WO2023015784A1 - Braze paste for fluxless brazing of stainless steel and preparation method therefor, copper-manganese-nickel-cobalt braze material, and application - Google Patents

Braze paste for fluxless brazing of stainless steel and preparation method therefor, copper-manganese-nickel-cobalt braze material, and application Download PDF

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WO2023015784A1
WO2023015784A1 PCT/CN2021/135209 CN2021135209W WO2023015784A1 WO 2023015784 A1 WO2023015784 A1 WO 2023015784A1 CN 2021135209 W CN2021135209 W CN 2021135209W WO 2023015784 A1 WO2023015784 A1 WO 2023015784A1
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stainless steel
parts
copper
brazing
solder paste
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PCT/CN2021/135209
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French (fr)
Chinese (zh)
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龙伟民
钟素娟
黄俊兰
裴夤崟
张冠星
薛行雁
聂孟杰
李文彬
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郑州机械研究所有限公司
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Publication of WO2023015784A1 publication Critical patent/WO2023015784A1/en

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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
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B23K35/025—Pastes, creams, slurries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/002—Soldering by means of induction heating
    • 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
    • B23K35/40—Making wire or rods for soldering or welding

Definitions

  • the invention belongs to the technical field of brazing materials, and in particular relates to a solder paste for stainless steel flux-free brazing, a preparation method thereof, a copper-manganese-nickel-cobalt solder and applications thereof.
  • stainless steel has superior high temperature performance and good corrosion resistance, and is widely used in the manufacture of heat exchanger piping.
  • stainless steel heat exchangers have become heat exchange devices commonly used in metallurgy, chemical industry, energy, transportation, light industry, food and other industrial sectors.
  • Brazing is a key link in the manufacture of stainless steel heat exchanger piping, which determines the service life of the heat exchanger. With the improvement of people's quality of life, the requirements for the welding quality of stainless steel heat exchangers are getting higher and higher. The welding quality of stainless steel heat exchangers is largely dependent on the brazing material used.
  • H1CuNi30-2-0.2 (Ni27 ⁇ 30; Si1.5 ⁇ 2.0; B0.2, Cu balance) widely used in the aviation industry has a melting temperature range of 1080 ⁇ 1200°C and a working temperature of up to 600°C (Zou Xi, Brazing Welding", high-temperature copper-based solder), has the advantages of good high-temperature performance, low cost, and good compatibility with stainless steel, and is often used for brazing stainless steel in protective atmosphere furnaces.
  • the existing H1CuNi30-2-0.2 solder does not have self-brazing properties. When brazing stainless steel in an atmosphere furnace, the dense oxide film on the surface of the stainless steel is difficult to remove when the brazing temperature is lower than 1000 ° C.
  • the purpose of the present invention is to provide a solder paste for stainless steel flux-free brazing, which can realize flux-free brazing of stainless steel in an atmospheric environment and improve joint strength.
  • the second object of the present invention is to provide a preparation method of the above-mentioned solder paste for stainless steel flux-free brazing.
  • the third object of the present invention is to provide a copper-manganese-nickel-cobalt solder for stainless steel brazing.
  • the fourth object of the present invention is to provide the application of the above solder paste in induction brazing stainless steel.
  • the technical scheme of the solder paste for stainless steel brazing without flux of the present invention is:
  • solder paste for stainless steel brazing without flux is mainly composed of water, sodium silicate, nano silicon dioxide and copper-based solder; the solder paste is made of the following raw materials in parts by weight : 70-80 parts of copper-based solder, 3-5 parts of nano silicon dioxide, 1-3 parts of sodium hydroxide, 10-15 parts of water; the copper-based solder is composed of the following components in mass percentage: Mn 26.0 ⁇ 30.0%, Ni 26.0 ⁇ 30.0%, Co 4.0 ⁇ 6.0%, B 0.1 ⁇ 0.5%, Li 0.1 ⁇ 0.6%, Na 0.1 ⁇ 0.2%, K 0.01 ⁇ 0.3%, Cu balance.
  • the solder paste of the present invention contains water, sodium silicate, and nano-silica paste, which is dehydrated at high temperature to form a thin film during brazing, and the nano-silica in it can build a three-dimensional network structure, which has a large surface area and a very large surface area.
  • High activity will enhance the strength and high temperature resistance of the film and form a high temperature resistant film.
  • the film isolates the air, protects the surface to be brazed, and the molten solder is not oxidized, and realizes flux-free brazing of stainless steel in an atmospheric environment; at the same time, nano-silica particles are pinned in the brazing seam, which also helps to strengthen the stainless steel joint strength.
  • the above-mentioned improved copper-based solder is based on H1CuNi30-2-0.2 solder, adding Mn, Co, and reducing Cu, so that the melting temperature of the solder is between 930 and 970 ° C, which can reduce the brazing temperature .
  • a certain amount of B and Li elements are added to the solder, and the solder has self-brazing properties. This is because B and Li can reduce oxides on the surface of stainless steel, such as Cr 2 O 3 , and the melting point of the reduction product is lower than the brazing temperature, and it floats in the form of a liquid film on the surface of the base metal and the molten solder to protect it.
  • the viscosity of B oxide is very high, which will hinder the spreading of solder. For this reason, a small amount of Na and K elements are added.
  • the viscosity of Na and K oxides is small, which can reduce the viscosity of the reduction product, promote the wetting of the film and the spreading of the solder, and enhance the self-brazing performance of the solder.
  • the solder paste is made of the following raw materials in parts by weight: 74 to 80 parts of copper-based solder, 3 to 5 parts of nano silicon dioxide, 1 to 3 parts of sodium hydroxide, water 12 to 15 servings. More preferably, the copper-based solder is composed of the following components by mass percentage: Mn 28.0-30.0%, Ni 28.0-30.0%, Co 4.0-6.0%, B 0.3-0.5%, Li 0.4-0.6%, Na 0.1 ⁇ 0.2%, K 0.15 ⁇ 0.3%, Cu balance.
  • the particle size of the nano silicon dioxide is 30-50 nm.
