WO2019119281A1 - 一种钎料外皮及其制备方法、原位合成金属覆层药芯银钎料及其制备方法、焊接方法和连接体 - Google Patents

一种钎料外皮及其制备方法、原位合成金属覆层药芯银钎料及其制备方法、焊接方法和连接体 Download PDF

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WO2019119281A1
WO2019119281A1 PCT/CN2017/117295 CN2017117295W WO2019119281A1 WO 2019119281 A1 WO2019119281 A1 WO 2019119281A1 CN 2017117295 W CN2017117295 W CN 2017117295W WO 2019119281 A1 WO2019119281 A1 WO 2019119281A1
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WIPO (PCT)
Prior art keywords
solder
core
silver
protective layer
brazing
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Application number
PCT/CN2017/117295
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English (en)
French (fr)
Inventor
龙伟民
钟素娟
路全彬
裴夤崟
何鹏
王德智
马佳
孙华为
纠永涛
王�琦
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郑州机械研究所有限公司
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Application filed by 郑州机械研究所有限公司 filed Critical 郑州机械研究所有限公司
Priority to CN201780096225.3A priority Critical patent/CN111344105B/zh
Priority to US16/073,537 priority patent/US10987747B2/en
Priority to PCT/CN2017/117295 priority patent/WO2019119281A1/zh
Publication of WO2019119281A1 publication Critical patent/WO2019119281A1/zh

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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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
    • B23K1/203—Fluxing, i.e. applying flux onto surfaces
    • 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
    • B23K35/362—Selection of compositions of fluxes
    • 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
    • B23K35/0227—Rods, wires
    • 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
    • B23K35/0233—Sheets, foils
    • 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
    • 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
    • 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
    • B23K2101/00—Articles made by soldering, welding or cutting
    • B23K2101/04—Tubular or hollow articles
    • B23K2101/06—Tubes
    • 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
    • B23K2101/00—Articles made by soldering, welding or cutting
    • B23K2101/32—Wires
    • 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
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/08—Non-ferrous metals or alloys
    • B23K2103/12—Copper or alloys thereof

Definitions

  • the invention relates to the technical field of welding materials, in particular to a brazing material outer skin and a preparation method thereof, an in-situ synthetic metal coating core silver core solder, a preparation method thereof, a welding method and a connecting body.
  • Induction brazing is easy to operate, relatively uniform in heating, economical, does not require heating of the entire part, allows for rapid local heating, and connects high-strength components with minimal loss of strength.
  • control the amount of solder used more and more pre-formed solder (pre-formed solder is customized according to the shape of the weld to form a certain form of solder), the most common The shape is a ring.
  • the solder flux composite solder ring used in pipeline brazing has a core solder ring and a coating solder ring.
  • the cored solder ring has the following disadvantages: the core flux of the core silver solder often contains inorganic substances such as boronic anhydride, potassium fluoride, potassium fluorohydride, etc., which are easy to absorb moisture, and the flux layer after moisture absorption is corroded. Sexually, the brazing filler metal covering the core flux is easily corroded and “rusted”. The “rust” of the brazing filler metal seriously affects the performance and storage stability of the core silver solder.
  • the main function of the flux is to remove the oxide film on the surface of the metal to be welded, to protect the metal to be welded from oxidation, and the flux activity mainly refers to the removal of the oxide film.
  • the flux activity mainly refers to the removal of the oxide film.
  • the surface of Cr 2 O 3 , TiO 2 and MnO 2 is relatively stable and difficult to remove; it seriously affects the brazing reliability of the core silver solder.
  • the electroplating or electroless plating adds a process, the operation is complicated, the cost is correspondingly increased, and the environmental pollution is serious.
  • the object of the present invention is to provide a solder outer skin and a preparation method thereof, an in-situ synthetic metal coated core silver solder, a preparation method thereof, a welding method and a joint body to improve storage stability and welding reliability.
  • a brazing filler skin in percentage by weight, comprising:
  • weight percent including:
  • a method for preparing a brazing material outer skin wherein each metal element of the brazing material outer skin is smelted and cast into an ingot, and is preheated at a temperature of 300 to 550 ° C for processing.
  • An in-situ synthetic metal coated core silver solder comprising a core and a brazing filler skin encasing the core, the solder skin comprising:
  • the drug core comprises, by weight percent,
  • Elemental boron micropowder 5.0 ⁇ 10.0%, sodium borohydride 5.0 ⁇ 10.0%, potassium fluoroborate 15.0 ⁇ 30.0%, boric anhydride 25.0 ⁇ 40.0%, sodium fluoride 10.0 ⁇ 30.0%, sodium hydrogen fluoride 2.0 ⁇ 4.0%, copper sulfate 1.0 ⁇ 5.0%.
  • weight percent including:
  • a protective layer formed on an inner surface of the brazing filler metal is further included.
  • the protective layer is a metal coating having a lower melting point than the solder outer skin and being waterproof.
  • the protective layer is a tin layer or an indium layer.
  • the protective layer has a thickness of 0.001 to 0.08 mm.
  • the in-situ synthetic metal coated core silver solder has an axial multi-turn spring structure.
  • a method for preparing an in-situ synthetic metal-clad core silver solder of the present invention comprising:
  • the metal elements of the brazing filler skin are smelted and cast into ingots, and preheated at a temperature of 300 to 550 ° C to be processed into a brazing tube;
  • the dried and pulverized core is loaded into the solder tube.
  • solder tube is passivated prior to filling the core.
  • the ingot is preheated, it is processed into a strip alloy, and the strip alloy is subjected to surface cleaning treatment, followed by passivation treatment, and then the passivated ribbon alloy is dried to be processed into a solder tube.
  • the surface cleaning treatment comprises pickling and ultrasonic water washing; preferably, the drying conditions are a temperature of 100 to 150 ° C and a time of 5 to 10 min.
  • a protective layer is coated on one surface of the strip alloy, and then the strip alloy is rolled into a solder tube, and the protective layer is placed on the inner surface of the solder tube;
  • the protective layer is a metal coating having a melting point lower than that of the solder skin and is waterproof; preferably, the protective layer is a tin layer or an indium layer; preferably, a surface of the strip alloy is sprayed.
