outer skin comprises the following chemical components in percentage by mass: 10% of silver, 1.8% of indium, 1.8% of antimony and the balance of copper.
The mass of the flux-cored powder accounts for 29 percent of the total mass of the flux-cored solder wire.
The grain size of the nanometer hexagonal boron nitride is 30nm-50 nm.
The particle size of the nano zinc carbonate is 30nm-50 nm.
The grain diameter of the zinc phosphide is 200 meshes-300 meshes.
The particle size of borax is 200-300 meshes, the particle size of boric acid is 200-300 meshes, and the particle size of potassium fluoride is 100-200 meshes.
The particle size of the tin powder is 5-10 μm.
The diameter of the flux-cored solder wire is 2.5 mm.
Drawing according to the conventional technology.
Example 3:
the copper-based flux-cored solder wire which is easy to prepare, strong in wettability and high in brazing seam strength comprises a sheath and flux-cored powder, wherein the sheath is in a seamless round tube shape, and the flux-cored powder is filled in the sheath.
The chemical components of the medicine core powder are as follows by mass percent: 8% of nano hexagonal boron nitride, 12% of nano zinc carbonate, 20% of zinc phosphide, 25% of borax, 18% of boric acid, 7% of potassium fluoride and the balance of tin powder.
The outer skin comprises the following chemical components in percentage by mass: 12% of silver, 2.5% of indium, 2.2% of antimony and the balance of copper.
The mass of the flux-cored powder accounts for 32 percent of the total mass of the flux-cored solder wire.
The grain size of the nanometer hexagonal boron nitride is 30nm-50 nm.
The particle size of the nano zinc carbonate is 30nm-50 nm.
The grain diameter of the zinc phosphide is 200-300 meshes.
The particle size of borax is 200-300 meshes, the particle size of boric acid is 200-300 meshes, and the particle size of potassium fluoride is 100-200 meshes.
The particle size of the tin powder is 5-10 μm.
The diameter of the flux-cored solder wire is 3.0 mm.
Drawing according to the conventional technology.
Comparative example 1:
the copper-based flux-cored solder wire is prepared according to the example 2, but the chemical components of the flux-cored powder do not contain nano hexagonal boron nitride, and the copper-based flux-cored solder wire is drawn according to the conventional technology.
Comparative example 2:
the copper-based flux-cored solder wire is prepared according to the example 2, but the chemical components of the flux-cored powder do not contain nano hexagonal boron nitride, and the mixed powder of talc of 700 meshes and sodium silicate of 320 meshes is placed in a die box during drawing.
Comparative example 3:
the copper-based flux-cored solder wire is prepared according to the example 2, but the nano hexagonal boron nitride in the chemical components of the flux-cored powder is changed into the nano cubic boron nitride, and the copper-based flux-cored solder wire is drawn according to the conventional technology.
Comparative example 4:
the copper-based flux-cored solder wire is prepared according to the example 2, but the nano hexagonal boron nitride in the chemical components of the flux-cored powder is changed into the nano cubic boron nitride, and the mixed powder of talc of 700 meshes and sodium silicate of 320 meshes is placed in a die box during drawing.
Comparative example 5:
the copper-based flux-cored solder wire is prepared according to the example 2, but the nano hexagonal boron nitride in the chemical components of the flux-cored powder is changed into the hexagonal boron nitride with the common grain diameter, and the wire is drawn according to the conventional technology.
Comparative example 6:
the copper-based flux-cored solder wire is prepared according to the example 2, but the nano hexagonal boron nitride in the chemical components of the flux-cored powder is changed into 320-mesh sodium silicate, and the wire is drawn according to the conventional technology.
Comparative example 7:
the copper-based flux-cored solder wire is prepared according to the example 2, but the nano hexagonal boron nitride in the chemical components of the flux-cored powder is changed into the talc with 700 meshes, and the wire is normally drawn according to the conventional technology.
Comparative example 8:
the copper-based flux-cored solder wire is prepared according to the example 2, but the nano hexagonal boron nitride in the chemical components of the flux-cored powder is changed into 700-mesh talc with 320-mesh sodium silicate with the same mass, the mass ratio of the talc to the sodium silicate is 85:15, and the copper-based flux-cored solder wire is drawn according to the conventional technology.
Comparative example 9:
a copper-based flux-cored solder wire was prepared as in example 2, but the chemical composition of the sheath contained 6% by mass of phosphorus, and drawn by a conventional technique.
Comparative example 10:
a copper-based flux-cored solder wire is prepared according to example 2, but the chemical composition of the sheath contains 6 mass percent of phosphorus, and the mixed powder of talc of 700 meshes and sodium silicate of 320 meshes is placed in a die box during drawing.
Comparative example 11:
the copper-based flux-cored solder wire is prepared according to the example 2, but the chemical components of the flux-cored powder are free of zinc phosphide, and the copper-based flux-cored solder wire is drawn according to the conventional technology.
Comparative example 12:
the copper-based flux-cored solder wire is prepared according to the example 2, but the chemical components of the flux-cored powder do not contain nano zinc carbonate, and the copper-based flux-cored solder wire is drawn according to the conventional technology.
Comparative example 13:
the copper-based flux-cored solder wire is prepared according to the example 2, but the nano zinc carbonate in the chemical components of the flux-cored powder is changed into the zinc carbonate with the common grain diameter, and the copper-based flux-cored solder wire is drawn according to the conventional technology.
Comparative example 14:
the copper-based flux-cored solder wire is prepared according to the example 2, but the chemical components of the flux-cored powder do not contain nano hexagonal boron nitride and nano zinc carbonate, and the copper-based flux-cored solder wire is drawn according to the conventional technology.