  • the technical scheme of copper-manganese-nickel-cobalt solder for stainless steel brazing of the present invention is:
  • a copper-manganese-nickel-cobalt solder for stainless steel brazing which consists of the following components in mass percentage: Mn 26.0-30.0%, Ni 26.0-30.0%, Co 4.0-6.0%, B 0.1-0.5%, Li 0.1-0.6 %, Na 0.1-0.2%, K 0.01-0.3%, Cu balance.
  • the copper-manganese-nickel-cobalt brazing material for stainless steel brazing of the present invention has low brazing temperature (beneficial for suppressing the growth of stainless steel crystal grains), strong wetting and spreading ability, and is aimed at conventional matching In the case of using flux, the amount of flux can be reduced or no flux can be used.
  • the copper-manganese-nickel-cobalt solder for stainless steel brazing consists of the following components in mass percentage: Mn 28.0-30.0%, Ni 28.0-30.0%, Co 4.0-6.0%, B 0.3-0.5%, Li 0.4 ⁇ 0.6%, Na 0.1 ⁇ 0.2%, K 0.15 ⁇ 0.3%, Cu balance.
  • the technical scheme of the preparation method of the solder paste for stainless steel brazing without flux of the present invention is:
  • a preparation method of solder paste for stainless steel flux-free brazing comprising the following steps:
  • step 2) reacting the alkaline aqueous solution obtained in step 1) with nano silicon dioxide under conditions higher than normal pressure to obtain a suspension;
  • the preparation method of the solder paste for stainless steel brazing without flux has a simple preparation process, the obtained solder paste has high stability, and can effectively improve the brazing effect of stainless steel brazing.
  • the above-atmospheric pressure condition refers to a steam pressure of 0.3-0.5 MPa.
  • the reaction time is 3.0-5.0 hours.
  • the technical solution for the application of the above-mentioned solder paste is: the application of the above-mentioned solder paste in induction brazing stainless steel.
  • the stainless steel is brazed and connected in an atmospheric environment without flux.
  • the above-mentioned solder paste is used without brazing flux, which can realize rapid induction brazing of stainless steel in the atmospheric environment, does not pollute the environment, and is green and environmentally friendly.
  • Fig. 1 is the preparation schematic diagram of solder paste of the present invention
  • Fig. 2 is the spreading morphology when the existing H1CuNi30-2-0.2 brazing filler metal is carried out without flux spreading performance test under atmospheric environment;
  • Fig. 3 is the spreading morphology of the solder paste obtained in Example 5 of the present invention when the flux-free spreading performance test is performed in an atmospheric environment.
  • the amount of nano silicon dioxide is controlled to be relatively excessive, and the reaction with sodium hydroxide consumes a part of the nano silicon dioxide, and the other part remains in the liquid to form a suspension.
  • the suspension is dehydrated at high temperature to form a thin film, in which the excess nano-silica is a three-dimensional network structure with a large surface area and great activity, which will enhance the strength and high temperature resistance of the film and form a high temperature resistant film.
  • the film isolates the air, protects the surface to be brazed and the molten solder from being oxidized.
  • the nano-silica particles are pinned into the brazing joint and also help to strengthen the stainless steel joint.
  • the above-mentioned suspension can enhance the high temperature resistance of the film formed by mucus dehydration, and on the other hand, the nano-silica in it will be pinned to the brazing joint to enhance the strength of the joint.
  • the parts by weight of the raw materials used consist of: 70 parts of copper-based solder powder, 3 parts of nano silicon dioxide, 3 parts of sodium hydroxide, 10 parts of deionized water; the mass percent of each component in the copper-based solder powder is: Mn26.0%, Ni26.0%, Co4.0%, B0.1%, Li0.1%, Na0.1% , K0.01%, Cu balance.
  • step (2) Add nano-silica (30-50nm) into step (1) alkaline aqueous solution, put it in a high-pressure reactor, and react for 3.0 hours under 0.3MPa steam pressure to form a suspension (transparent colloidal liquid + a small amount of silicon dioxide); the reaction process schematic diagram is as shown in Figure 1;
  • step (3) Add copper-based solder powder into the suspension liquid in step (2), mix and stir to form a uniform paste, and obtain solder paste.
  • the preparation method of the solder paste for stainless steel flux-free brazing of the present embodiment the parts by weight of the raw materials used consist of: 72 parts of copper-based solder powder, 4 parts of nano silicon dioxide, 2 parts of sodium hydroxide, 11 parts of deionized water; the mass percent of each component in the copper-based solder powder is: Mn27.0%, Ni27.0%, Co5.0%, B0.2%, Li0.2%, Na0.1% , K0.1%, Cu balance.
  • the specific preparation method is basically the same as that of Example 1, except that in step (2), the steam pressure is 0.4 MPa, and the reaction time is 4.0 h.
  • the parts by weight of the raw materials used consist of: 74 parts of copper-based solder powder, 5 parts of nano silicon dioxide, 1 part of sodium hydroxide, 12 parts deionized water.
  • the mass percentage of each component in copper-based solder powder is: Mn28.0%, Ni28.0%, Co6.0%, B0.3%, Li0.4%, Na0.2%, K0.15%, Cu margin.
  • the specific preparation method is basically the same as that of Example 1, except that in step (2), the steam pressure is 0.5 MPa, and the reaction time is 5.0 h.
  • the preparation method of the solder paste for stainless steel flux-free brazing of the present embodiment the parts by weight of the raw materials used consist of: 76 parts of copper-based solder powder, 3 parts of nano silicon dioxide, 3 parts of sodium hydroxide, 14 parts deionized water.
  • the mass percentage of each component in copper-based solder powder is: Mn29.0%, Ni29.0%, Co4.0%, B0.4%, Li0.5%, Na0.1%, K0.2%, Cu margin.
  • Concrete preparation method is with embodiment 1.
  • the preparation method of the solder paste for stainless steel flux-free brazing of the present embodiment the parts by weight of the raw materials used consist of: 80 parts of copper-based solder powder, 5 parts of nano silicon dioxide, 2 parts of sodium hydroxide, 15 parts deionized water.