  • the protective layer is formed.
  • the drying condition of the drug core is dried at 100-120 ° C for 240 min and above.
  • a brazing method using the in-situ synthetic metal coated core silver solder of the present invention is at least one selected from the group consisting of flame brazing, induction brazing, and electric resistance brazing.
  • the brazing method includes the step of integrally joining the mounting object and the mounted object using the in-situ synthetic metal-clad core silver core solder of the present invention; the mounting object and the mounted object At least one of them is a brazed stainless steel or manganese brass tubing assembly.
  • At least one of the mount and the mounted object is a brazed stainless steel or manganese brass tubing assembly.
  • the in-situ synthetic metal coated core silver solder prepared by the invention realizes self-reaction in the brazing process to apply a copper film on the surface of the brazed metal, the solder core has good wettability, good fluidity, and self-control Brazing action, zinc is not volatile, and the activity of the coating is high, the moisture absorption is weak, the carbon residue is small, the plastic toughness is good, etc.; it is especially suitable for brazing stainless steel, manganese brass and other pipeline components.
  • the stainless steel brazing filler metal of the present invention is used to braze the stainless steel, the brazing efficiency is greatly improved, the operation of plating the nickel layer on the surface of the stainless steel is avoided, and the cost and time are saved.
  • Figure 1 is a schematic view showing the structure of a multi-turn spring-shaped core silver solder
  • Figure 2 is a schematic cross-sectional view of the core silver solder wire
  • Figure 3 is a schematic view of the structure of the core silver solder wire.
  • the present embodiment provides an in-situ synthetic metal coated core silver solder comprising a core 1 and a solder skin 2 encasing the core.
  • the brazing filler skin comprises:
  • solder skin comprises, by weight percent,:
  • the core includes:
  • Elemental boron micropowder 5.0 ⁇ 10.0%, sodium borohydride 5.0 ⁇ 10.0%, potassium fluoroborate 15.0 ⁇ 30.0%, boric anhydride 25.0 ⁇ 40.0%, sodium fluoride 10.0 ⁇ 30.0%, sodium hydrogen fluoride 2.0 ⁇ 4.0%, copper sulfate 1.0 ⁇ 5.0%.
  • the invention adds tin Sn, phosphorus P, nickel Ni, germanium Ge and lithium Li to the conventional silver solder.
  • the addition of several metals cooperates to improve the storage reliability of the core silver solder on the one hand and to improve the soldering reliability on the other hand.
  • brazing filler metal reduces the melting point of the brazing filler metal and improves the fluidity of the brazing filler metal.
  • the addition of nickel to the brazing filler metal improves the reliability after brazing, for example, the strength of the stainless steel joint can be increased.
  • lithium when the brazing metal is stainless steel, lithium can be oxidized to lithium oxide, and the chromium oxide and the chromium oxide on the surface of the stainless steel can form a low melting point composite compound (for example, Li 2 CrO 4 is a low melting point). Substance, its melting point is about 520 ° C).
  • lithium oxide can react with the surrounding water vapor to form a low melting point compound LiOH (melting point of about 450 ° C).
  • the liquid lithium hydroxide can dissolve the oxide film on the surface of the brazed metal which is difficult to remove by the flux, and the lithium hydroxide is in a liquid state.
  • the film is covered on the surface of the brazed metal to protect the brazed metal from oxidation.
  • lithium is a surface active material, which can improve the wettability of the core, and has a large solid solubility in the silver solder, and it is difficult to form an intermetallic compound.
  • solder skin further comprises 0.1 to 0.5% of silicon Si in terms of weight percentage.
  • the zinc volatilizes, causing the melting point of the brazing material to rise, causing pores in the joint to destroy the compactness of the brazing seam; in addition, the zinc vapor is toxic and endangers the health of the operator.
  • the addition of a small amount of silicon to the silver brazing filler metal prevents zinc from volatilizing during brazing. Since the silicon is easily oxidized during brazing and forms a low-melting silicate with the borate in the core, it covers the surface of the solder which is melted into a liquid state, preventing the volatilization of zinc.
  • a certain amount of elemental boron micropowder is added into the drug core to make the drug core have the advantages of high activity and strong membrane removal ability.
  • the drug core has diffused elemental boron micropowder, and the boron powder can quickly remove the oxygen in the brazing micro region after being heated: 4B+3O 2 ⁇ 2B 2 O 3 .
  • the boric anhydride can form a fusible borate with elemental oxides such as copper, iron, zinc and nickel in the bran outer skin: MeO+B 2 O 3 ⁇ MeO ⁇ B 2 O 3 , which easily floats onto the surface of the brazing seam. The flow spreadability of the solder is improved.
  • sodium metaborate reacts with oxygen to form sodium metaborate: NaBH 4 +2O 2 ⁇ NaBO 2 +2H 2 O; sodium metaborate can form a composite compound with lower melting temperature with borate: MeO+2NaBO 2 +B 2 O 3 ⁇ (NaBO 2 ) 2 ⁇ Me(BO 2 ) 2 , easy to float to the surface of the brazing seam.
  • Potassium fluoroborate can reduce chromium oxide in stainless steel, and potassium fluoroborate is thermally decomposed into potassium fluoride and boron trifluoride: KBF 4 ⁇ KF + BF 3 , potassium fluoride can reduce the melting point and surface tension of the flux, and improve Membrane capacity; boron trifluoride reacts with chromium oxide: BF 3 +Cr 2 O 3 ⁇ 2CrF 3 +B 2 O 3 , boronic anhydride can act as a flow aid.
  • sodium fluoride serves to dissolve the base material and the oxide film on the surface of the solder, improve the film removal ability, and has a weaker moisture absorption than the potassium fluoride, and can effectively prevent the core silver solder from absorbing moisture and falling off the skin.
  • Sodium fluorohydride has a melting point of only 160 ° C, which can lower the melting point of the core, and decomposes into sodium fluoride and hydrogen fluoride at high temperature: NaHF 2 ⁇ NaF+HF, and the decomposed components are favorable for removing oxides.
