CN105345304A - Supersaturated brazing filler metal and preparation method thereof - Google Patents
Supersaturated brazing filler metal and preparation method thereof Download PDFInfo
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- CN105345304A CN105345304A CN201510867587.0A CN201510867587A CN105345304A CN 105345304 A CN105345304 A CN 105345304A CN 201510867587 A CN201510867587 A CN 201510867587A CN 105345304 A CN105345304 A CN 105345304A
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- solder
- metal
- brazing filler
- filler metal
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Classifications
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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
-
- 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
- B23K35/001—Interlayers, transition pieces for metallurgical bonding of workpieces
-
- 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
Abstract
The invention discloses supersaturated brazing filler metal. The supersaturated brazing filler metal comprises base brazing filler metal and a metal electroforming layer covering the base brazing filler metal, and a transition layer formed by diffusion reaction between solid solutions in the base brazing filler metal and the metal electroforming layer is arranged between the base brazing filler metal and the metal electroforming layer. A preparation method comprises the steps of placing raw metal material of the base brazing filler metal into a smelting furnace and prefabricating the raw metal material to form the base brazing filler metal through casting, annealing, extruding and rolling or drawing formation; electroforming the metal layer on the surface of the base brazing filler metal through the electroforming process, placing the base brazing filler metal into a vacuum drying oven of 25-250 DEG C for permeation for 0.5-10 minutes after the electroforming process is completed, placing the permeated base brazing filler metal into a thermal treatment furnace of 20-230 DEG C for diffusion for 2-30 hours and finally cooling the base brazing filler metal naturally in the furnace so as to obtain the supersaturated brazing filler metal. The supersaturated brazing filler metal is low in melting temperature and good in wettability and can be applied to the medium-temperature brazing field after being machined into strip shapes or thread shapes or rod shapes. The preparation method provides a new technological approach for manufacturing and producing of the brazing filler metal.
Description
Technical field
The present invention relates to brazing material, especially relate to a kind of supersaturation solder, the invention still further relates to the preparation method of this supersaturation solder.
Background technology
Soldering is one of important method of material connection, in brazing process, the liquid phase relying on the solder of fusing or rely on the diffusion between mother metal joint face and solder and formed, fill the gap between mother metal under capillary action, and mother metal and solder interact, then cooled and solidified, forms metallurgical binding.
Solder, as packing material during soldering, refers in heating-up temperature lower than melting during mother metal fusing point and filling the metal or alloy in mother metal gap.The performance of solder determines the quality and performance of soldered fitting to a great extent, and therefore, development of new solder is the key of development soldering tech.Different according to brazing filler metal melts temperature, solder can be divided into hard solder (fusion temperature is higher than 450 ° of C) and the large class of soft solder (fusion temperature is lower than 450 ° of C) two.Wherein hard solder mainly comprises the 5 class solders such as money base, copper base, aluminium base, Ni-based, manganese base.
Silver-base solder is as a most widely used class hard solder at present, and fusion temperature is moderate, wetability is good, seam-filling ability is excellent, has good bonding strength, toughness and electric conductivity, is widely used in fields such as refrigeration, household electrical appliances, sintered carbide toolses.GB GB/T10046-2008 has carried out specification to the chemical composition of silver-base solder, fusion temperature.
The main alloy element of silver-base solder is Cu, Zn, for reducing solder cost and meeting different process demand, usually also adds In, Ga, Sn, Cd etc. and reduces melting element.Particularly containing cadmium (Cd) silver solder, compared with cadmium-free silver brazing alloy, there is lower solid-liquid liquidus temperature, good mechanical property and corrosion resistance, but Cd is toxic element, has significant damage to the mankind.In cadmium-free silver-base solder, the solders such as silver-bearing copper tin, silver-bearing copper zinc-tin, Ag-Cu-Zn indium, Ag-Cu-Zn gallium, tin or the beneficial element such as indium or gallium is added by traditional molten alloy method, then utilize rolling or extruding, drawing manufactures, and nontoxic, environmental protection, meet RoHs and WEEE command request.But In(or Sn or Ga or bianry alloy in the solder such as silver-bearing copper indium, silver-bearing copper gallium, silver-bearing copper tin, silver-bearing copper zinc-tin, Ag-Cu-Zn indium, Ag-Cu-Zn gallium that above-mentioned molten alloy method is manufactured) all there is the limit in constituent content, otherwise solder is difficult to processing, affects applying of silver-base solder.