  • the mass percentage of each component in copper-based solder powder is: Mn30.0%, Ni30.0%, Co5.0%, B0.5%, Li0.6%, Na0.2%, K0.3%, Cu margin.
  • Concrete preparation method is with embodiment 1.
  • step (3) the reaction is controlled under a pressure of 0.3 to 0.5 MPa for 3.0 to 5.0 hours, for example, the reaction is carried out at 0.5 MPa for 3.0 hours. h, or under 0.4MPa to react for 5.0h, the reaction effect is basically equivalent to that of Example 1.
  • solder paste for stainless steel flux-free brazing of the present invention respectively correspond to the solder paste obtained by the preparation methods of the above-mentioned Examples 1-5, and will not be described in detail here.
  • the purpose of this experiment example is to compare the shear strength of brazing joints with different solders.
  • the base metal of the test is a stainless steel plate with a thickness of 3 mm, a width of 20 mm, and a length of 80 mm.
  • Brazing gas-shielded brazing temperature needs to be maintained between 1170 ° C ⁇ 1200 ° C), and then respectively adopt the solder paste of embodiments 1 to 5 to carry out the flux-free induction brazing of 304 stainless steel plates in the atmosphere (brazing The welding temperature is between 1050°C and 1100°C), and the six joints are processed into standard shear specimens (according to the provisions of GB/T 11364-2008), and the shear strength of the comparison joints is tested.
  • Table 1 The results are shown in Table 1.

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Abstract

Disclosed is a braze paste for fluxless brazing of stainless steel. The braze paste is mainly composed of water, sodium silicate, nanosilicon dioxide and a copper-based braze material. The braze paste is prepared from the following raw materials in parts by weight: 70-80 parts of a copper-based braze material, 3-5 parts of nanosilicon dioxide, 1-3 parts of sodium hydroxide, and 10-15 parts of water. According to the braze paste, the paste comprising water, sodium silicate, and nanosilicon dioxide is dehydrated at a high temperature during brazing to form a thin film, wherein the nanosilicon dioxide can construct a three-dimensional network structure that has a large surface area and great activity and would enhance the strength and high temperature resistance of the thin film, so that a high-temperature-resistant thin film is formed. The thin film isolates air, protects a surface to be brazed and a molten braze material from being oxidized, and achieves fluxless brazing of stainless steel in an atmospheric environment; in addition, nanosilicon dioxide particles are pinned in a brazing seam and also facilitate the enhancement of the strength of a stainless steel joint. Also disclosed are a preparation method for a braze paste, an application, and a copper-manganese-nickel-cobalt braze material.

Description

一种不锈钢无钎剂钎焊用钎料膏及其制备方法、铜锰镍钴钎料和应用A kind of solder paste for stainless steel flux-free brazing and its preparation method, copper-manganese-nickel-cobalt solder and application 技术领域technical field
本发明属于钎焊材料技术领域，具体涉及一种不锈钢无钎剂钎焊用钎料膏及其制备方法、铜锰镍钴钎料和应用。The invention belongs to the technical field of brazing materials, and in particular relates to a solder paste for stainless steel flux-free brazing, a preparation method thereof, a copper-manganese-nickel-cobalt solder and applications thereof.
背景技术Background technique
不锈钢具有优越的高温性能和良好的耐腐蚀性能，被广泛用于换热器管路的制造。近年来，不锈钢换热器成为冶金、化工、能源、交通、轻工、食品等工业部门普遍采用的热交换装置。钎焊是不锈钢换热器管路制造的关键环节，决定着换热器的使用寿命。随着人们生活质量的提升，对不锈钢换热器焊接质量的要求越来越高。不锈钢换热器的焊接质量很大程度上依赖于所用的钎焊材料。Stainless steel has superior high temperature performance and good corrosion resistance, and is widely used in the manufacture of heat exchanger piping. In recent years, stainless steel heat exchangers have become heat exchange devices commonly used in metallurgy, chemical industry, energy, transportation, light industry, food and other industrial sectors. Brazing is a key link in the manufacture of stainless steel heat exchanger piping, which determines the service life of the heat exchanger. With the improvement of people's quality of life, the requirements for the welding quality of stainless steel heat exchangers are getting higher and higher. The welding quality of stainless steel heat exchangers is largely dependent on the brazing material used.
航空工业广泛使用的H1CuNi30-2-0.2(Ni27～30；Si1.5～2.0；B0.2，Cu余量)，熔化温度范围1080～1200℃，工作温度可达600℃(邹喜，《钎焊》，高温铜基钎料)，具有高温性能好、成本低廉、与不锈钢相容性好的优点，常用于保护气氛炉中钎焊不锈钢。但是，现有的H1CuNi30-2-0.2钎料不具有自钎性，气氛炉中钎焊不锈钢时，钎焊温度低于1000℃时不锈钢表面致密的氧化膜较难去除，温度高于1000℃时不锈钢晶粒长大，均影响不锈钢焊接质量且成本较高。H1CuNi30-2-0.2铜基钎料采用钎剂在大气环境下钎焊不锈钢时，可以获得较好接头，但是，钎剂大多含有氟化物，钎焊过程中易挥发，污染环境、危害人体健康；残留的钎剂残渣腐蚀性强，易腐蚀不锈钢管路，造成泄漏，影响不锈钢换热器的使用寿命。H1CuNi30-2-0.2 (Ni27～30; Si1.5～2.0; B0.2, Cu balance) widely used in the aviation industry has a melting temperature range of 1080～1200°C and a working temperature of up to 600°C (Zou Xi, Brazing Welding", high-temperature copper-based solder), has the advantages of good high-temperature performance, low cost, and good compatibility with stainless steel, and is often used for brazing stainless steel in protective atmosphere furnaces. However, the existing H1CuNi30-2-0.2 solder does not have self-brazing properties. When brazing stainless steel in an atmosphere furnace, the dense oxide film on the surface of the stainless steel is difficult to remove when the brazing temperature is lower than 1000 ° C. When the temperature is higher than 1000 ° C The growth of stainless steel grains affects the welding quality of stainless steel and the cost is high. When H1CuNi30-2-0.2 copper-based solder uses flux to braze stainless steel in an atmospheric environment, a better joint can be obtained. However, most of the flux contains fluoride, which is volatile during brazing, pollutes the environment, and endangers human health; The remaining flux residues are highly corrosive and easily corrode the stainless steel pipeline, causing leakage and affecting the service life of the stainless steel heat exchanger.