  • the copper sulfate added to the core of the invention reacts after heating, and a copper film is coated on the surface of the metal to be welded, especially after coating the copper film on the surface of the difficult brazing metal (such as stainless steel, manganese brass, etc.). Helps the brazing to proceed smoothly.
  • the difficult brazing metal such as stainless steel, manganese brass, etc.
  • a protective layer formed on the inner surface of the brazing filler metal is further included.
  • the protective layer can further protect the solder skin from corrosion by the core. As shown in FIG. 2, the protective layer 3 separates the core 1 from the solder skin 2.
  • the protective layer 3 protects the brazing filler metal 2 from being rusted by the intermediate core 1 and improves the oxidation resistance and corrosion resistance of the brazing filler metal 2.
  • the protective layer is a metal coating having a lower melting point than the outer skin of the solder and being waterproof.
  • the thickness of the protective layer is 0.001 to 0.08 mm.
  • the protective layer is a tin layer or an indium layer.
  • Tin or indium has a lower melting point (tin melting point of about 232 ° C, indium melting point of about 156.6 ° C), preferentially melted into a liquid state, followed by liquid tin wet spreading (tin wettability is better), liquid tin can dissolve the solder core and Alloying with the core diffusion greatly reduces the melting point of the core and improves its fluidity and wettability.
  • the tin or indium layer is firmly bonded to the brazing material outer skin, and the adhesion is good, the coating layer is complete, the distribution is uniform, the crystal grains are fine and compact, and the porosity is small.
  • the in-situ synthetic metal coated core silver solder has an axial multi-turn spring structure.
  • the form of the in-situ synthetic metal coated core silver solder can be referred to FIG.
  • brazing filler metal of the in-situ synthetic metal-coated core silver solder is a tubular solder tube, and the core is filled in the solder tube.
  • solder tube has a diameter of 1.8 to 3.0 mm, and the solder tube has a wall thickness of 0.3 to 0.5 mm.
  • the cross section of the solder tube is circular or flat, and the cross section can be referred to FIG.
  • the axial multi-turn spring-like structure is wound by a solder tube coated with a core.
  • the shape of the solder tube before winding can be referred to FIG.
  • the embodiment further provides a preparation method of the in-situ synthetic metal coated core silver solder of the invention, comprising:
  • S2 preheats the ingot at a temperature of 300-550 ° C to process into a solder tube; further, the ingot may be pre-heated and then processed into a strip alloy, and the strip alloy is subjected to surface cleaning treatment and then blunt Processing. Further, the surface cleaning treatment includes pickling and ultrasonic washing. The passivated ribbon alloy is then dried to be processed into a solder tube. Further, the drying conditions are a temperature of 100 to 150 ° C and a time of 5 to 10 min.
  • S3 is coated with a protective layer on one surface of the ribbon alloy. Further, before processing into a solder tube, a protective layer is applied to one surface of the strip alloy, and then the strip alloy is rolled into a solder tube, and the protective layer is placed on the inner surface of the solder tube.
  • the protective layer is a metal coating having a melting point lower than that of the brazing filler metal and being waterproof. Further, the protective layer is a tin layer or an indium layer; further, a protective layer is formed on one surface of the strip alloy by spraying. In other embodiments, a protective layer may also be applied to all surfaces of the ribbon alloy.
  • S4 rolls the strip-shaped alloy coated with the protective layer into a solder tube, wherein the side with the protective layer is the inner surface of the silver solder tube.
  • S5 fills the dried and pulverized core in a solder tube. Further, the drying conditions of the core are dried at 100-120 ° C for 240 min and above.
  • S6 is rolled or drawn to form a core silver solder of the desired diameter.
  • steps S2, S6 or S7 may be omitted in some embodiments.
  • the present embodiment also provides a brazing method using the in-situ synthetic metal coated core silver solder of the present invention. Further, the brazing is at least one selected from the group consisting of flame brazing, induction brazing, and electric resistance brazing.
  • the brazing method comprises the step of joining the mounting object and the mounted object by using the in-situ synthetic metal-clad core silver core solder of the present invention; at least one of the mounting object and the mounted object is brazed stainless steel Or manganese brass tubing components.
  • the present embodiment also provides a connecting body in which the in-situ synthetic metal-coated core silver solder of the present invention is used to join the mounting object and the mounted object into one body.
  • At least one of the mounting and the mounted object is a brazed stainless steel or manganese brass tubing assembly.
  • the in-situ synthetic metal-coated core silver solder provided by the embodiment is an axial multi-turn spring structure wound by a core silver solder, and the core silver solder is composed of a drug core 1.
  • the solder skin 2 and the protective layer 3 are composed; wherein the solder skin 2 is coated on the outside of the drug core 1, and the tin layer is on the inner side surface of the solder skin.
  • the solder skin consists of the following components in terms of weight percent:
  • each component of the core is: 8% of elemental boron micropowder, 7% of sodium borohydride, 22% of potassium fluoroborate, 33% of boronic anhydride, 23% of sodium fluoride, 3% of sodium hydrogen fluoride, and 4% of copper sulfate.
  • the in-situ synthetic metal-coated core silver solder of the present embodiment has the same preparation method and core component as the first embodiment, except that the content of each element of the brazing filler metal is: silver Ag 25%, copper Cu 39%, zinc. Zn32%, tin Sn1.75%, phosphorus P0.5%, nickel Ni1.5%, ⁇ Ge0.1%, lithium Li0.15%.
  • the in-situ synthetic metal coated core silver solder of the present embodiment has the same preparation method and core component as the first embodiment, except that the content of each element of the brazing filler metal is: silver Ag 30%, copper Cu 35.4% , zinc Zn31%, tin Sn1.8%, phosphorus P0.4%, nickel Ni1%, ⁇ Ge0.2%, lithium Li0.2%; the weight percentage of each component of the core is: elemental boron micropowder 9% Sodium borohydride 6%, potassium fluoroborate 20%, boronic anhydride 35%, sodium fluoride 24%, sodium hydrogen hydride 2%, copper sulfate 4%.