Along with new material, new technology in industry development application and structural member to the requirements at the higher level of soldered fitting, more and more higher to the requirement of beneficial element in the solder comprising silver-base solder, only adopt the structure property of traditional molten alloy method regulation and control solder to be difficult to meet the demand to beneficial element in industrial production.How to break through the conventional limit that molten alloy prepares beneficial element in solder, to prepare the high-quality solder of new component neomorph, the manufacture for solder is produced and is provided a kind of new technological approaches, is puzzlement one of difficult problem of welding academia and industrial circle both at home and abroad.
Summary of the invention
The object of the invention is to low for beneficial element content in existing solder and that fusion temperature is high defect and a kind of supersaturation solder is provided, not only increase the content of beneficial element in solder, and reduce the fusion temperature of solder, improve wetability, reduce to a certain extent, save the content of noble metal in solder.
For achieving the above object, the present invention can take following technical proposals:
Supersaturation solder of the present invention comprises matrix solder and is coated on the metal electric cast layer outside described matrix solder, it is the transition zone that solid solution in matrix solder and metal electric cast layer generation diffusion reaction are formed between described matrix solder and metal electric cast layer, described matrix solder, weight percent between transition zone and metal electric cast layer consist of: matrix solder 85.0 ~ 97.0%, transition zone 2.5 ~ 13.0%, metal level 0.1 ~ 2.0%.
Described matrix solder is silver-base solder, copper base solder, aluminium base solder, nickel-based solder, manganese based solder or cobalt-based solder.
Described silver-base solder is made up of silver or yellow gold or AgCuZn alloy, and described metal electric cast layer is the alloy electroformation layer of monometallic electroformed layer in indium, gallium, tin or two kinds and two or more metal.
The preparation method of supersaturation solder of the present invention is as follows:
First the raw metal of matrix solder is put into smelting furnace, shaping through casting, annealing, extruding, rolling or drawing, be prefabricated into matrix solder; Then adopt electroforming process at matrix solder surface electrical ingot metal layer, treat that electroforming process is complete, put it in the vacuum drying chamber of 25 ~ 250 ° of C and permeate 0.5 ~ 10min, after then putting into the heat-treatment furnace diffusion 2 ~ 30h of 20 ~ 230 ° of C, with stove cooling, obtained supersaturation solder.
Supersaturation brazing filler metal melts temperature prepared by the present invention is low, wetability good, be processed into band shape according to a conventional method, thread, bar-shaped after, can be applicable to middle temperature brazing field.
The present invention adopts electroforming to spread the preparation method of combination, have that sedimentation rate is fast, the enforcement time is short, forming efficiency advantages of higher, simple to operation, breach the metal solid solubility limit that traditional molten alloy method prepares solder, high-quality solder for neomorph provides a kind of new Method of Green Manufacture, and the manufacture for solder is produced and provided a kind of new technological approaches.Concerning silver-base solder, improve the content of the beneficial elements such as indium in silver-base solder, gallium, tin, and reduce, save the content of noble silver in silver-base solder to a certain extent, reduce the cost of raw material.
Accompanying drawing explanation
Fig. 1 is the structure chart of supersaturation solder of the present invention.
Detailed description of the invention
As shown in Figure 1, the metal electric cast layer 2 that supersaturation solder of the present invention comprises matrix solder 1 and is coated on outside matrix solder 1, it is the transition zone 3 that solid solution in matrix solder and metal electric cast layer generation diffusion reaction are formed between matrix solder 1 and metal electric cast layer 2, matrix solder 1, weight percent between transition zone 3 and metal electric cast layer 2 consist of: matrix solder 85.0 ~ 97.0%, transition zone 2.5 ~ 13.0%, metal level 0.1 ~ 2.0%.Matrix solder of the present invention not only comprises silver-base solder, also can be the hard solders such as copper base solder, aluminium base solder, nickel-based solder, manganese based solder or cobalt-based solder.
Silver-base solder of the present invention is made up of silver or yellow gold or AgCuZn alloy, and metal electric cast layer is the alloy electroformation layer of monometallic electroformed layer in indium, gallium, tin or two kinds and two or more metal.