发明内容Contents of the invention
本发明的目的在于提供一种不锈钢无钎剂钎焊用钎料膏，可在大气环境下实现不锈钢的无钎剂钎焊，提高接头强度。The purpose of the present invention is to provide a solder paste for stainless steel flux-free brazing, which can realize flux-free brazing of stainless steel in an atmospheric environment and improve joint strength.
本发明的第二个目的是提供上述不锈钢无钎剂钎焊用钎料膏的制备方法。The second object of the present invention is to provide a preparation method of the above-mentioned solder paste for stainless steel flux-free brazing.
本发明的第三个目的是提供一种不锈钢钎焊用铜锰镍钴钎料。The third object of the present invention is to provide a copper-manganese-nickel-cobalt solder for stainless steel brazing.
本发明的第四个目的是提供上述钎料膏在感应钎焊不锈钢方面的应用。The fourth object of the present invention is to provide the application of the above solder paste in induction brazing stainless steel.
为实现上述目的，本发明的不锈钢无钎剂钎焊用钎料膏的技术方案是：For achieving the above object, the technical scheme of the solder paste for stainless steel brazing without flux of the present invention is:
一种不锈钢无钎剂钎焊用钎料膏，所述钎料膏主要由水、硅酸钠、纳米二氧化硅和铜基钎料组成；所述钎料膏由以下重量份的原料制成：铜基钎料70～80份，纳米二氧化硅3～5 份，氢氧化钠1～3份，水10～15份；所述铜基钎料由以下质量百分比的组分组成：Mn 26.0～30.0％、Ni 26.0～30.0％、Co 4.0～6.0％、B 0.1～0.5％、Li 0.1～0.6％、Na 0.1～0.2％、K 0.01～0.3％，Cu余量。A solder paste for stainless steel brazing without flux, the solder paste is mainly composed of water, sodium silicate, nano silicon dioxide and copper-based solder; the solder paste is made of the following raw materials in parts by weight : 70-80 parts of copper-based solder, 3-5 parts of nano silicon dioxide, 1-3 parts of sodium hydroxide, 10-15 parts of water; the copper-based solder is composed of the following components in mass percentage: Mn 26.0 ～30.0%, Ni 26.0～30.0%, Co 4.0～6.0%, B 0.1～0.5%, Li 0.1～0.6%, Na 0.1～0.2%, K 0.01～0.3%, Cu balance.
本发明的钎料膏，含有水、硅酸钠、纳米二氧化硅的膏体，在钎焊时高温脱水形成薄膜，其中的纳米二氧化硅可构建三维网状结构，具有庞大的表面积和极大活性，会增强薄膜的强度和耐高温性，形成耐高温薄膜。该薄膜隔绝空气，保护被钎焊表面、熔融钎料不被氧化，实现大气环境下不锈钢的无钎剂钎焊；同时，纳米二氧化硅粒子钉扎在钎缝中，还有助于增强不锈钢接头强度。The solder paste of the present invention contains water, sodium silicate, and nano-silica paste, which is dehydrated at high temperature to form a thin film during brazing, and the nano-silica in it can build a three-dimensional network structure, which has a large surface area and a very large surface area. High activity will enhance the strength and high temperature resistance of the film and form a high temperature resistant film. The film isolates the air, protects the surface to be brazed, and the molten solder is not oxidized, and realizes flux-free brazing of stainless steel in an atmospheric environment; at the same time, nano-silica particles are pinned in the brazing seam, which also helps to strengthen the stainless steel joint strength.
本发明中，上述改进的铜基钎料，是以H1CuNi30-2-0.2钎料为基，添Mn、Co，降Cu，使钎料熔化温度在930～970℃之间，可以降低钎焊温度。同时，钎料中加入一定含量的B、Li元素，钎料具自钎性能。这是因为B、Li能还原不锈钢表面氧化物，如Cr 2O 3，且还原产物熔点低于钎焊温度，以液态薄膜形式浮在母材和熔化钎料表面起保护作用。但是，B氧化物的黏度很大，会妨碍钎料铺展。为此，又加入微量的Na、K元素，Na、K氧化物黏度小，可以减小还原产物的黏度，促进去膜润湿及钎料铺展，增强钎料自钎性能。 In the present invention, the above-mentioned improved copper-based solder is based on H1CuNi30-2-0.2 solder, adding Mn, Co, and reducing Cu, so that the melting temperature of the solder is between 930 and 970 ° C, which can reduce the brazing temperature . At the same time, a certain amount of B and Li elements are added to the solder, and the solder has self-brazing properties. This is because B and Li can reduce oxides on the surface of stainless steel, such as Cr 2 O 3 , and the melting point of the reduction product is lower than the brazing temperature, and it floats in the form of a liquid film on the surface of the base metal and the molten solder to protect it. However, the viscosity of B oxide is very high, which will hinder the spreading of solder. For this reason, a small amount of Na and K elements are added. The viscosity of Na and K oxides is small, which can reduce the viscosity of the reduction product, promote the wetting of the film and the spreading of the solder, and enhance the self-brazing performance of the solder.
为进一步提高接头强度，优选的，所述钎料膏由以下重量份的原料制成：铜基钎料74～80份，纳米二氧化硅3～5份，氢氧化钠1～3份，水12～15份。更优选的，所述铜基钎料由以下质量百分比的组分组成：Mn 28.0～30.0％、Ni 28.0～30.0％、Co 4.0～6.0％、B 0.3～0.5％、Li 0.4～0.6％、Na 0.1～0.2％、K 0.15～0.3％，Cu余量。In order to further improve the joint strength, preferably, the solder paste is made of the following raw materials in parts by weight: 74 to 80 parts of copper-based solder, 3 to 5 parts of nano silicon dioxide, 1 to 3 parts of sodium hydroxide, water 12 to 15 servings. More preferably, the copper-based solder is composed of the following components by mass percentage: Mn 28.0-30.0%, Ni 28.0-30.0%, Co 4.0-6.0%, B 0.3-0.5%, Li 0.4-0.6%, Na 0.1～0.2%, K 0.15～0.3%, Cu balance.