  • the present embodiment provides a brazing method comprising welding two stainless steel tubes to form a joint body by using the in-situ synthetic metal-clad core silver core solder prepared in Example 1. Brazing is performed by induction brazing.
  • This embodiment also provides a connector in which the above brazing method is welded.
  • the silver core solder of the present embodiment has the same preparation method and core component as the first embodiment. The difference is that the content of each element of the brazing filler metal is: silver Ag 25%, copper Cu 39%, zinc Zn 32%, tin Sn1. 75%.
  • the silver core solder of the present embodiment has the same preparation method and core component as the first embodiment. The difference is that the content of each element of the brazing filler metal is: silver Ag 25%, copper Cu 39%, zinc Zn 32%, tin Sn1. 75%, phosphorus P0.5%.
  • the silver core solder of the present embodiment has the same preparation method and core component as the first embodiment. The difference is that the content of each element of the brazing filler metal is: silver Ag 25%, copper Cu 39%, zinc Zn 32%, tin Sn1. 75%, phosphorus P0.5%, nickel Ni1.5%, ⁇ Ge 0.1%.
  • 100 in-situ synthetic metal coated core silver solders were prepared as experimental samples by the preparation methods of Examples 1-3; 100 core silver solders were prepared as control samples by the preparation methods of Comparative Examples 1-3.
  • 100 in-situ synthetic metal coated core silver solders were prepared as experimental samples by the preparation methods of Examples 1-3; 100 core silver solders were prepared as control samples by the preparation methods of Comparative Examples 1-3.
  • Example 1 370
  • Example 2 375
  • Example 3 380 Comparative example 1 345 Comparative example 2 350 Comparative example 3 370
  • the in-situ synthetic metal coated core silver solder prepared by the invention realizes self-reaction in the brazing process to apply a copper film on the surface of the brazed metal, the solder core has good wettability, good fluidity, and self-control Brazing action, zinc is not volatile, and the activity of the coating is high, the moisture absorption is weak, the carbon residue is small, the plastic toughness is good, etc.; it is especially suitable for brazing stainless steel, manganese brass and other pipeline components.

Abstract

