CN1759974A - Mesothermal copper based solder without cadmium, and preparation method - Google Patents
Mesothermal copper based solder without cadmium, and preparation method Download PDFInfo
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- CN1759974A CN1759974A CN 200510010466 CN200510010466A CN1759974A CN 1759974 A CN1759974 A CN 1759974A CN 200510010466 CN200510010466 CN 200510010466 CN 200510010466 A CN200510010466 A CN 200510010466A CN 1759974 A CN1759974 A CN 1759974A
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Abstract
A medium-temp non-Cd Cu-based soldering wire contains Cu (74.9-82.96 Wt%), Ni (1-5.5), Sn (10-12), P (6-7), Ce (0.02-0.3) and La (0.02-0.3). Its preparing process features that after the electrolytic Cu and Ni in the graphite crucible of MF induction furnace is heated to 600-800 deg.C, the covering agent is added. Its advantages are low smelting temp, narrow smelting zone, better wet spreading performance and certain plasticity.
Description
Technical field
The present invention relates to a kind of preparation method who is used for solder and this solder thereof of soldering.
Background technology
Nearly 30 years is lasting rising of household electrical appliance demand of representative with refrigerator, air-conditioning, and building and ornament materials and manufacturing industry thereof are also flourish, and soldering tech has been played the part of the key player in these industries.According to incompletely statistics, only household electrical appliances are made one, and the domestic annual consumption silver solder that needs has 100 tons, one of construction material machining tool, and need to consume silver solder domestic every year 200 tons.In order to pursue brazing manufacturability and Technological Economy, soldering person usually preferentially selects for use money base to contain the cadmium solder, and the production of the accessory that especially freezes is almost all adopted to contain the cadmium solder.This is owing to adding Cd in the Ag-Cu-Zn ternary alloy three-partalloy can significantly reduce the liquidus curve of alloy, dwindles molten temperature region, improve brazing manufacturability.Fusion temperature as BAg45CuZnCd is 607～618 ℃, and the fusion temperature of BAg40CuZnCdNi is 595～605 ℃, is to use intermediate temperature solder the most widely.Yet, contain the health that a large amount of uses of cadmium solder not only directly endanger the welding operator, also influence surrounding enviroment, contain the production of cadmium solder and use pollution to become a global problem environment.The domestic and international also development of underway always temperature solder without cadmium, what replace present use contains the cadmium solder.Mainly comprise two series of silver-base solder and copper base solder, but aspect the technical indicator of fusion temperature and melting region with contain the cadmium solder and compare and also have certain gap, the silver-base solder that has has in addition been dosed a large amount of valuable alloying elements, make this kind solder be difficult to obtain extensive use, though the copper base solder price is low, but the alloying element that adds in order to obtain lower fusion temperature makes that the fragility of solder is very big, be difficult to be processed into welding wire, can only make foil-shaped brazing material or make powdered filler metal with rapid solidification method, limit its scope of application.
Summary of the invention
The objective of the invention is to contain the cadmium solder in order to solve to replacement, copper base solder aspect the technical indicator of fusion temperature and melting region with contain the cadmium solder and compare and also have certain gap, the alloying element that adds in order to obtain lower fusion temperature makes that the fragility of copper base solder is very big, be difficult to be processed into the problem of welding wire, provide a kind of in warm copper based solder without cadmium and preparation method thereof.Warm copper based solder without cadmium has lower fusion temperature and narrower melting region in of the present invention, and the Microstructure Uniformity of solder is higher, has the characteristics of certain plasticity; In the preparation method of warm copper based solder without