优选的，所述纳米二氧化硅的粒度为30～50nm。Preferably, the particle size of the nano silicon dioxide is 30-50 nm.
本发明的不锈钢钎焊用铜锰镍钴钎料的技术方案是：The technical scheme of copper-manganese-nickel-cobalt solder for stainless steel brazing of the present invention is:
一种不锈钢钎焊用铜锰镍钴钎料，由以下质量百分比的组分组成：Mn 26.0～30.0％、Ni 26.0～30.0％、Co 4.0～6.0％、B 0.1～0.5％、Li 0.1～0.6％、Na 0.1～0.2％、K 0.01～0.3％，Cu余量。A copper-manganese-nickel-cobalt solder for stainless steel brazing, which consists of the following components in mass percentage: Mn 26.0-30.0%, Ni 26.0-30.0%, Co 4.0-6.0%, B 0.1-0.5%, Li 0.1-0.6 %, Na 0.1-0.2%, K 0.01-0.3%, Cu balance.
本发明的不锈钢钎焊用铜锰镍钴钎料，与H1CuNi30-2-0.2钎料相比，钎焊温度低(有利于抑制不锈钢晶粒的长大)，润湿铺展能力强，针对常规匹配钎剂使用的情形，可减少钎剂用量或不用钎剂。Compared with the H1CuNi30-2-0.2 brazing filler metal, the copper-manganese-nickel-cobalt brazing material for stainless steel brazing of the present invention has low brazing temperature (beneficial for suppressing the growth of stainless steel crystal grains), strong wetting and spreading ability, and is aimed at conventional matching In the case of using flux, the amount of flux can be reduced or no flux can be used.
更优选的，所述不锈钢钎焊用铜锰镍钴钎料由以下质量百分比的组分组成Mn 28.0～30.0％、Ni 28.0～30.0％、Co 4.0～6.0％、B 0.3～0.5％、Li 0.4～0.6％、Na 0.1～0.2％、K 0.15～0.3％，Cu余量。More preferably, the copper-manganese-nickel-cobalt solder for stainless steel brazing consists of the following components in mass percentage: Mn 28.0-30.0%, Ni 28.0-30.0%, Co 4.0-6.0%, B 0.3-0.5%, Li 0.4 ~0.6%, Na 0.1~0.2%, K 0.15~0.3%, Cu balance.
本发明的不锈钢无钎剂钎焊用钎料膏的制备方法的技术方案是：The technical scheme of the preparation method of the solder paste for stainless steel brazing without flux of the present invention is:
一种不锈钢无钎剂钎焊用钎料膏的制备方法，包括以下步骤：A preparation method of solder paste for stainless steel flux-free brazing, comprising the following steps:
1)将氢氧化钠和水配置碱性水溶液；1) Sodium hydroxide and water are configured into an alkaline aqueous solution;
2)将步骤1)所得碱性水溶液和纳米二氧化硅在高于常压条件下进行反应，得到悬浊液；2) reacting the alkaline aqueous solution obtained in step 1) with nano silicon dioxide under conditions higher than normal pressure to obtain a suspension;
3)悬浊液和铜基钎料粉混匀形成均匀膏状，得到钎料膏。3) The suspension and the copper-based solder powder are mixed evenly to form a uniform paste to obtain a solder paste.
本发明的不锈钢无钎剂钎焊用钎料膏的制备方法，制备工艺简单，所得钎料膏的稳定性高，可有效改善不锈钢钎焊的钎焊效果。The preparation method of the solder paste for stainless steel brazing without flux has a simple preparation process, the obtained solder paste has high stability, and can effectively improve the brazing effect of stainless steel brazing.
优选的，步骤2)中，所述高于常压条件指蒸汽压力为0.3～0.5MPa。所述反应的时间为3.0～5.0h。Preferably, in step 2), the above-atmospheric pressure condition refers to a steam pressure of 0.3-0.5 MPa. The reaction time is 3.0-5.0 hours.
上述钎料膏的应用的技术方案是：上述钎料膏在感应钎焊不锈钢中的应用。The technical solution for the application of the above-mentioned solder paste is: the application of the above-mentioned solder paste in induction brazing stainless steel.
优选的，应用时，在大气环境、无钎剂下钎焊连接不锈钢。Preferably, during application, the stainless steel is brazed and connected in an atmospheric environment without flux.
钎焊连接不锈钢时，使用上述钎料膏，不含钎剂，可在大气环境下实现不锈钢的快速感应钎焊，不污染环境，绿色环保。When brazing to connect stainless steel, the above-mentioned solder paste is used without brazing flux, which can realize rapid induction brazing of stainless steel in the atmospheric environment, does not pollute the environment, and is green and environmentally friendly.
附图说明Description of drawings
图1为本发明的钎料膏的制备示意图；Fig. 1 is the preparation schematic diagram of solder paste of the present invention;
图2为现有H1CuNi30-2-0.2钎料在大气环境下进行无钎剂铺展性能试验时的铺展形貌；Fig. 2 is the spreading morphology when the existing H1CuNi30-2-0.2 brazing filler metal is carried out without flux spreading performance test under atmospheric environment;
图3为本发明实施例5所得钎料膏在大气环境下进行无钎剂铺展性能试验时的铺展形貌。Fig. 3 is the spreading morphology of the solder paste obtained in Example 5 of the present invention when the flux-free spreading performance test is performed in an atmospheric environment.
具体实施方式Detailed ways
本发明中，纳米二氧化硅与氢氧化钠发生的反应如下：SiO 2+2NaOH＝Na 2SiO 3+H 2O。 In the present invention, the reaction between nano silicon dioxide and sodium hydroxide is as follows: SiO 2 +2NaOH=Na 2 SiO 3 +H 2 O.