The preparation method of supersaturation solder of the present invention is:
First the raw metal of matrix solder is put into HRJ-13 smelting furnace, shaping through casting, annealing, extruding, rolling or drawing, be prefabricated into matrix solder; Then adopt conventional electroforming process at matrix solder surface electrical ingot metal layer (electroforming apparatus model EFT6300); after treating electroforming process; the thermograde method of diffusion of protection atmosphere is utilized to be penetrated into by metal level in matrix solder; concrete operation step is: first putting it into its reaction principle of infiltration 0.5 ~ 10min(in the VDF-7160 vacuum drying chamber of 25 ~ 250 ° of C is atomic thermal motion); put into HTL-30 heat-treatment furnace diffusion 2 ~ 30h(metallurgical reaction of 20 ~ 230 ° of C again; form Compound Phase); then with stove cooling, obtained supersaturation solder.
Below by specific embodiment, more detailed explanation is done to the present invention.
embodiment 1
Prepare a kind of supersaturation silver-base solder, matrix solder is BAg60Cu, and metal level is indium electroformed layer, and transition zone is AgIn Compound Phase and CuIn Compound Phase composition.The percentage by weight of matrix solder, transition zone, metal level is as follows, matrix solder 87.5%, transition zone 11.9%, metal level 0.6%.
First argent 600g, copper 400g are inserted smelting furnace, through casting, annealing, extruding, rolling or drawing forming, be made as the flaky matrix solder BAg60Cu of thickness 0.35mm in advance; Then adopt electroforming indium technique at the positive and negative electroforming indium (one side thickness 21 μm) of BAg60Cu matrix solder; After treating electroforming process, the thermograde method of diffusion of protection atmosphere is utilized to be penetrated into by indium metal layer in BAg60Cu matrix solder, concrete operation step is: first the BAg60Cu solder of band indium electroformed layer is carried out rapid osmotic, time 1.5min in the vacuum drying chamber of 155 ~ 165 ° of C; After rapid osmotic, then the heat-treatment furnace put under 150 ~ 155 ° of C conditions is to its diffusion 24h; Finally with stove cooling, AgCuIn supersaturation solder can be obtained.
The fusion temperature of the AgCuIn supersaturation silver-base solder adopting said method to prepare is 582 ~ 706 ° of C, according to GB GB/T11364-2008 " solder wetting test method ", 200mgAgCuIn supersaturation solder is 485mm in the wetting areas on 316LN stainless steel (40mm40mm2mm) surface
2.Compared with matrix solder BAg60Cu, silver content reduces by 8.1%, and wetting areas improves 11.3%, and liquidus temperature reduces by 14 ° of C, and solidus reduces by 18 ° of C.
embodiment 2
Prepare a kind of supersaturation silver-base solder, matrix solder is BAg50Cu, and metal level is indium stannum alloy electroformed layer, and transition zone is AgCuSn Compound Phase, AgCuIn Compound Phase, CuIn Compound Phase, CuSn Compound Phase composition.The percentage by weight of matrix solder, transition zone, metal level is as follows: matrix solder 90.0%, transition zone 9.5%, metal level 0.5%.
First argent 500g, copper 500g are inserted smelting furnace, through casting, annealing, extruding, rolling or drawing forming, be made as the flaky matrix solder BAg50Cu that thickness is 0.30mm in advance; Then adopt alloy electroformation indium process of tin in BAg50Cu matrix solder positive and negative electroforming indium tin (one side thickness 16 μm); After treating alloy electroformation technique, the thermograde method of diffusion of protection atmosphere is utilized to be penetrated into by indium tin metal layer in BAg50Cu matrix solder, concrete operation step is: first the BAg50Cu solder of band indium tin electroformed layer is carried out rapid osmotic, time 2.0min in the vacuum drying chamber of 115 ~ 125 ° of C; After rapid osmotic, then the heat-treatment furnace putting into 105 ~ 115 ° of C spreads 20h to it; Finally with stove cooling, AgCuInSn supersaturation solder can be obtained.