Comparative example 15:
preparing a solid copper-based solder wire, which comprises the following chemical components: 6 percent of phosphorus, 10 percent of silver, 1.8 percent of indium, 1.8 percent of antimony and the balance of copper, mixed powder of talc with 700 meshes and sodium silicate with 320 meshes is placed in a die box during drawing, and welding fluxes (50 percent of borax, 36 percent of boric acid and 14 percent of potassium fluoride) are matched during brazing.
Comparative example 16:
preparing a solid copper-based solder wire, which comprises the following chemical components: 6 percent of phosphorus, 10 percent of silver, 1.8 percent of indium, 1.8 percent of antimony, 8 percent of nano hexagonal boron nitride, 12 percent of nano zinc carbonate and the balance of copper, wherein mixed powder of talc with 700 meshes and sodium silicate with 320 meshes is placed in a die box during drawing, and a welding flux (50 percent of borax, 36 percent of boric acid and 14 percent of potassium fluoride) is matched during brazing.
Examples 1 to 3 and comparative examples 1 to 16 were tested, and 10 results were averaged after 10 experiments were performed for each example. The wettability test of the solder wire is carried out by adopting a muffle furnace, and the test plate is QSn8-0.3 copper alloy (the trade mark in the national standard GB/T2040-; the joint filling test of the brazing filler metal is carried out by flame brazing, and the base material is a copper alloy extruded rod with QAL10-3-1.5 (trade mark in the industry standard YS/T649-.
The results of the examples and comparative examples are shown in Table 1.
TABLE 1
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. The self-fluxing copper-based flux-cored solder wire with easy preparation, strong wettability and high brazing seam strength comprises a sheath and flux-cored powder, and is characterized in that:
the outer skin is in a shape of a seamed/seamless round tube, and the inner part of the outer skin is filled with medicine core powder;
the chemical components of the medicine core powder are as follows by mass percent: 5-8% of nano hexagonal boron nitride, 8-12% of nano zinc carbonate, 16-20% of zinc phosphide, 25% of borax, 18% of boric acid, 7% of potassium fluoride and the balance of tin powder;
the outer skin comprises the following chemical components in percentage by mass: 8 to 12 percent of silver, 1.2 to 2.5 percent of indium, 1.5 to 2.2 percent of stibium and the balance of copper;
the mass of the flux-cored powder accounts for 25-32% of the total mass of the flux-cored solder wire.
2. The self-fluxing copper-based flux-cored solder wire easy to prepare, strong in wettability and high in brazing seam strength according to claim 1, wherein: the particle size of the nanometer hexagonal boron nitride is 30nm-50 nm.
3. The self-fluxing copper-based flux-cored solder wire easy to prepare, strong in wettability and high in brazing seam strength according to claim 1, wherein: the particle size of the nano zinc carbonate is 30nm-50 nm.
4. The self-fluxing copper-based flux-cored solder wire easy to prepare, strong in wettability and high in brazing seam strength according to claim 1, wherein: the particle size of the zinc phosphide is 200-300 meshes.
5. The self-fluxing copper-based flux-cored solder wire easy to prepare, strong in wettability and high in brazing seam strength according to claim 1, wherein: the particle size of the borax is 200-300 meshes, and the particle size of the boric acid is 200-300 meshes.
6. The self-fluxing copper-based flux-cored solder wire easy to prepare, strong in wettability and high in brazing seam strength according to claim 1, wherein: the particle size of the potassium fluoride is 100-200 meshes.
7. The self-fluxing copper-based flux-cored solder wire easy to prepare, strong in wettability and high in brazing seam strength according to claim 1, wherein: the particle size of the tin powder is 5-10 mu m.
8. The self-fluxing copper-based flux-cored solder wire easy to prepare, strong in wettability and high in brazing seam strength according to claim 1, wherein: the diameter of the flux-cored solder wire is 2.0mm-3.0 mm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS56128698A (en) * | 1980-03-14 | 1981-10-08 | Sumitomo Metal Ind Ltd | Composite wire for hard facing padding |
| CN1433868A (en) * | 2003-01-28 | 2003-08-06 | 江汉石油钻头股份有限公司 | Tube shape tungsten carbide welding rod containing cubic boron nitride grain |
| CN107052621A (en) * | 2016-11-30 | 2017-08-18 | 安徽华众焊业有限公司 | High rigidity self protection pile-up welding flux core welding wire and preparation method thereof |
| CN110936064A (en) * | 2019-12-17 | 2020-03-31 | 中机智能装备创新研究院(宁波)有限公司 | Flux-cored silver brazing filler metal |
| CN112195055A (en) * | 2020-09-30 | 2021-01-08 | 郑州机械研究所有限公司 | Drawing lubricant for flux-cored copper-based solder wire, drawing lubrication method, flux-cored copper-based solder wire and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56128698A (en) * | 1980-03-14 | 1981-10-08 | Sumitomo Metal Ind Ltd | Composite wire for hard facing padding |
| CN1433868A (en) * | 2003-01-28 | 2003-08-06 | 江汉石油钻头股份有限公司 | Tube shape tungsten carbide welding rod containing cubic boron nitride grain |
| CN107052621A (en) * | 2016-11-30 | 2017-08-18 | 安徽华众焊业有限公司 | High rigidity self protection pile-up welding flux core welding wire and preparation method thereof |
| CN110936064A (en) * | 2019-12-17 | 2020-03-31 | 中机智能装备创新研究院(宁波)有限公司 | Flux-cored silver brazing filler metal |
| CN112195055A (en) * | 2020-09-30 | 2021-01-08 | 郑州机械研究所有限公司 | Drawing lubricant for flux-cored copper-based solder wire, drawing lubrication method, flux-cored copper-based solder wire and application thereof |
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