一种原位合成金属覆层药芯银钎料，包括药芯(1)以及包裹所述药芯的钎料外皮(2)，按照重量百分比计，所述钎料外皮包括：银 Ag20.0~36%，铜 Cu35.0~45.0%，锌 Zn27.0~37.0%，锡 Sn1.0~3.0%，磷 P0.1~0.5%，镍 Ni0.5~2.0%，锗 Ge0.1~0.3%，锂 Li0.1~0.3%。按照重量百分比计，所述药芯包括：单质硼微粉 5.0~10.0%，硼氢化钠 5.0~10.0%，氟硼酸钾 15.0~30.0%，硼酐 25.0~40.0%，氟化钠10.0~30.0%，氟氢化钠 2.0~4.0%，硫酸铜 1.0~5.0%。该原位合成金属覆层药芯银钎料实现了钎焊过程中自反应，在被钎焊金属表面涂覆一层铜膜，钎料芯润湿性好、流动性佳、有自钎作用、锌不易挥发，且药皮活性高、吸潮性弱、碳残留少、塑韧性好，适合钎焊不锈钢、锰黄铜等管路组件。还公开了一种钎料外皮及其制备方法，原位合成金属覆层药芯钎料的制备方法，钎焊方法和连接体。

Description

一种钎料外皮及其制备方法、原位合成金属覆层药芯银钎料及其制备方法、焊接方法和连接体 技术领域
本发明涉及焊接材料技术领域，特别是涉及一种钎料外皮及其制备方法、原位合成金属覆层药芯银钎料及其制备方法、焊接方法和连接体。
背景技术
目前，随着高频感应焊机的发展，感应钎焊工艺在管路连接中的应用得到了突飞猛进的发展。感应钎焊操作简便、加热相对均匀、经济性好，不需要加热整个部件，允许快速局部加热，以最小的强度损失连接高强度的元件。为了节约钎料并产生质量稳定的接头，控制钎料的使用量，预成型钎料应用越来越多(预成型钎料是依据焊缝形态定制而成具有一定形态的钎料)，最常见的形态是环状。
管路钎焊中应用的钎料钎剂复合型钎料环有药芯钎料环和药皮钎料环。目前药芯钎料环存在以下缺点：药芯银钎料的芯部钎剂中常含有硼酐、氟化钾、氟氢化钾等无机物，容易吸潮，且吸潮后的钎剂层具有腐蚀性，严重腐蚀包覆芯部钎剂的钎料外皮，易被腐蚀而“生锈”，钎料外皮“生锈”后严重影响药芯银钎料的使用性能和储存稳定性。
为了避免芯部钎剂腐蚀钎料外皮，不得不选用活性较低的钎剂(钎剂主要作用是去除被焊金属表面氧化膜、保护被焊金属不被氧化，钎剂活性主要指去除氧化膜的能力)。钎焊不锈钢和锰黄铜时表面的Cr 2O 3、TiO 2和MnO 2比较稳定，难以去除；严重影响药芯银钎料的钎焊可靠性。目前工程中将难钎焊金属表面镀覆一层铜或镍来改善其钎焊性，但是无论采用电镀还是化学镀增加一道工序、操作复杂、成本也相应增加且对环境污染严重。
发明内容
本发明的目的是提供一种钎料外皮及其制备方法、原位合成金属覆层药芯银钎料及其制备方法、焊接方法和连接体，以提高储存稳定性和焊接可靠性。
本发明解决其技术问题所采用的技术方案是：
一种钎料外皮，按照重量百分比计，包括：
银Ag20.0～36.0％，铜Cu35.0～45.0％，锌Zn27.0～37.0％，锡Sn1.0～3.0％，磷P0.1％～ 0.5％，镍Ni0.5～2.0％，锗Ge0.1～0.3％，锂Li0.1～0.3％。
进一步地，按照重量百分比计，包括：
银Ag25～35％，铜Cu35.0～40.0％，锌Zn27.0～37.0％，锡Sn1.5～3.0％，磷P0.1％～0.4％，镍Ni1.0～1.5％，锗Ge0.15～0.2％，锂Li0.15～0.2％。
一种钎料外皮的制备方法，将所述钎料外皮各金属元素进行熔炼、浇注成铸锭，在300～550℃温度条件下预热后加工成型。
一种原位合成金属覆层药芯银钎料，包括药芯以及包裹所述药芯的钎料外皮，按照重量百分比计，所述钎料外皮包括：
银Ag20.0～36.0％，铜Cu35.0～45.0％，锌Zn27.0～37.0％，锡Sn1.0～3.0％，磷P0.1％～0.5％，镍Ni0.5～2.0％，锗Ge0.1～0.3％，锂Li0.1～0.3％。
按照重量百分比计，所述药芯包括：
单质硼微粉5.0～10.0％，硼氢化钠5.0～10.0％，氟硼酸钾15.0～30.0％，硼酐25.0～40.0％，氟化钠10.0～30.0％，氟氢化钠2.0～4.0％，硫酸铜1.0～5.0％。
进一步地，按照重量百分比计，包括：
银Ag25～35％，铜Cu35.0～40.0％，锌Zn27.0～37.0％，锡Sn1.5～3.0％，磷P0.1％～0.4％，镍Ni1.0～1.5％，锗Ge0.15～0.2％，锂Li0.15～0.2％。
进一步地，还包括形成于所述钎料外皮内表面的保护层。
进一步地，所述保护层为熔点低于所述钎料外皮且防水的金属涂层。
进一步地，所述保护层为锡层或铟层。
进一步地，所述保护层的厚度为0.001～0.08mm。
进一步地，所述原位合成金属覆层药芯银钎料呈轴向多圈簧状结构。
一种本发明的原位合成金属覆层药芯银钎料的制备方法，包括：
将所述钎料外皮的各金属元素进行熔炼、浇注成铸锭，在300～550℃温度条件下预热后加工成钎料管；
将干燥、粉碎后的所述药芯装填在所述钎料管内。
进一步地，在装填药芯前，所述钎料管经过钝化处理。
进一步地，所述铸锭预热后先加工成带状合金，将所述带状合金进行表面清洁处理后进行钝化处理，然后将钝化后的带状合金烘干以加工成钎料管；优选地，表面清洁处理包括酸洗和超声波水洗；优选地，烘干条件为温度100～150℃、时间5～10min。
进一步地，在加工成钎料管前，在带状合金的一个表面涂覆保护层，然后将带状合金卷制成钎料管，并使所述保护层位于钎料管的内表面；优选地，所述保护层为熔点低于所述钎料外皮且防水的金属涂层；优选地，所述保护层为锡层或铟层；优选地，采用喷涂的 方式在带状合金的一个表面形成所述保护层。
进一步地，所述药芯的干燥条件为100-120℃干燥240min及以上。
一种钎焊方法，采用本发明的原位合成金属覆层药芯银钎料。进一步地，钎焊为选自火焰钎焊、感应钎焊和电阻钎焊的至少一种。
进一步地，所述钎焊方法包括采用本发明所述的原位合成金属覆层药芯银钎料将安装物和被安装物接合为一体的步骤；所述安装物和所述被安装物中的至少一者为钎焊不锈钢或者锰黄铜管路组件。
一种连接体，采用本发明的原位合成金属覆层药芯银钎料，使安装物和被安装物接合为一体。
进一步地，所述安装物和所述被安装物中的至少一者为钎焊不锈钢或者锰黄铜管路组件。
