CN113579559A - Flux-cored silver solder with indium protective layer and preparation method - Google Patents
Flux-cored silver solder with indium protective layer and preparation method Download PDFInfo
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- CN113579559A CN113579559A CN202110422943.3A CN202110422943A CN113579559A CN 113579559 A CN113579559 A CN 113579559A CN 202110422943 A CN202110422943 A CN 202110422943A CN 113579559 A CN113579559 A CN 113579559A
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- indium
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- silver solder
- metal
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- 229910052738 indium Inorganic materials 0.000 title claims abstract description 116
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 56
- 239000011241 protective layer Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 75
- 239000002184 metal Substances 0.000 claims abstract description 75
- 238000005219 brazing Methods 0.000 claims abstract description 44
- 230000004907 flux Effects 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052709 silver Inorganic materials 0.000 claims abstract description 17
- 239000004332 silver Substances 0.000 claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 17
- 239000010410 layer Substances 0.000 claims description 11
- 238000003618 dip coating Methods 0.000 claims description 8
- 238000005476 soldering Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 12
- 229910001338 liquidmetal Inorganic materials 0.000 abstract description 5
- 238000003892 spreading Methods 0.000 abstract description 5
- 230000007480 spreading Effects 0.000 abstract description 5
- 238000009736 wetting Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 3
- 239000002932 luster Substances 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000003466 welding Methods 0.000 abstract 1
- 238000011056 performance test Methods 0.000 description 10
- 229910052793 cadmium Inorganic materials 0.000 description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005491 wire drawing Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910000746 Structural steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Coating With Molten Metal (AREA)
Abstract
The invention discloses a flux-cored silver brazing filler metal with an indium protective layer, which comprises a brazing flux core and a metal sheath for coating the brazing flux core, wherein the outer surface of the metal sheath is coated with the indium protective layer; preferably, the indium protective layer accounts for 1.7 to 7.7 percent of the mass of the flux-cored silver solder; the invention also discloses a preparation method of the flux-cored silver solder with the indium protective layer; the protective layer on the surface of the brazing filler metal effectively prevents the metal sheath from being oxidized and prevents the surface of the metal sheath from gradually losing luster and becoming dark; when the indium is melted, the welding workpiece can be wetted, and the wetting and spreading performance of the brazing filler metal is improved; after the indium is melted, the indium can be dissolved in the liquid metal sheath containing Ag, so that the melting point of the brazing filler metal is effectively reduced; the indium coating can play a role in moisture prevention, the storage stability of the flux core of the brazing flux is enhanced, and the service life of the brazing flux is prolonged; the preparation method is simple, has few processes, and improves the utilization rate of indium.
Description
Technical Field
The invention relates to the technical field of brazing filler metal, in particular to a flux-cored silver brazing filler metal with an indium protective layer and a preparation method thereof.
Background
The silver solder has good strength, toughness, thermal conductivity, electrical conductivity and corrosion resistance, and can be used for connecting low-carbon steel, structural steel, high-temperature alloy, copper and alloy thereof and the like. At present, the brazing material used in the brazing process at home and abroad is generally a brazing filler metal containing cadmium and silver, and the chemical components of the brazing filler metal contain a large amount of toxic elements cadmium. With the issuance of the RoHS directive and the directive No. 39 by the seven ministries of the information industry sector in china, the use of cadmium element in solder is limited. Therefore, the research on the novel environment-friendly cadmium-free silver solder instead of cadmium has very important practical significance.
Disclosure of Invention
The invention aims to provide a flux-cored silver solder with an indium protective layer, which effectively prevents oxidation of a metal sheath through the protective layer on the surface of the solder, and improves the wetting and spreading performance of the solder after indium is melted when the solder is used.
In order to solve the technical problem, the technical scheme of the invention is as follows: the flux-cored silver solder with the indium protective layer comprises a soldering flux core and a metal sheath coating the soldering flux core, wherein the surface of the metal sheath is coated with the indium protective layer.
Preferably, the indium protective layer accounts for 1.7 to 7.7 percent of the mass of the flux-cored silver solder.
Preferably, the metal sheath coating the flux core of the brazing flux comprises the following substances in percentage by mass:
silver 12.8% to 22.5%;
zinc 18.8% to 31.5%;
the balance being copper.