反应时，控制纳米二氧化硅的量相对过量，与氢氧化钠反应消耗掉一部分纳米二氧化硅，另一部分残留在液体中形成悬浊液。此悬浊液高温脱水形成一层薄膜，其中多余的纳米二氧化硅为三维网状结构，具有庞大的表面积和极大活性，会增强薄膜的强度和耐高温性，形成耐高温薄膜。该薄膜隔绝空气，保护被钎焊表面、熔融钎料不被氧化。纳米二氧化硅粒子钉扎在钎缝中，还有助于增强不锈钢接头强度。During the reaction, the amount of nano silicon dioxide is controlled to be relatively excessive, and the reaction with sodium hydroxide consumes a part of the nano silicon dioxide, and the other part remains in the liquid to form a suspension. The suspension is dehydrated at high temperature to form a thin film, in which the excess nano-silica is a three-dimensional network structure with a large surface area and great activity, which will enhance the strength and high temperature resistance of the film and form a high temperature resistant film. The film isolates the air, protects the surface to be brazed and the molten solder from being oxidized. The nano-silica particles are pinned into the brazing joint and also help to strengthen the stainless steel joint.
总之，上述悬浊液一方面可增强粘液脱水所形成薄膜的耐高温性，另一方面其中的纳米二氧化硅会钉扎在钎缝，增强接头强度。In short, on the one hand, the above-mentioned suspension can enhance the high temperature resistance of the film formed by mucus dehydration, and on the other hand, the nano-silica in it will be pinned to the brazing joint to enhance the strength of the joint.
进一步配合铜基钎料的改进，可以更好地实现不锈钢在大气环境下的无钎剂快速感应钎焊，获得高强度接头。Further cooperation with the improvement of copper-based solder can better realize flux-free rapid induction brazing of stainless steel in an atmospheric environment and obtain high-strength joints.
一、本发明的不锈钢无钎剂钎焊用钎料膏的制备方法的具体实施例One, the specific embodiment of the preparation method of solder paste for stainless steel flux-free brazing of the present invention
实施例1Example 1
本实施例的不锈钢无钎剂钎焊用钎料膏的制备方法，所用原料的重量份组成为：70份的铜基钎料粉、3份的纳米二氧化硅、3份的氢氧化钠、10份的去离子水；铜基钎料粉中各组分的质量百分比为：Mn26.0％、Ni26.0％、Co4.0％、B0.1％、Li0.1％、Na0.1％、K0.01％，Cu余量。The preparation method of the solder paste for stainless steel flux-free brazing of the present embodiment, the parts by weight of the raw materials used consist of: 70 parts of copper-based solder powder, 3 parts of nano silicon dioxide, 3 parts of sodium hydroxide, 10 parts of deionized water; the mass percent of each component in the copper-based solder powder is: Mn26.0%, Ni26.0%, Co4.0%, B0.1%, Li0.1%, Na0.1% , K0.01%, Cu balance.
采用以下步骤进行制备：Prepared using the following steps:
(1)按比例称取各组分，先将氢氧化钠溶解在去离子水中，形成碱性水溶液备用；(1) Take each component in proportion, and first dissolve sodium hydroxide in deionized water to form an alkaline aqueous solution for subsequent use;
(2)将纳米二氧化硅(30～50nm)加入步骤(1)碱性水溶液中，放入高压反应釜内，在0.3MPa蒸汽压力下反应3.0h，形成悬浊液(透明胶状液体+少量二氧化硅)；反应过程示意图如图1所示；(2) Add nano-silica (30-50nm) into step (1) alkaline aqueous solution, put it in a high-pressure reactor, and react for 3.0 hours under 0.3MPa steam pressure to form a suspension (transparent colloidal liquid + a small amount of silicon dioxide); the reaction process schematic diagram is as shown in Figure 1;
(3)将铜基钎料粉加入步骤(2)的悬浊液体中，混合搅拌形成均匀膏状，即得到钎料膏。(3) Add copper-based solder powder into the suspension liquid in step (2), mix and stir to form a uniform paste, and obtain solder paste.
实施例2Example 2
本实施例的不锈钢无钎剂钎焊用钎料膏的制备方法，所用原料的重量份组成为：72份的铜基钎料粉、4份的纳米二氧化硅、2份的氢氧化钠、11份的去离子水；铜基钎料粉中各组分的质量百分比为：Mn27.0％、Ni27.0％、Co5.0％、B0.2％、Li0.2％、Na0.1％、K0.1％，Cu余量。具体制备方法与实施例1基本相同，区别仅在于：步骤(2)中，蒸汽压力为0.4MPa，反应时间为4.0h。The preparation method of the solder paste for stainless steel flux-free brazing of the present embodiment, the parts by weight of the raw materials used consist of: 72 parts of copper-based solder powder, 4 parts of nano silicon dioxide, 2 parts of sodium hydroxide, 11 parts of deionized water; the mass percent of each component in the copper-based solder powder is: Mn27.0%, Ni27.0%, Co5.0%, B0.2%, Li0.2%, Na0.1% , K0.1%, Cu balance. The specific preparation method is basically the same as that of Example 1, except that in step (2), the steam pressure is 0.4 MPa, and the reaction time is 4.0 h.
实施例3Example 3
本实施例的不锈钢无钎剂钎焊用钎料膏的制备方法，所用原料的重量份组成为：74份的铜基钎料粉、5份的纳米二氧化硅、1份的氢氧化钠、12份的去离子水。铜基钎料粉中各组分的质量百分比为：Mn28.0％、Ni28.0％、Co6.0％、B0.3％、Li0.4％、Na0.2％、K0.15％，Cu余量。The preparation method of the solder paste for stainless steel flux-free brazing of the present embodiment, the parts by weight of the raw materials used consist of: 74 parts of copper-based solder powder, 5 parts of nano silicon dioxide, 1 part of sodium hydroxide, 12 parts deionized water. The mass percentage of each component in copper-based solder powder is: Mn28.0%, Ni28.0%, Co6.0%, B0.3%, Li0.4%, Na0.2%, K0.15%, Cu margin.
具体制备方法与实施例1基本相同，区别仅在于：步骤(2)中，蒸汽压力为0.5MPa，反应时间为5.0h。The specific preparation method is basically the same as that of Example 1, except that in step (2), the steam pressure is 0.5 MPa, and the reaction time is 5.0 h.