与现有技术相比，本发明的优点包括：
本发明制备的原位合成金属覆层药芯银钎料实现了钎焊过程中自反应在被钎焊金属表面涂覆一层铜膜，钎料芯润湿性好、流动性佳、有自钎作用、锌不易挥发，且药皮活性高、吸潮性弱、碳残留少、塑韧性好等优点；特别适合钎焊不锈钢、锰黄铜等管路组件。
进一步地，采用本发明的药芯银钎料钎焊不锈钢时钎焊效率大大提高、避免了在不锈钢表面镀覆镍层操作，节约了成本和时间。
附图说明
图1多圈簧状药芯银钎料结构示意图；
图2药芯银钎料丝横截面结构示意图；
图3药芯银钎料丝结构示意图。
图中：1-药芯，2-钎料外皮，3-保护层。
具体实施方式
在本申请的描述中，还需要说明的是，除非另有明确的规定和限定，术语“设置”、“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以具体情况理解上述术语在本申请中的具体含义。
以下结合附图及实施例对本发明作进一步说明。
如图1和图2所示，本实施方式提供了一种原位合成金属覆层药芯银钎料，包括药芯1以及包裹药芯的钎料外皮2。
其中，按照重量百分比计，钎料外皮包括：
银Ag20.0～36.0％，铜Cu35.0～45.0％，锌Zn27.0～37.0％，锡Sn1.0～3.0％，磷P0.1～0.5％，镍Ni0.5～2.0％，锗Ge0.1～0.3％，锂Li0.1～0.3％。
进一步地，按照重量百分比计，钎料外皮包括：
银Ag25～35％，铜Cu35.0～40.0％，锌Zn27.0～37.0％，锡Sn1.5～3.0％，磷P0.1～0.4％，镍Ni1.0～1.5％，锗Ge0.15～0.2％，锂Li0.15～0.2％。
按照重量百分比计，药芯包括：
单质硼微粉5.0～10.0％，硼氢化钠5.0～10.0％，氟硼酸钾15.0～30.0％，硼酐25.0～40.0％，氟化钠10.0～30.0％，氟氢化钠2.0～4.0％，硫酸铜1.0～5.0％。
本发明在传统银钎料的基础上增加了锡Sn、磷P、镍Ni、锗Ge和锂Li。增加的几种金属相互配合，一方面可以提高药芯银钎料的储存可靠性，另一方面可以提高焊接可靠性。
钎料外皮中加入少量的磷可降低钎料熔点、提高钎料流动性。
钎料外皮加入镍可提高钎焊后的可靠性，例如可以提高不锈钢接头的强度。
加入少量锂具有自钎作用，例如，被钎焊金属为不锈钢时，锂可被氧化成氧化锂，同时氧化锂与不锈钢表面的氧化铬能形成低熔点复合化合物(如Li 2CrO 4为低熔点物质，其熔点约520℃)。
此外，氧化锂能与周围水蒸气反应，形成低熔点化合物LiOH(熔点约450℃)，液态氢氧化锂能溶解钎剂难以去除的被钎焊金属表面的氧化膜，同时，氢氧化锂呈液态薄膜状覆盖于被钎焊金属表面，能保护被钎焊金属不被氧化。另外，锂是表面活性物质，能提高药芯的润湿性，且在银钎料中固溶度较大，不易形成金属间化合物。
锂的含量过少则自钎作用会被削弱甚至消失，而且表面活性变差，锂的含量过高，则会增加钎料外皮的脆性，导致无法实施机械加工。
进一步地，按照重量百分比计，钎料外皮还包括硅Si0.1～0.5％
钎焊时锌挥发，使钎料的熔点升高，接头中产生气孔，破坏钎缝的致密性；另外，锌蒸气有毒，危害操作工健康。在银钎料外皮中加入少量硅可以防止在钎焊时锌挥发。由于钎焊时硅易氧化，并和药芯中的硼酸盐形成低熔点的硅酸盐，覆盖在熔化成液态的钎料表面，阻止锌的挥发。
药芯中加入一定量的单质硼微粉，使药芯具有活性高、去膜能力强等优点，药芯有弥散的单质硼微粉，硼粉受热后能迅速脱去钎缝微区的氧并：4B+3O 2→2B 2O 3。硼酐又能与钎料外皮中的铜、铁、锌、镍等元素氧化物形成易熔的硼酸盐：MeO+B 2O 3→MeO·B 2O 3，容易浮到钎缝表面，提高了钎料的流动铺展性。硼氢化钠与氧气反应生成偏硼酸钠： NaBH 4+2O 2→NaBO 2+2H 2O；偏硼酸钠又能与硼酸盐形成熔化温度更低的复合化合物：MeO+2NaBO 2+B 2O 3→(NaBO 2) 2·Me(BO 2) 2，容易浮到钎缝表面。氟硼酸钾能还原不锈钢中的氧化铬，氟硼酸钾受热分解为氟化钾和三氟化硼：KBF 4→KF+BF 3，氟化钾可以降低钎剂的熔点和表面张力，并提高去膜能力；三氟化硼与氧化铬反应：BF 3+Cr 2O 3→2CrF 3+B 2O 3，硼酐能起到助流作用。
加入氟化钠起到溶解母材和钎料表面氧化膜的作用，提高去膜能力，比氟化钾吸潮性弱，可有效避免药芯银钎料吸潮而脱落掉皮。氟氢化钠的熔点只有160℃，能降低药芯的熔点，在高温时分解为氟化钠和氟化氢：NaHF 2→NaF+HF，分解的组分有利于清除氧化物。
本发明所述药芯中加入硫酸铜经过加热后发生反应会在被焊金属表面涂覆一层铜膜，尤其是在难钎焊金属表面(如不锈钢、锰黄铜等)涂覆铜膜后有助于钎焊顺利进行。
进一步地，还包括形成于钎料外皮内表面的保护层。保护层可以进一步保护钎料外皮不被药芯腐蚀。如图2所示，保护层3可将药芯1和钎料外皮2隔开。保护层3可保护钎料外皮2不被中间药芯1腐蚀而“生锈”，提高钎料外皮2的抗氧化性和耐腐蚀性。
进一步地，保护层为熔点低于钎料外皮且防水的金属涂层。
进一步地，保护层的厚度为0.001～0.08mm。
进一步地，保护层为锡层或铟层。
锡或铟的熔点较低(锡熔点约232℃，铟熔点约156.6℃)，优先熔化成液态，随后液态锡润湿铺展(锡的润湿性较好)，液态锡能溶解钎料芯并与药芯扩散合金化，大大降低了药芯熔点，提高其流动性和润湿性。
锡或铟层与钎料外皮结合牢固、附着力好，涂覆层完整、分布均匀、晶粒细致紧密且孔隙率小。
进一步地，原位合成金属覆层药芯银钎料呈轴向多圈簧状结构。原位合成金属覆层药芯银钎料的形态可以参考图1。
进一步地，原位合成金属覆层药芯银钎料的钎料外皮为管状的钎料管，药芯装填于钎料管内。
进一步地，所述钎料管直径为1.8～3.0mm，钎料管的壁厚为0.3～0.5mm。钎料管横截面为圆形或扁平圆形，截面可以参考图2。轴向多圈簧状结构是由包覆有药芯的钎料管绕制而成，在绕制前钎料管的形态可参考图3。