The silver-based solid solution and the copper-based solid solution have higher strength, better toughness and comprehensive performance, and can obviously improve the processing and mechanical properties of the brazing filler metal; the addition of zinc can reduce the melting temperature and improve the mechanical property, the process property and other defects; the addition of indium element can obviously reduce the solid-liquid phase line temperature of the silver solder, improve the flowing spreading performance of the solder, simultaneously improve the strength of a soldered joint to a certain extent and improve the microhardness of the solder to a certain extent.
Preferably, the flux core of the brazing flux comprises the following substances in percentage by mass:
boric acid 1.6% to 7.2%;
4.8 to 14.4 percent of potassium fluoborate.
In a further improvement, a groove is formed in the outer side of the metal outer skin, and the indium protection layer is filled in the groove and attached to the surface of the metal outer skin. According to the invention, the groove is arranged on the surface of the metal sheath to increase the contact area of the indium protection layer and the metal sheath, so that on one hand, the firmness of combination between the indium protection layer and the metal sheath is improved, on the other hand, the contact between indium and silver is promoted, and the indium is dissolved in the liquid metal sheath containing Ag after being melted.
The second purpose of the invention is to provide a preparation method of the flux-cored silver solder with the indium protective layer, the preparation process is simple, and the flux-cored silver solder with the indium protective layer with excellent performance is prepared.
In order to solve the technical problem, the technical scheme of the invention is as follows: the preparation method of the flux-cored silver solder comprises the following steps: and putting the metal indium into a dip-coating tank, heating and melting to form liquid indium, dip-coating the metal sheath coated with the flux core of the brazing flux at a constant speed, hot-dipping the outside of the metal sheath with a layer of liquid indium, and cooling and solidifying the liquid indium to prepare the flux-cored silver brazing filler metal with the indium protective layer.
By adopting the technical scheme, the invention has one of the following beneficial effects:
1. the metal indium is easy to form a firm coating on the metal surface, the metal sheath coated with the flux core of the brazing flux is dip-coated at a constant speed, a layer of liquid indium is hot-dipped and coated outside the metal sheath, and after the liquid indium is cooled and solidified, the metal sheath is coated with an indium protective layer; the indium protective layer effectively prevents the oxidation of the metal sheath and prevents the surface of the metal sheath from gradually losing luster and becoming dark;
2. according to the invention, the melting point of the solder is effectively reduced by utilizing the fact that the melting point of indium is low, the melting point of indium is 156.61 ℃, and the indium is dissolved in the liquid metal sheath containing Ag after being melted; indium is preferentially melted into liquid in the brazing process, the wettability of the indium is good, the lower melting temperature of the brazing filler metal also effectively avoids coarsening of base metal grains in the brazing process, and the wetting spreading performance of the brazing filler metal on the surface of the base metal is improved; the indium and the silver form a substitutional solid solution to play a role in solid solution strengthening, so that the mechanical property of the brazing seam joint is improved;
3. the indium coating can also improve the metal air tightness, plays a role in moisture prevention, enhances the storage stability of the flux core of the brazing flux and prolongs the service life of the brazing flux;
4. according to the preparation method, the metal outer skin layer of the flux-cored silver solder is provided with the groove in the drawing process and then is dip-coated in the molten indium, so that the indium protective layer is obtained, and the amount of indium in the solder is quantitatively controlled, so that the method is simple and the manufacturing process is simplified; in the prior art, metal indium is added in the smelting process to prepare the indium-containing silver solder, the burning loss rate of the indium is up to 25-30%, and the utilization rate of the indium is low; therefore, compared with the prior art, the method has the advantages that the indium burning loss rate is low in the production process, and the indium utilization rate is effectively improved;
5. the brazing process performance of the flux-cored silver brazing filler metal prepared by the invention is superior to that of the traditional cadmium-containing silver brazing filler metal.
Thereby achieving the above object of the present invention.
Drawings
Fig. 1 is a schematic sectional structure diagram of a flux-cored silver solder with an indium protective layer according to the invention.