cadmium have technological process weak point, constant product quality, characteristics that extrusion yield is high.Warm copper based solder without cadmium is made by weight percentage by following ingredients in of the present invention: Cu:74.9～82.96%, Ni:1～5.5%, Sn:10～12%, P:6～7%, Ce:0.02～0.3%, La:0.02～0.3%.The preparation method of warm copper based solder without cadmium is realized by the following step in of the present invention: one, take off row composition: Cu:74.9～82.96%, Ni:1～5.5%, Sn:10～12%, P:6～7%, Ce:0.02～0.3%, La.0.02～0.3% by weight percentage; Two, the preparation of rare earth intermediate alloy: salt-mixture is put into crucible melt, salt-mixture is made of by weight percentage following ingredients: LiCl50%, KCl50%; After treating that salt melts fully, the Sn that removes oxide-film with rare HCl is put into crucible, the salt of fusing is with the complete submergence of Sn; After treating that Sn melts fully, add rare earth element ce and La, the weight ratio of Ce and La is Ce: La=1: 1～2, and the weight of Ce and La accounts for 4～6% of rare earth intermediate alloy gross weight; Stirred once in per 4～6 minutes, and be incubated and pour out salting liquid after 25～35 minutes, again rare earth intermediate alloy is poured into the porcelain boat cooling; Three, the melting of middle temperature copper based solder without cadmium: cathode copper and Ni are put into the graphite crucible of Medium Frequency Induction Heating Furnace, be warmed up to 600～800 ℃, add coverture, coverture is the charcoal through destructive distillation, continue to be warmed up to 1000～1150 ℃, treat that cathode copper and Ni melt fully after, add copper-phosphorus alloy, stir the fusing back, add Sn, add coverture, be cooled to 960～1000 ℃ after 3～5 minutes, fast rare earth intermediate alloy is added, fully stir; Look when the stove cigarette changes milky and stir, drag for slag, be cooled to 920～950 ℃ and come out of the stove, pour ready tundish degasification into,, water mold before the casting and be heated to 250～300 ℃ after funnel is poured into and watered mold; Four, extruding: with ingot casting scale removal and cut rising head on lathe, in stove, be preheated to 420～460 ℃, the barrel of putting into extruder pushes, the matrix of extruder is preheated to 430～460 ℃, barrel temperature is 390～410 ℃, extrusion speed is 8～12cm/s, and extrusion ratio is 100～180.The interpolation that the invention has the advantages that optimization by alloy formula and rare earth element make of the present invention in warm copper based solder without cadmium have lower fusion temperature and narrower melting region, and good wetting and spreading performance, the cadmium solder is suitable with containing, the microstructure of solder is even, has certain plasticity; It is 0.8～2.0 welding wire that preparation method of the present invention can obtain diameter.Warm copper based solder without cadmium precious metal such as argentiferous does not contain any poisonous element yet in of the present invention, and Costco Wholesale is very low.Can replace and contain the cadmium solder, be particularly suitable for the soldering at a lower temperature of copper and copper alloy.
The specific embodiment
The specific embodiment one: the middle temperature copper based solder without cadmium of present embodiment is made by weight percentage by following ingredients: Cu:74.9～82.96%, Ni:1～5.5%, Sn:10～12%, P:6～7%, Ce:0.02～0.3%, La:0.02～0.3%.
The specific embodiment two: the middle temperature copper based solder without cadmium of present embodiment is made by weight percentage by following ingredients: Cu:79.52%, Ni:1.1%, Sn:11.9%, P:6.9%, Ce:0.29%, La:0.29%.
The specific embodiment three: the middle temperature copper based solder without cadmium of present embodiment is made by weight percentage by following ingredients: Cu:78.24%, Ni:5.4%, Sn:10.2%, P:6.1%, Ce:0.03%, La:0.03%.
The specific embodiment four: the middle temperature copper based solder without cadmium of present embodiment is made by weight percentage by following ingredients: Cu:76.9%, Ni:4.5%, Sn:11.5%, P:7%, Ce:0.05%, La:0.05%.
The specific embodiment five: the middle temperature copper based solder without cadmium of present embodiment is made by weight percentage by following ingredients: Cu:80.6%, Ni:1.8%, Sn:10.5%, P:7%, Ce:0.05%, La:0.05%.