The fusion temperature of the AgCuInSn supersaturation silver-base solder adopting said method to prepare is 745 ~ 812 ° of C, according to GB GB/T11364-2008 " solder wetting test method ", 200mgAgCuInSn supersaturation solder is 454mm in the wetting areas on 316LN stainless steel (40mm40mm2mm) surface
2.Compared with matrix solder BAg50Cu, silver content reduces by 4.8%, and wetting areas improves 7.9%, and liquidus temperature reduces by 38 ° of C, and solidus reduces by 34 ° of C.
embodiment 3
Prepare a kind of supersaturation silver-base solder, matrix solder is BAg60CuZn, and metal level is gallium electroformed layer, and transition zone is AgCuGa Compound Phase, CuZnGa Compound Phase, CuGa Compound Phase, AgGa Compound Phase composition.The percentage by weight of matrix solder, transition zone, metal level is as follows: matrix solder 89.0%, transition zone 10.2%, metal level 0.8%.
First argent 600g, copper 260g, zinc 140g are inserted smelting furnace, through casting, annealing, extruding, roll forming, be made as the flaky matrix solder BAg60CuZn that thickness is 0.5mm in advance; Then adopt electroforming gallium technique in BAg60CuZn matrix solder positive and negative electroforming gallium (one side thickness 24.5 μm); After treating electroforming gallium technique, the thermograde method of diffusion of protection atmosphere is utilized to be penetrated into by gallium metal layer in BAg60CuZn matrix solder, concrete operation step is: first the BAg60CuZn solder of band gallium electroformed layer is carried out rapid osmotic, time 0.5min in the vacuum drying chamber of 30 ~ 35 ° of C; After rapid osmotic, then the heat-treatment furnace putting into 25 ~ 30 ° of C spreads 8h to it; Finally with stove cooling, AgCuZnGa supersaturation solder can be obtained.
The fusion temperature of the AgCuZnGa supersaturation silver-base solder adopting said method to prepare is 658 ~ 691 ° of C, according to GB GB/T11364-2008 " solder wetting test method ", 200mgAgCuZnGa supersaturation solder is 472mm in the wetting areas on 316LN stainless steel (40mm40mm2mm) surface
2.Compared with matrix solder BAg60CuZn, silver content reduces by 5.2%, and wetting areas improves 8.6%, and in fusion temperature, liquidus curve reduces by 39 ° of C, and solidus reduces by 37 ° of C.
embodiment 4
Prepare a kind of supersaturation copper base solder, matrix solder is BCu70Ag, and metal level is gallium-indium alloy electroformed layer, and transition zone is CuAgGa Compound Phase, CuAgIn Compound Phase, CuGa Compound Phase, AgGa Compound Phase composition.The percentage by weight of matrix solder, transition zone, metal level is as follows: matrix solder 87.3%, transition zone 12.6%, metal level 0.1%.
First metallic copper 700g, silver-colored 250g, phosphorus 50g are inserted smelting furnace, through casting, annealing, extruding, roll forming, be made as the flaky matrix solder BCu70Ag that thickness is 0.40mm in advance; Then adopt alloy electroformation gallium indium technique in BCu70Ag matrix solder positive and negative electroforming gallium indium (one side thickness 26.1 μm); After treating electroforming gallium indium technique, the thermograde method of diffusion of protection atmosphere is utilized to be penetrated into by gallium indium metal level in BCu70Ag matrix solder, concrete operation step is: first the BCu70Ag solder of band gallium indium electroformed layer is carried out rapid osmotic, time 0.5min in the vacuum drying chamber of 30 ~ 35 ° of C; After rapid osmotic, then the heat-treatment furnace putting into 25 ~ 30 ° of C spreads 8h to it; Finally with stove cooling, CuAgGaIn supersaturation solder can be obtained.
The fusion temperature of the CuAgGaIn supersaturation copper base solder adopting said method to prepare is 622 ~ 689 ° of C, according to GB GB/T11364-2008 " solder wetting test method ", 200mgCuAgGaIn supersaturation solder is 393mm in the wetting areas on Q235 carbon steel (40mm40mm2mm) surface
2.Compared with matrix solder BCu70Ag, silver content reduces by 4.1%, and wetting areas improves 9.5%, and in fusion temperature, liquidus curve reduces by 21 ° of C, and solidus reduces by 28 ° of C.
embodiment 5
Prepare a kind of supersaturation aluminium base solder, matrix solder is BAl67CuSi, and metal level is gallium ashbury metal electroformed layer, and transition zone is AlCuGa Compound Phase, AlCuSn Compound Phase, CuSiSn Compound Phase, CuSiGa Compound Phase composition.The percentage by weight of matrix solder, transition zone, metal level is as follows: matrix solder 87.6%, transition zone 10.4%, metal level 2.0%.