In the figure:
a flux core 1; a metal sheath 2; and an indium protective layer 3.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
The embodiment discloses a flux-cored silver solder with an indium protective layer, which comprises a flux core 1 and a metal outer skin 2 covering the flux core 1, wherein the outer surface of the metal outer skin 2 is coated with an indium protective layer 3. The outer side of the metal outer skin 2 is provided with a groove, and the indium protection layer 3 is filled in the groove and attached to the surface of the metal outer skin 2. This embodiment increases indium protective layer 3 and metal crust 2 area of contact through being provided with the recess on metal crust 2 surface, has improved the firm degree that combines between indium protective layer 3 and the metal crust 2 on the one hand, and on the other hand promotes the contact of indium and silver, does benefit to the indium and melts the back, dissolves in the liquid metal crust that contains Ag admittedly.
The specific amounts of flux core 1 and metal sheath 2 used in this example are shown in table 1.
The preparation method of the flux-cored silver solder with the indium protective layer 3 in the embodiment comprises the following steps:
step one, putting metal indium into a dip coating tank, heating and melting to form liquid indium;
and step two, dip-coating liquid indium in the flux-cored silver solder with the groove formed in the metal sheath 2, allowing the liquid indium to enter the groove and attach to the metal sheath 2, and cooling and solidifying the liquid indium to obtain the flux-cored silver solder with the indium protective layer 3.
When the metal sheath 2 coated with the brazing flux core 1 is reduced to obtain the required size through a wire drawing machine set, the last wire drawing die adopts a diamond special-shaped wire drawing die, angular protrusions with different quantities and sizes are arranged according to the difference of the mass proportion of the indium protection layer 3 in the flux-cored silver brazing filler metal, the angular protrusions are uniformly distributed on the wire drawing die, so that grooves with uniform distribution and different sizes appear on the surface of the metal sheath 2 passing through the special-shaped wire drawing die, and the sizes of the grooves are shown in table 1. By controlling the size and the number of the grooves, the mass percentage of the indium protection layer 3 in the flux-cored silver solder can be quantitatively controlled.
The method comprises the steps of putting metal indium into a dip-coating groove, heating and melting the metal indium to form liquid indium, dip-coating a metal sheath 2 coated with a brazing flux core 1 at a constant speed, hot-dipping a layer of liquid indium outside the metal sheath 2, and cooling and solidifying the liquid indium to obtain the flux-cored silver brazing filler metal with an indium protective layer 3.
The specific performance test of the indium-containing flux-cored silver solder obtained by the above component proportions is shown in table 2.
Example 2
The main differences between this example and example 1 are detailed in table 1; the performance test of the flux-cored silver solder with the indium protective layer 3 prepared in this example is detailed in table 2.
Example 3
The main differences between this example and example 1 are detailed in table 1; the performance test of the flux-cored silver solder with the indium protective layer 3 prepared in this example is detailed in table 2.
Example 4
The main differences between this example and example 1 are detailed in table 1; the performance test of the flux-cored silver solder with the indium protective layer 3 prepared in this example is detailed in table 2.
Example 5
The main differences between this example and example 1 are detailed in table 1; the performance test of the flux-cored silver solder with the indium protective layer 3 prepared in this example is detailed in table 2.
Example 6
The main differences between this example and example 1 are detailed in table 1; the performance test of the flux-cored silver solder with the indium protective layer 3 prepared in this example is detailed in table 2.
Example 7
The main differences between this example and example 1 are detailed in table 1; the performance test of the flux-cored silver solder with the indium protective layer 3 prepared in this example is detailed in table 2.
Comparative example 1
The main differences between this example and example 1 are detailed in table 1; the performance test of the prepared flux-cored silver solder without the indium protective layer 3 is detailed in table 2.
Comparative example 2
The metal sheath 2 of the prepared flux-cored silver solder comprises the following substances in percentage by mass:
18.4% Ag,23.0% Zn,36.8% Cu and 13.8% Cd;
the amounts of the remaining materials are detailed in table 1.
The performance test of the silver solder with flux core prepared in this example is shown in Table 2.