The specific embodiment six: the preparation method of the middle temperature copper based solder without cadmium of present embodiment is realized by the following step: one, take off row composition: Cu:74.9～82.96%, Ni:1～5.5%, Sn:10～12%, P:6～7%, Ce:0.02～0.3%, La:0.02～0.3% by weight percentage; Two, the preparation of rare earth intermediate alloy: salt-mixture is put into crucible melt, salt-mixture is made of by weight percentage following ingredients: LiCl50%, KCl 50%; After treating that salt melts fully, the Sn that removes oxide-film with rare HCl is put into crucible, the salt of fusing is with the complete submergence of Sn; After treating that Sn melts fully, add rare earth element ce and La, the weight ratio of Ce and La is Ce: La=1: 1～2, and the weight of Ce and La accounts for 4～6% of rare earth intermediate alloy gross weight; Stirred once in per 4～6 minutes, and be incubated and pour out salting liquid after 25～35 minutes, again rare earth intermediate alloy is poured into the porcelain boat cooling; Three, the melting of middle temperature copper based solder without cadmium: cathode copper and Ni are put into the graphite crucible of Medium Frequency Induction Heating Furnace, be warmed up to 600～800 ℃, add coverture, coverture is the charcoal through destructive distillation, continue to be warmed up to 1000～1150 ℃, treat that cathode copper and Ni melt fully after, add copper-phosphorus alloy, stir the fusing back, add Sn, add coverture, be cooled to 960～1000 ℃ after 3～5 minutes, fast rare earth intermediate alloy is added, fully stir; Look when the stove cigarette changes milky and stir, drag for slag, be cooled to 920～950 ℃ and come out of the stove, pour ready tundish (casting ladle) degasification into,, water mold before the casting and be heated to 250～300 ℃ after funnel is poured into and watered mold; Four, extruding: with ingot casting scale removal and cut rising head on lathe, in stove, be preheated to 420～460 ℃, the barrel of putting into extruder pushes, the matrix of extruder is preheated to 430～460 ℃, barrel temperature is 390～410 ℃, extrusion speed is 8～12cm/s, and extrusion ratio is 100～180.
The specific embodiment seven: the Ce of present embodiment and the weight ratio of La are Ce: La=1: 1.1.Other method is identical with the specific embodiment six with step.
The specific embodiment eight: the Ce of present embodiment and the weight ratio of La are Ce: La=1: 1.5.Other method is identical with the specific embodiment six with step.
The specific embodiment nine: the Ce of present embodiment and the weight ratio of La are Ce: La=1: 1.9.Other method is identical with the specific embodiment six with step.
Claims (9)
1, warm copper based solder without cadmium in a kind of is characterized in that it is made by weight percentage by following ingredients: Cu:74.9～82.96%, Ni:1～5.5%, Sn:10～12%, P:6～7%, Ce:0.02～0.3%, La:0.02～0.3%.
2, warm copper based solder without cadmium in according to claim 1 is characterized in that it is made by Cu:79.52%, Ni:1.1%, Sn:11.9%, P:6.9%, Ce:0.29%, La:0.29%.
3, warm copper based solder without cadmium in according to claim 1 is characterized in that it is made by Cu:78.24%, Ni:5.4%, Sn:10.2%, P:6.1%, Ce:0.03%, La:0.03%.
4, warm copper based solder without cadmium in according to claim 1 is characterized in that it is made by Cu:76.9%, Ni:4.5%, Sn:11.5%, P:7%, Ce:0.05%, La:0.05%.
5, warm copper based solder without cadmium in according to claim 1 is characterized in that it is made by Cu:80.6%, Ni:1.8%, Sn:10.5%, P:7%, Ce:0.05%, La:0.05%.