First metallic aluminium 670g, copper 270g, silicon 60g are inserted smelting furnace, through casting, annealing, extruding, roll forming, be made as the flaky matrix solder BAl67CuSi that thickness is 0.20mm in advance; Then adopt alloy electroformation gallium process of tin in BAl67CuSi matrix solder positive and negative electroforming gallium tin (one side thickness 12.8 μm); After treating electroforming gallium process of tin, the thermograde method of diffusion of protection atmosphere is utilized to be penetrated into by gallium tin metal layer in BAl67CuSi matrix solder, concrete operation step is: first the BAl67CuSi solder of band gallium tin electroformed layer is carried out rapid osmotic, time 0.5min in the vacuum drying chamber of 35 ~ 40 ° of C; After rapid osmotic, then the heat-treatment furnace putting into 25 ~ 30 ° of C spreads 10h to it; Finally with stove cooling, AlCuSiGaSn supersaturation solder can be obtained.
The fusion temperature of the AlCuSiGaSn supersaturation aluminium base solder adopting said method to prepare is 490 ~ 556 ° of C, according to GB GB/T11364-2008 " solder wetting test method ", 200mgAlCuSiGaSn supersaturation solder is 288mm in the wetting areas on 3003 aluminium alloys (40mm40mm2mm) surface
2.Compared with matrix solder BAl67CuSi, wetting areas improves 7.6%, and in fusion temperature, liquidus curve reduces by 29 ° of C, and solidus reduces by 30 ° of C.
Claims (4)
1. a supersaturation solder, it is characterized in that: comprise matrix solder and be coated on the metal electric cast layer outside described matrix solder, it is the transition zone that solid solution in matrix solder and metal electric cast layer generation diffusion reaction are formed between described matrix solder and metal electric cast layer, described matrix solder, weight percent between transition zone and metal electric cast layer consist of: matrix solder 85.0 ~ 97.0%, transition zone 2.5 ~ 13.0%, metal level 0.1 ~ 2.0%.
2. supersaturation solder according to claim 1, is characterized in that: described matrix solder is silver-base solder, copper base solder, aluminium base solder, nickel-based solder, manganese based solder or cobalt-based solder.
3. supersaturation solder according to claim 2, it is characterized in that: described silver-base solder is made up of silver or yellow gold or AgCuZn alloy, described metal electric cast layer is the alloy electroformation layer of monometallic electroformed layer in indium, gallium, tin or two kinds and two or more metal.
4. the preparation method of supersaturation solder described in claim 1, is characterized in that:
First the raw metal of matrix solder is put into smelting furnace, shaping through casting, annealing, extruding, rolling or drawing, be prefabricated into matrix solder; Then adopt electroforming process at matrix solder surface electrical ingot metal layer, treat that electroforming process is complete, put it in the vacuum drying chamber of 25 ~ 250 ° of C and permeate 0.5 ~ 10min, after then putting into the heat-treatment furnace diffusion 2 ~ 30h of 20 ~ 230 ° of C, with stove cooling, obtained supersaturation solder.
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| CN106334882A (en) * | 2016-11-03 | 2017-01-18 | 华北水利水电大学 | AgCuTi brazing filler metal and preparation method thereof |
| CN106392384A (en) * | 2016-11-21 | 2017-02-15 | 郑州航空工业管理学院 | Electroforming method of silver solder with high tin content |
| CN106514039A (en) * | 2016-11-03 | 2017-03-22 | 华北水利水电大学 | Copper-tin-titanium brazing filler metal and preparation method thereof |
| CN106757205A (en) * | 2016-12-23 | 2017-05-31 | 华北水利水电大学 | A kind of electrotyping process preparation method of high indium content silver solder |
| CN110238557A (en) * | 2019-06-04 | 2019-09-17 | 清华大学 | A kind of ZnSn base high-temperature leadless solder and preparation method thereof |
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| CN110238557A (en) * | 2019-06-04 | 2019-09-17 | 清华大学 | A kind of ZnSn base high-temperature leadless solder and preparation method thereof |
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| CN105345304B (en) | 2017-07-25 |
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