Table 1 compositions and structures of silver solder flux-cored wires obtained in examples 1 to 7 and comparative examples 1 and 2
Table 2 list of property tests of flux cored silver solders obtained in examples 1 to 7 and comparative examples 1 and 2
As can be seen by combining the performance test data in tables 1 and 2, the invention utilizes the low melting point of indium, the melting point of indium is 156.61 ℃, and the indium is preferentially melted into liquid in the brazing process; compared with the comparative examples 1 and 2, the indium has better wetting and spreading performance, and after the indium is melted, the indium can be dissolved in the liquid metal sheath 2 containing Ag, so that the melting point of the brazing filler metal is effectively reduced.
According to the preparation method, the metal sheath 2 of the flux-cored silver solder is provided with the groove in the drawing process and then is dip-coated in the molten indium, so that the indium protective layer 3 is obtained, the amount of indium in the solder is quantitatively controlled, the method is simple, and the manufacturing process is simplified; in the prior art, metal indium is added in the smelting process to prepare the indium-containing silver solder, the burning loss rate of the indium is up to 25-30%, and the utilization rate of the indium is low; therefore, compared with the prior art, the method has the advantages that the indium burning loss rate is low in the production process, and the indium utilization rate is effectively improved.
The indium coating of the invention can also improve the metal air tightness, play a role of moisture protection, enhance the storage stability of the flux core 1 of the brazing flux and prolong the service life of the brazing flux.
The indium-containing flux-cored silver solder has good wettability when being used for soldering red copper-brass, brass-carbon steel and stainless steel-nickel base alloy composite materials, and soldered joints have good comprehensive mechanical properties. The brazing process performance of the flux-cored silver brazing filler metal prepared by the invention is superior to that of the traditional cadmium-containing silver brazing filler metal.
Claims (9)
1. The flux-cored silver solder with the indium protective layer is characterized in that: the brazing flux-cored wire comprises a brazing flux core and a metal sheath coating the brazing flux core, wherein an indium protective layer is coated on the surface of the metal sheath.
2. The flux cored silver solder with an indium protective layer of claim 1, wherein: the indium protective layer accounts for 1.7-7.7% of the mass of the flux-cored silver solder.
3. The flux cored silver solder with an indium protective layer of claim 1, wherein: the metal sheath coating the flux core of the soldering flux comprises the following substances in percentage by mass:
silver 12.8% to 22.5%;
zinc 18.8% to 31.5%;
the balance being copper.
4. The flux cored silver solder with an indium protective layer of claim 1, wherein: the filling coefficient of the flux core of the soldering flux is 8% -18%.
5. The flux cored silver solder with an indium protective layer of claim 1, wherein: the flux core of the soldering flux comprises the following substances in percentage by mass:
boric acid 1.6% to 7.2%;
4.8 to 14.4 percent of potassium fluoborate.
6. The flux cored silver solder with an indium protective layer of claim 1, wherein: the outer side of the metal outer skin is provided with a groove, and the indium protection layer is filled in the groove and attached to the surface of the metal outer skin.
7. A method for preparing the flux-cored silver solder as claimed in any one of claims 1 to 6, characterized in that: the method comprises the following steps:
step one, putting metal indium into a dip coating tank, heating and melting to form liquid indium;
and step two, dip-coating indium on the flux-cored silver solder with the groove formed in the metal sheath, allowing liquid indium to enter the groove and attach to the metal sheath, and cooling and solidifying the liquid indium to obtain the flux-cored silver solder with the indium protective layer.
8. The method of claim 7, wherein: the diameter of the flux-cored silver solder with the indium protective layer is phi 4.0 +/-0.1 mm-5.5 +/-0.1 mm.
9. The method of claim 7, wherein: the width of one side of the opening of the groove is 0.3mm to 0.7 mm; the depth of the groove is 0.3mm to 0.4 mm.
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| CN202110422943.3A CN113579559A (en) | 2021-09-14 | 2021-09-14 | Flux-cored silver solder with indium protective layer and preparation method |
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| CN202110422943.3A CN113579559A (en) | 2021-09-14 | 2021-09-14 | Flux-cored silver solder with indium protective layer and preparation method |
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| CN115488543A (en) * | 2022-09-06 | 2022-12-20 | 郑州机械研究所有限公司 | Flux-cored welding ring and preparation method thereof |
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