本实施方式还提供了一种本发明的原位合成金属覆层药芯银钎料的制备方法，包括：
S1将钎料外皮的各金属元素进行熔炼、浇注成铸锭。
S2将铸锭在300～550℃温度条件下预热以加工成钎料管；进一步地，可以先将铸锭预热后先加工成带状合金，将带状合金进行表面清洁处理后进行钝化处理。进一步地，表面 清洁处理包括酸洗和超声波水洗。然后将钝化后的带状合金烘干以加工成钎料管。进一步地，烘干条件为温度100～150℃、时间5～10min。
S3在带状合金的一个表面涂覆保护层。进一步地，在加工成钎料管前，在带状合金的一个表面涂覆保护层，然后将带状合金卷制成钎料管，并使保护层位于钎料管的内表面。保护层为熔点低于钎料外皮且防水的金属涂层。进一步地，保护层为锡层或铟层；进一步地，采用喷涂的方式在带状合金的一个表面形成保护层。在其他实施方式中，也可也在带状合金的所有表面涂覆保护层。
S4将涂覆有保护层的带状合金卷制成钎料管，其中带有保护层的一侧为银钎料管内表面。
S5将干燥、粉碎后的药芯装填在钎料管内。进一步地，药芯的干燥条件为100-120℃干燥240min及以上。
S6通过轧制或拉拔，制成所需直径的药芯银钎料。
S7将药芯银钎料丝绕制成轴向多圈簧状结构。
在一些实施方式中可以省略步骤S2、S6或S7中的至少一个。
本实施方式还提供了一种钎焊方法，采用本发明的原位合成金属覆层药芯银钎料。进一步地，钎焊为选自火焰钎焊、感应钎焊和电阻钎焊的至少一种。
进一步地，钎焊方法包括采用本发明的原位合成金属覆层药芯银钎料将安装物和被安装物接合为一体的步骤；安装物和被安装物中的至少一者为钎焊不锈钢或者锰黄铜管路组件。
本实施方式还提供了一种连接体，采用本发明的原位合成金属覆层药芯银钎料，使安装物和被安装物接合为一体。
进一步地，安装物和被安装物中的至少一者为钎焊不锈钢或者锰黄铜管路组件。
下面结合具体实施例对本发明做进一步的说明。
实施例1
本实施例提供的一种原位合成金属覆层药芯银钎料，由药芯银钎料绕制而成的轴向多圈簧状结构，所述药芯银钎料由药芯1、钎料外皮2和保护层3组成；其中，钎料外皮2包覆在所述药芯1外部，锡层在钎料外皮的内侧表面。
按照重量百分比计，钎料外皮由以下组分组成：
银Ag34％，铜Cu35.8％，锌Zn27％，锡Sn1.5％，磷P0.4％，镍Ni1％，锗Ge 0.15％，锂Li0.15％。
药芯各组分的重量百分比为：单质硼微粉8％，硼氢化钠7％，氟硼酸钾22％，硼酐33％，氟化钠23％，氟氢化钠3％，硫酸铜4％。
本实施例的一种原位合成金属覆层药芯银钎料的制备方法如下：
a)按比例配制钎料外皮所需的各种金属元素并熔炼、浇注成钎料铸锭；并在450℃电阻加热炉内预热，将预热好的铸锭放入挤压设备中挤压，并经轧制、分切制备成厚度0.3～0.5mm、宽度7.0～8.5mm的带状合金，然后经酸洗、再进行超声波(用水)清洗，随后在钝化剂中进行钝化处理，将钝化后的带状合金放入100～150℃的烘箱中烘干5～10min，备用；
b)用喷涂法在的带状合金其中一侧表面涂覆一层厚度为0.001mm的锡；
c)将单质硼微粉、硼氢化钠、氟硼酸钾、硼酐、氟化钠、氟氢化钠、硫酸铜按比例称取各原料配制药芯，混合均匀后在110℃的低真空(真空度0Pa)干燥箱中烘干240min，冷却、粉碎、筛分后待用；
d)将制备好的带状钎料卷制成钎料管(带有涂覆层锡的一侧为钎料管的内表面)，在卷制过程中将制备好的药芯加入钎料管中，通过轧制或拉拔，制成所需直径的药芯银钎料；
e)将药芯银钎料绕制成轴向多圈簧状结构。
实施例2
本实施例的原位合成金属覆层药芯银钎料，其制备方法以及药芯组分与实施例1相同，区别在于，钎料外皮各元素含量为：银Ag25％，铜Cu39％，锌Zn32％，锡Sn1.75％，磷P0.5％，镍Ni1.5％，锗Ge0.1％，锂Li0.15％。
实施例3
本实施例的原位合成金属覆层药芯银钎料，其制备方法以及药芯组分与实施例1相同，区别在于，钎料外皮各元素含量为：银Ag30％，铜Cu35.4％，锌Zn31％，锡Sn1.8％，磷P0.4％，镍Ni1％，锗Ge0.2％，锂Li0.2％；所述药芯各组分的重量百分比为：单质硼微粉9％，硼氢化钠6％，氟硼酸钾20％，硼酐35％，氟化钠24％，氟氢化钠2％，硫酸铜4％。
实施例4
本实施例提供一种钎焊方法，包括采用实施例1制备得到的原位合成金属覆层药芯银钎料将两个不锈钢管焊接形成一个连接体。钎焊采用感应钎焊。
本实施例还提供上述钎焊方法焊接而成的连接体。
对比例1
本实施例的药芯银钎料，其制备方法以及药芯组分与实施例1相同，区别在于，钎料外皮各元素含量为：银Ag25％，铜Cu39％，锌Zn32％，锡Sn1.75％。
对比例2
本实施例的药芯银钎料，其制备方法以及药芯组分与实施例1相同，区别在于，钎料外皮各元素含量为：银Ag25％，铜Cu39％，锌Zn32％，锡Sn1.75％，磷P0.5％。
对比例3
本实施例的药芯银钎料，其制备方法以及药芯组分与实施例1相同，区别在于，钎料外皮各元素含量为：银Ag25％，铜Cu39％，锌Zn32％，锡Sn1.75％，磷P0.5％，镍Ni1.5％，锗Ge0.1％。
试验例
一、“生锈”试验
采用实施例1-3的制备方法分别制备100个原位合成金属覆层药芯银钎料作为实验样品；采用对比例1-3的制备方法分别制备100个药芯银钎料作为对照样品。
将所有的实验样品和对照样品放置在同一个盐雾环境(温度为35℃，NaCl水溶液浓度5％)中；记录样品从开始试验到开始“生锈”所经历的时间，以时间长短作为储存稳定性的评定判据。
表1.实验样品及对照样品的储存稳定性结果
  开始生锈时间(第n天)
实施例1 115
实施例2 120
实施例3 130
对比例1 110
对比例2 112
对比例3 120
二、钎焊可靠性试验
2.1焊缝泄露率