6, the preparation method of middle temperature copper based solder without cadmium is characterized in that it is realized by the following step: one, take off row composition: Cu:74.9～82.96%, Ni:1～5.5%, Sn:10～12%, P:6～7%, Ce:0.02～0.3%, La:0.02～0.3% by weight percentage; Two, the preparation of rare earth intermediate alloy: salt-mixture is put into crucible melt, salt-mixture is made of by weight percentage following ingredients: LiCl 50%, KCl 50%; After treating that salt melts fully, the Sn that removes oxide-film with rare HCl is put into crucible, the salt of fusing is with the complete submergence of Sn; After treating that Sn melts fully, add rare earth element ce and La, the weight ratio of Ce and La is Ce: La=1: 1～2, and the weight of Ce and La accounts for 4～6% of rare earth intermediate alloy gross weight; Stirred once in per 4～6 minutes, and be incubated and pour out salting liquid after 25～35 minutes, again rare earth intermediate alloy is poured into the porcelain boat cooling; Three, the melting of middle temperature copper based solder without cadmium: cathode copper and Ni are put into the graphite crucible of Medium Frequency Induction Heating Furnace, be warmed up to 600～800 ℃, add coverture, coverture is the charcoal through destructive distillation, continue to be warmed up to 1000～1150 ℃, treat that cathode copper and Ni melt fully after, add copper-phosphorus alloy, stir the fusing back, add Sn, add coverture, be cooled to 960～1000 ℃ after 3～5 minutes, fast rare earth intermediate alloy is added, fully stir; Look when the stove cigarette changes milky and stir, drag for slag, be cooled to 920～950 ℃ and come out of the stove, pour ready tundish degasification into,, water mold before the casting and be heated to 250～300 ℃ after funnel is poured into and watered mold; Four, extruding: with ingot casting scale removal and cut rising head on lathe, in stove, be preheated to 420～460 ℃, the barrel of putting into extruder pushes, the matrix of extruder is preheated to 430～460 ℃, barrel temperature is 390～410 ℃, extrusion speed is 8～12cm/s, and extrusion ratio is 100～180.
7, the preparation method of warm copper based solder without cadmium in according to claim 6, the weight ratio that it is characterized in that Ce and La is Ce: La=1: 1.1.
8, the preparation method of warm copper based solder without cadmium in according to claim 6, the weight ratio that it is characterized in that Ce and La is Ce: La=1: 1.5.
9, the preparation method of warm copper based solder without cadmium in according to claim 6, the weight ratio that it is characterized in that Ce and La is Ce: La=1: 1.9.
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| CNB2005100104660A CN100443244C (en) | 2005-10-25 | 2005-10-25 | Mesothermal copper based solder without cadmium, and preparation method |
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| CNB2005100104660A CN100443244C (en) | 2005-10-25 | 2005-10-25 | Mesothermal copper based solder without cadmium, and preparation method |
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| CN1759974A true CN1759974A (en) | 2006-04-19 |
| CN100443244C CN100443244C (en) | 2008-12-17 |
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Cited By (15)
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| CN101829860A (en) * | 2010-04-20 | 2010-09-15 | 哈尔滨工业大学 | Welding wire for unpreheated welding of red copper thick and large part and preparation method thereof |
| CN101890592A (en) * | 2010-07-19 | 2010-11-24 | 周炳刚 | Novel brazing material and manufacturing method thereof |
| CN101664864B (en) * | 2009-09-24 | 2011-08-03 | 哈尔滨工业大学 | Moderate temperature copper based brazing filler metal and preparation method thereof |
| CN102179642A (en) * | 2011-05-06 | 2011-09-14 | 郴州格瑞特焊业有限公司 | Copper-based brazing filler metal and preparation method thereof |
| CN101342644B (en) * | 2007-07-13 | 2012-05-23 | 浙江信和科技股份有限公司 | High-ductility environment friendly silver-saving medium-temperature brazing filler metal |
| CN102581516A (en) * | 2012-03-27 | 2012-07-18 | 郑州机械研究所 | Super-plastic copper and phosphorous welding rod and preparation method thereof |