实施例4Example 4
本实施例的不锈钢无钎剂钎焊用钎料膏的制备方法，所用原料的重量份组成为：76份的铜基钎料粉、3份的纳米二氧化硅、3份的氢氧化钠、14份的去离子水。铜基钎料粉中各组分的质量百分比为：Mn29.0％、Ni29.0％、Co4.0％、B0.4％、Li0.5％、Na0.1％、K0.2％， Cu余量。具体制备方法同实施例1。The preparation method of the solder paste for stainless steel flux-free brazing of the present embodiment, the parts by weight of the raw materials used consist of: 76 parts of copper-based solder powder, 3 parts of nano silicon dioxide, 3 parts of sodium hydroxide, 14 parts deionized water. The mass percentage of each component in copper-based solder powder is: Mn29.0%, Ni29.0%, Co4.0%, B0.4%, Li0.5%, Na0.1%, K0.2%, Cu margin. Concrete preparation method is with embodiment 1.
实施例5Example 5
本实施例的不锈钢无钎剂钎焊用钎料膏的制备方法，所用原料的重量份组成为：80份的铜基钎料粉、5份的纳米二氧化硅、2份的氢氧化钠、15份的去离子水。铜基钎料粉中各组分的质量百分比为：Mn30.0％、Ni30.0％、Co5.0％、B0.5％、Li0.6％、Na0.2％、K0.3％，Cu余量。具体制备方法同实施例1。The preparation method of the solder paste for stainless steel flux-free brazing of the present embodiment, the parts by weight of the raw materials used consist of: 80 parts of copper-based solder powder, 5 parts of nano silicon dioxide, 2 parts of sodium hydroxide, 15 parts deionized water. The mass percentage of each component in copper-based solder powder is: Mn30.0%, Ni30.0%, Co5.0%, B0.5%, Li0.6%, Na0.2%, K0.3%, Cu margin. Concrete preparation method is with embodiment 1.
在本发明的不锈钢无钎剂钎焊用钎料膏的制备方法的其他实施例中，步骤(3)中，控制0.3～0.5MPa的压力下反应3.0～5.0h，例如在0.5MPa下反应3.0h，或者在0.4MPa下反应5.0h，反应效果与实施例1基本相当。In other embodiments of the preparation method of the solder paste for stainless steel flux-free brazing of the present invention, in step (3), the reaction is controlled under a pressure of 0.3 to 0.5 MPa for 3.0 to 5.0 hours, for example, the reaction is carried out at 0.5 MPa for 3.0 hours. h, or under 0.4MPa to react for 5.0h, the reaction effect is basically equivalent to that of Example 1.
二、本发明的不锈钢无钎剂钎焊用钎料膏的具体实施例，分别对应上述实施例1～5的制备方法所得钎料膏，在此不再详述。2. The specific examples of the solder paste for stainless steel flux-free brazing of the present invention respectively correspond to the solder paste obtained by the preparation methods of the above-mentioned Examples 1-5, and will not be described in detail here.
三、本发明的不锈钢钎焊用铜锰镍钴钎料的具体实施例，分别对应上述实施例1～5的铜基钎料，在此不再详述。3. Specific examples of the copper-manganese-nickel-cobalt brazing filler metal for stainless steel brazing of the present invention correspond to the copper-based brazing filler metals of the above-mentioned embodiments 1-5 respectively, and will not be described in detail here.
四、实验例钎料膏的应用说明4. Application instructions of solder paste in experimental example
实验例1Experimental example 1
采用H1CuNi30-2-0.2钎料和实施例5的钎料膏，在304不锈钢板(长40mm×宽40mm×厚3mm)上进行无钎剂铺展性能试验，在大气环境下，快速感应加热到1000℃，对比两种接头的润湿铺展形貌，试验结果见图2和图3。Adopt H1CuNi30-2-0.2 brazing filler metal and the brazing filler metal paste of embodiment 5, on 304 stainless steel plates (long 40mm * wide 40mm * thick 3mm), carry out no brazing flux spreading performance test, under atmospheric environment, rapid induction heating is to 1000 ℃, comparing the wetting and spreading morphology of the two joints, the test results are shown in Figure 2 and Figure 3.
由图2和图3可以看出，H1CuNi30-2-0.2钎料不在钢板上铺展，几乎完全氧化，而实施例5的钎料膏可在钢板上铺展润湿，且润湿性能较好。It can be seen from Figure 2 and Figure 3 that the H1CuNi30-2-0.2 solder does not spread on the steel plate, and is almost completely oxidized, while the solder paste of Example 5 can be spread and wetted on the steel plate, and has better wettability.
实验例2Experimental example 2
本实验例的目的是对比不同钎料钎焊接头的剪切强度，试验母材为3mm厚、20mm宽、80mm长的不锈钢板，先采用H1CuNi30-2-0.2钎料进行304不锈钢板的气保护钎焊(气保护钎焊温度需维持在1170℃～1200℃之间)，接着再分别采用实施例1～5的钎料膏在大气环境下进行304不锈钢板的无钎剂感应钎焊(钎焊温度在1050℃～1100℃)，并将六种接头加工成标准剪切试样(按照GB/T 11364-2008的规定)，测试对比接头的剪切强度，结果如表1所示。The purpose of this experiment example is to compare the shear strength of brazing joints with different solders. The base metal of the test is a stainless steel plate with a thickness of 3 mm, a width of 20 mm, and a length of 80 mm. Brazing (gas-shielded brazing temperature needs to be maintained between 1170 ° C ~ 1200 ° C), and then respectively adopt the solder paste of embodiments 1 to 5 to carry out the flux-free induction brazing of 304 stainless steel plates in the atmosphere (brazing The welding temperature is between 1050°C and 1100°C), and the six joints are processed into standard shear specimens (according to the provisions of GB/T 11364-2008), and the shear strength of the comparison joints is tested. The results are shown in Table 1.