采用实施例1-3的制备方法分别制备100个原位合成金属覆层药芯银钎料作为实验样品；采用对比例1-3的制备方法分别制备100个药芯银钎料作为对照样品。
将所有的实验样品和对照样品按照相同感应钎焊工艺钎焊两个不锈钢管焊接形成一个连接体，每种钎料焊接1000个连接体。采用氦质谱检漏法检测连接体是否泄漏。记录泄漏的连接体数量，用来评价焊缝泄漏率。
表2.实验样品及对照样品的焊缝泄漏率结果
  焊缝泄漏连接体数量
实施例1 1
实施例2 2
实施例3 1
对比例1 5
对比例2 4
对比例3 3
2.2机械性能试验
采用实施例1-3的制备方法分别制备5个原位合成金属覆层药芯银钎料作为实验样品；采用对比例1-3的制备方法分别制备5个药芯银钎料作为对照样品。
将所有的实验样品和对照样品按照相同感应钎焊工艺钎焊两个不锈钢板，形成对接接头，每种钎料焊接5个对接接头。采用力学试验机检测焊接接头的抗拉强度。记录焊接接头抗拉强度值，用来评价焊接接头的机械性能。
表3.实验样品及对照样品的机械性能结果
  抗拉强度MPa
实施例1 370
实施例2 375
实施例3 380
对比例1 345
对比例2 350
对比例3 370
以上所述仅为本发明的优选实施方式而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
工业实用性
本发明制备的原位合成金属覆层药芯银钎料实现了钎焊过程中自反应在被钎焊金属表面涂覆一层铜膜，钎料芯润湿性好、流动性佳、有自钎作用、锌不易挥发，且药皮活性高、吸潮性弱、碳残留少、塑韧性好等优点；特别适合钎焊不锈钢、锰黄铜等管路组件。

Claims (16)

  1. 一种钎料外皮，其特征在于，按照重量百分比计，包括：
    银Ag20.0～36.0％，铜Cu35.0～45.0％，锌Zn27.0～37.0％，锡Sn1.0～3.0％，磷P0.1～0.5％，镍Ni0.5～2.0％，锗Ge0.1～0.3％，锂Li0.1～0.3％。
  2. 根据权利要求1所述的钎料外皮，其特征在于，按照重量百分比计，包括：
    银Ag25～35％，铜Cu35.0～40.0％，锌Zn27.0～37.0％，锡Sn1.5～3.0％，磷P0.1～0.4％，镍Ni1.0～1.5％，锗Ge0.15～0.2％，锂Li0.15～0.2％；优选地，还包括硅Si0.1～0.5％。
  3. 一种根据权利要求1或2所述的钎料外皮的制备方法，其特征在于，将所述钎料外皮各金属元素进行熔炼、浇注成铸锭，在300～550℃温度条件下预热后加工成型。
  4. 一种原位合成金属覆层药芯银钎料，包括药芯以及包裹所述药芯的钎料外皮，其特征在于，
    按照重量百分比计，所述钎料外皮包括：
    银Ag20.0～36.0％，铜Cu35.0～45.0％，锌Zn27.0～37.0％，锡Sn1.0～3.0％，磷P0.1～0.5％，镍Ni0.5～2.0％，锗Ge0.1～0.3％，锂Li0.1～0.3％。
    按照重量百分比计，所述药芯包括：
    单质硼微粉5.0～10.0％，硼氢化钠5.0～10.0％，氟硼酸钾15.0～30.0％，硼酐25.0～40.0％，氟化钠10.0～30.0％，氟氢化钠2.0～4.0％，硫酸铜1.0～5.0％。
  5. 根据权利要求4所述的原位合成金属覆层药芯银钎料，其特征在于，按照重量百分比计，包括：
    银Ag25～35％，铜Cu35.0～40.0％，锌Zn27.0～37.0％，锡Sn1.5～3.0％，磷P0.1～0.4％，镍Ni1.0～1.5％，锗Ge0.15～0.2％，锂Li0.15～0.2％；优选地，所述钎料外皮还包括硅Si0.1～0.5％。
  6. 根据权利要求4或5所述的原位合成金属覆层药芯银钎料，其特征在于，还包括形成于所述钎料外皮内表面的保护层。
  7. 根据权利要求4至6任一项所述的原位合成金属覆层药芯银钎料，其特征在于，所述保护层为熔点低于所述钎料外皮且防水的金属涂层。
  8. 根据权利要求4至7任一项所述的原位合成金属覆层药芯银钎料，其特征在于，所述保护层为锡层或铟层。
  9. 根据权利要求4至8任一项所述的原位合成金属覆层药芯银钎料，其特征在于，所述保护层的厚度为0.001～0.08mm。
  10. 根据权利要求4至9任一项所述的原位合成金属覆层药芯银钎料，其特征在于，所述原位合成金属覆层药芯银钎料呈轴向多圈簧状结构。
  11. 一种根据权利要求4至10任一项所述的原位合成金属覆层药芯银钎料的制备方法，其特征在于，包括：
    将所述钎料外皮的各金属元素进行熔炼、浇注成铸锭，在300～550℃温度条件下预热后加工成钎料管；
    将干燥、粉碎后的所述药芯装填在所述钎料管内。
  12. 根据权利要求11所述的制备方法，其特征在于，在装填药芯前，所述钎料管经过钝化处理。
  13. 根据权利要求11或12所述的制备方法，其特征在于，所述铸锭预热后先加工成带状合金，将所述带状合金进行表面清洁处理后进行钝化处理，然后将钝化后的带状合金烘干以加工成钎料管；优选地，表面清洁处理包括酸洗和超声波水洗；优选地，烘干条件为温度100～150℃、时间5～10min。
  14. 根据权利要求11至13任一项所述的制备方法，其特征在于，在加工成钎料管前，在带状合金的一个表面涂覆保护层，然后将带状合金卷制成钎料管，并使所述保护层位于钎料管的内表面；优选地，所述保护层为熔点低于所述钎料外皮且防水的金属涂层；优选地，所述保护层为锡层或铟层；优选地，采用喷涂的方式在带状合金的一个表面形成所述保护层。
  15. 一种钎焊方法，其特征在于，采用根据权利要求4至10任一项所述的原位合成金属覆层药芯银钎料。
  16. 一种连接体，其特征在于，采用如权利要求4至10任一项所述的原位合成金属覆层药芯银钎料，使安装物和被安装物接合为一体。
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