| CN102626837A (en) * | 2012-05-09 | 2012-08-08 | 哈尔滨工业大学 | Moderate temperature copper-based solder and preparation method thereof |
| CN102744534A (en) * | 2012-07-27 | 2012-10-24 | 张国华 | Preparation method of silver-free solder and product |
| CN103624418A (en) * | 2013-12-12 | 2014-03-12 | 杭州华光焊接新材料股份有限公司 | Low-silver-copper-based brazing filler metal and preparation method thereof |
| CN104096988A (en) * | 2013-04-07 | 2014-10-15 | 江西金世纪特种焊接材料有限公司 | Rare earth La and Ce-containing low-Ag-Cu-P brazing filler metal |
| CN104625471A (en) * | 2014-12-18 | 2015-05-20 | 郴州市金贵银业股份有限公司 | Cadmium-free silver filler metal for vacuum electron brazing and preparation method thereof |
| CN106041355A (en) * | 2016-07-20 | 2016-10-26 | 安徽华众焊业有限公司 | Copper-based soldering paste |
| CN106141496A (en) * | 2016-07-28 | 2016-11-23 | 华南理工大学 | A kind of copper phosphor tin nickel solder and its preparation method and application |
| CN110952017A (en) * | 2019-12-27 | 2020-04-03 | 华北水利水电大学 | High-entropy ultra-silver solder alloy and preparation method thereof |
| CN114367764A (en) * | 2022-03-07 | 2022-04-19 | 金华市步扬焊材有限公司 | Bronze welding wire and production process and extrusion equipment thereof |
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| DE1508331B1 (en) * | 1966-05-25 | 1971-04-29 | Jurid Werke Gmbh | SOLDER MATERIAL FOR SINTER MATERIALS |
| JPS5658941A (en) * | 1979-10-18 | 1981-05-22 | Honda Motor Co Ltd | Solder alloy for sintered alloy |
| JPS6040688A (en) * | 1983-08-15 | 1985-03-04 | Toyota Motor Corp | Brazing filler metal |
| CA2022271C (en) * | 1989-07-31 | 1996-03-12 | Soya Takagi | Dispersion strengthened copper-base alloy for overlay |
| JPH11179588A (en) * | 1997-12-16 | 1999-07-06 | Nhk Spring Co Ltd | Brazing filler metal for stainless steel |
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| CN101342644B (en) * | 2007-07-13 | 2012-05-23 | 浙江信和科技股份有限公司 | High-ductility environment friendly silver-saving medium-temperature brazing filler metal |
| CN101664864B (en) * | 2009-09-24 | 2011-08-03 | 哈尔滨工业大学 | Moderate temperature copper based brazing filler metal and preparation method thereof |
| CN101829860A (en) * | 2010-04-20 | 2010-09-15 | 哈尔滨工业大学 | Welding wire for unpreheated welding of red copper thick and large part and preparation method thereof |
| CN101890592A (en) * | 2010-07-19 | 2010-11-24 | 周炳刚 | Novel brazing material and manufacturing method thereof |
| CN102179642A (en) * | 2011-05-06 | 2011-09-14 | 郴州格瑞特焊业有限公司 | Copper-based brazing filler metal and preparation method thereof |
| CN102581516A (en) * | 2012-03-27 | 2012-07-18 | 郑州机械研究所 | Super-plastic copper and phosphorous welding rod and preparation method thereof |
| CN102626837A (en) * | 2012-05-09 | 2012-08-08 | 哈尔滨工业大学 | Moderate temperature copper-based solder and preparation method thereof |
| CN102626837B (en) * | 2012-05-09 | 2014-06-04 | 哈尔滨工业大学 | Moderate temperature copper-based solder and preparation method thereof |
| CN102744534A (en) * | 2012-07-27 | 2012-10-24 | 张国华 | Preparation method of silver-free solder and product |
| CN104096988A (en) * | 2013-04-07 | 2014-10-15 | 江西金世纪特种焊接材料有限公司 | Rare earth La and Ce-containing low-Ag-Cu-P brazing filler metal |
| CN103624418A (en) * | 2013-12-12 | 2014-03-12 | 杭州华光焊接新材料股份有限公司 | Low-silver-copper-based brazing filler metal and preparation method thereof |
| CN103624418B (en) * | 2013-12-12 | 2015-10-07 | 杭州华光焊接新材料股份有限公司 | A kind of low silver copper-base filler metals and preparation method thereof |
| CN104625471A (en) * | 2014-12-18 | 2015-05-20 | 郴州市金贵银业股份有限公司 | Cadmium-free silver filler metal for vacuum electron brazing and preparation method thereof |
| CN106041355A (en) * | 2016-07-20 | 2016-10-26 | 安徽华众焊业有限公司 | Copper-based soldering paste |
| CN106141496A (en) * | 2016-07-28 | 2016-11-23 | 华南理工大学 | A kind of copper phosphor tin nickel solder and its preparation method and application |
| CN110952017A (en) * | 2019-12-27 | 2020-04-03 | 华北水利水电大学 | High-entropy ultra-silver solder alloy and preparation method thereof |
| CN114367764A (en) * | 2022-03-07 | 2022-04-19 | 金华市步扬焊材有限公司 | Bronze welding wire and production process and extrusion equipment thereof |
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