表1钎缝的剪切强度The shear strength of table 1 brazing joint
Figure PCTCN2021135209-appb-000001
Figure PCTCN2021135209-appb-000001
Figure PCTCN2021135209-appb-000002
Figure PCTCN2021135209-appb-000002
由表1可以看出，实施例1～5钎料膏钎缝的剪切强度平均值均高于H1CuNi30-2-0.2料钎缝的剪切强度平均值，显示出了较高的接头强度。It can be seen from Table 1 that the average shear strength of solder paste joints in Examples 1 to 5 is higher than that of H1CuNi30-2-0.2 solder joints, showing higher joint strength.

Claims (10)

  1. 一种不锈钢无钎剂钎焊用钎料膏，其特征在于，所述钎料膏主要由水、硅酸钠、纳米二氧化硅和铜基钎料组成；所述钎料膏由以下重量份的原料制成：铜基钎料70～80份，纳米二氧化硅3～5份，氢氧化钠1～3份，水10～15份；所述铜基钎料由以下质量百分比的组分组成：Mn 26.0～30.0％、Ni 26.0～30.0％、Co 4.0～6.0％、B 0.1～0.5％、Li 0.1～0.6％、Na 0.1～0.2％、K 0.01～0.3％，Cu余量。A kind of solder paste for stainless steel without flux brazing, it is characterized in that, described solder paste mainly is made up of water, sodium silicate, nano silicon dioxide and copper-based solder; Described solder paste consists of the following parts by weight Made of raw materials: 70-80 parts of copper-based solder, 3-5 parts of nano-silicon dioxide, 1-3 parts of sodium hydroxide, and 10-15 parts of water; the copper-based solder consists of the following components in mass percentage Composition: Mn 26.0-30.0%, Ni 26.0-30.0%, Co 4.0-6.0%, B 0.1-0.5%, Li 0.1-0.6%, Na 0.1-0.2%, K 0.01-0.3%, Cu balance.
  2. 如权利要求1所述的不锈钢无钎剂钎焊用钎料膏，其特征在于，所述钎料膏由以下重量份的原料制成：铜基钎料74～80份，纳米二氧化硅3～5份，氢氧化钠1～3份，水12～15份。The solder paste for stainless steel flux-free brazing according to claim 1, wherein the solder paste is made of the following raw materials in parts by weight: 74 to 80 parts of copper-based solder, 3 parts of nano silicon dioxide ～5 parts, 1～3 parts of sodium hydroxide, 12～15 parts of water.
  3. 如权利要求2所述的不锈钢无钎剂钎焊用钎料膏，其特征在于，所述铜基钎料由以下质量百分比的组分组成：Mn 28.0～30.0％、Ni 28.0～30.0％、Co 4.0～6.0％、B 0.3～0.5％、Li 0.4～0.6％、Na 0.1～0.2％、K 0.15～0.3％，Cu余量。The solder paste for stainless steel flux-free brazing according to claim 2, wherein the copper-based solder is composed of the following components by mass percentage: Mn 28.0-30.0%, Ni 28.0-30.0%, Co 4.0～6.0%, B 0.3～0.5%, Li 0.4～0.6%, Na 0.1～0.2%, K 0.15～0.3%, Cu balance.
  4. 如权利要求1～3中任一项所述的不锈钢无钎剂钎焊用钎料膏，其特征在于，所述纳米二氧化硅的粒度为30～50nm。The solder paste for stainless steel flux-free brazing according to any one of claims 1-3, characterized in that the particle size of the nano silicon dioxide is 30-50 nm.
  5. 一种不锈钢钎焊用铜锰镍钴钎料，其特征在于，由以下质量百分比的组分组成：Mn 26.0～30.0％、Ni 26.0～30.0％、Co 4.0～6.0％、B 0.1～0.5％、Li 0.1～0.6％、Na 0.1～0.2％、K 0.01～0.3％，Cu余量。A copper-manganese-nickel-cobalt solder for stainless steel brazing, characterized in that it consists of the following components in mass percentage: Mn 26.0-30.0%, Ni 26.0-30.0%, Co 4.0-6.0%, B 0.1-0.5%, Li 0.1-0.6%, Na 0.1-0.2%, K 0.01-0.3%, Cu balance.
  6. 一种如权利要求1～4中任一项所述的不锈钢无钎剂钎焊用钎料膏的制备方法，其特征在于，包括以下步骤：A preparation method of the solder paste for stainless steel flux-free brazing according to any one of claims 1 to 4, characterized in that it comprises the following steps:
    1)将氢氧化钠和水配置碱性水溶液；1) Sodium hydroxide and water are configured into an alkaline aqueous solution;
    2)将步骤1)所得碱性水溶液和纳米二氧化硅在高于常压条件下进行反应，得到悬浊液；2) reacting the alkaline aqueous solution obtained in step 1) with nano silicon dioxide under conditions higher than normal pressure to obtain a suspension;
    3)悬浊液和铜基钎料粉混匀形成均匀膏状，得到钎料膏。3) The suspension and the copper-based solder powder are mixed evenly to form a uniform paste to obtain a solder paste.
  7. 如权利要求6所述的不锈钢无钎剂钎焊用钎料膏的制备方法，其特征在于，步骤2)中，所述高于常压条件指蒸汽压力为0.3～0.5MPa。The preparation method of solder paste for stainless steel flux-free brazing according to claim 6, characterized in that, in step 2), the above normal pressure condition means that the steam pressure is 0.3-0.5 MPa.
  8. 如权利要求7所述的不锈钢无钎剂钎焊用钎料膏的制备方法，其特征在于，步骤2)中，所述反应的时间为3.0～5.0h。The preparation method of solder paste for stainless steel flux-free brazing according to claim 7, characterized in that, in step 2), the reaction time is 3.0-5.0 h.
  9. 一种如权利要求1～4中任一项所述的不锈钢无钎剂钎焊用钎料膏在感应钎焊不锈钢中的应用。An application of the solder paste for stainless steel flux-free brazing as described in any one of claims 1 to 4 in induction brazing stainless steel.
  10. 如权利要求9所述的应用，其特征在于，在大气环境、无钎剂下钎焊连接不锈钢。The application according to claim 9, characterized in that the stainless steel is brazed in an atmospheric environment without flux.
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