CN1390672A - Leadfree SnZn-base alloy solder containing rare-earth elements - Google Patents

Leadfree SnZn-base alloy solder containing rare-earth elements Download PDF

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Publication number
CN1390672A
CN1390672A CN 02109623 CN02109623A CN1390672A CN 1390672 A CN1390672 A CN 1390672A CN 02109623 CN02109623 CN 02109623 CN 02109623 A CN02109623 A CN 02109623A CN 1390672 A CN1390672 A CN 1390672A
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China
Prior art keywords
alloy
weight
solder
lead
earth elements
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Granted
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CN 02109623
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Chinese (zh)
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CN1175956C (en
Inventor
赵杰
黄明亮
于大全
王来
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Dalian University of Technology
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Dalian University of Technology
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Priority to CNB021096236A priority Critical patent/CN1175956C/en
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Publication of CN1175956C publication Critical patent/CN1175956C/en
Anticipated expiration legal-status Critical
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Abstract

A lead-free alloy as solder contains Zn (5-10 wt.%), the rare-earth elements chosen from La, Ce, Pr and Nd (0.05-1), one or more of Bi (0.1-6), Cu (0.1-3), In (0.5-3), Al (0.1-1), Ni (0.01-1) and P (0.001-1), and Sn (rest). Its advantages are better wettability, fine structure, excellent mechanical performance, low cost and no poison and pollution.

Description

The tin zinc-base contains the lead-free solder alloy of rare earth element
Technical field
The invention belongs to the metal material engineering technical field, relate to electronic packaging and brazing material technical field, specially refer to a kind of especially low-cost lead-free solder alloy of using of household electrical appliance of electronic industry that is applicable to.
Background technology
Because traditional tin-lead solder contains the lead element that human body and environment is had very big harm, the development lead-free brazing has become present material scientific worker's a urgent task.The U.S., Japan and other countries were just actively made laws and are forbidden plumbous use, and European Union is according to the instruction of the waste of legislation case electrical and electronic product machinery, will completely forbid the uses of poisonous and harmful element electronic industry such as leaded, cadmium from January 1st, 2008.Thereby, in order to eliminate plumbous pollution, press for unleaded solder and replace the Sn-Pb solder and be applied in the Electronic Packaging welding technique.
In order to make the lead-free solder alloy composition satisfy relevant laws and regulations requirement, and make solder alloy have excellent mechanical property and brazed joint has higher reliability, solder alloy must have appropriate melting point, good wettability, component does not contain poisonous, hazardous property element, the feed rate abundance can satisfy the requirement of industrialization, alloy structure good stability, non-corrosiveness etc.In currently known binary and multicomponent alloy system, to Sn-Ag, Sn-Bi-Ag, Sn-Ag-Cu solder and brazed joint research thereof are more, have application promise in clinical practice.But the fusing point of these alloys is compared higher for 183 ℃ with the fusing point of Sn-37Pb solder between 216 ℃-227 ℃.In addition, these cost of alloy are higher, are about 3 times of tinsel cost.For some solder application scenarios, for example household electrical appliance or requirement condition are not extra high Application Areass, need the solder of developing low-cost to meet the demands.
The Sn-9Zn alloy has 199 ℃ eutectic temperature, very near Sn-37Pb solder fusing point.And the Sn-9Zn alloy has good and economic and mechanical property.But because the Zn element is more active, make the wettability of this alloy and erosion resistance relatively poor, influenced application.
Summary of the invention
The objective of the invention is, provide a kind of tin zinc-base to contain the lead-free brazing of rare earth element,, its wettability, erosion resistance and mechanical property are further improved to solve the problem that present red brass exists, thereby can be widely used in Electronic Packaging, especially in the middle of the household electrical appliance.
More specifically purpose of the present invention provides the lead-free solder alloy with following character:
1) 250 ℃ of following brazing temperatures are used, and avoid the thermal damage of electronic component in brazing process;
2) has good weldability;
3) brazed joint of Xing Chenging has sufficiently high bonding strength, and the brazed joint structure stability is good;
4) be processed to form wire rod easily, can carry out soldering with soldering bit.
Technical scheme of the present invention is, in the Sn-Zn alloy, added trace rare-earth element RE (by La, Ce, Pr, among the Nd one or more are elementary composition), one or more among the P of Ni, the 0.001-1 weight % of Al, the 0.01-1 weight % of In, the 0.1-1 weight % of Cu, the 0.1-3 weight % of optional simultaneously Bi, the 0.1-3 weight % that contains 0.1-6 weight %.
Describing now the present invention in detail, in the following description, all is weight percentage all about the percentage ratio of alloying constituent.
Can be according to lead-free solder alloy of the present invention as the equivalent material of traditional Sn-Pb alloy.The fusing point of these alloys is close with 183 ℃ of temperature of Sn-Pb alloy eutectic, between 185~200 ℃; The obvious refinement of these alloy structures, mechanical property is superior; The wettability of alloy has had large increase than Sn-Zn alloy phase ratio; Anti-oxidant, erosion resistance is also obviously improved.
Alloying constituent according to following reason is:
RE:0.05%~1.0%
Rare earth element is by La, Ce, and Pr, one or more among the Nd are elementary composition, and trace rare-earth element can suppress thick β-Sn crystal grain and generate, and makes the obvious refinement of alloy structure, and then has improved the mechanical property of alloy.The adding of rare earth element simultaneously significantly improves the wettability of alloy.Select the active brazing flux of RA rosin for use, in 245 ℃ of air, the mixed rare-earth elements of interpolation 0.05% can make wetting power improve 5~6 times.RE content preferably 0.05%~0.5%, more preferably 0.05%~0.25%.
Bi:0.1%~6%,In:0.5%~3%
Optional In, Bi improves wettability, the reduction fusing point of alloy as alloy element.A spot of Bi element adds can effectively reduce the melt temperature of alloy, and can play the effect of solution strengthening.But too much Bi element can make the melting range of alloy widen, and ductility sharply descends.Therefore the Bi element preferably 0.1%~6%, and more preferably 1%~3%.
Indium (In) can play the reduction fusing point, improve the effect of wettability, but In is a precious metal, and content preferably 1%~3% during interpolation, and more preferably 2%~3%
Cu:0.1%~3%,Ni:0.01%~1%
The adding of Cu, Ni can refinement alloy graining tissue in crystal grain, effectively improve the mechanical property of alloy.Cu content preferably 0.1%~3%, more preferably 0.7%~1.5%; Ni content preferably 0.01%~1%, more preferably 0.05%~0.2%.Less than or to exceed this range effect all not obvious.
Al:0.1%~1%,P:0.001%~1%
Al, P improve anti-oxidant, the corrosion resistance of alloy as alloy element.The effect of adding Al, P in the solder alloy that contains Zn is the oxidation that stops solder alloy effectively, improves anticorrosive effect.Especially having under rare earth element acts on simultaneously, can promote Al to form oxide film, hinder solder alloy and directly contact with air on the solder surface.But Al, P content are too much, can reduce the weldability of alloy.Therefore Al content preferably 0.1%~1%, and more preferably 0.1%~0.5%.P content preferably 0.001%~0.5%, more preferably 0.001%~0.1%.
Effect of the present invention and benefit be, because the adding of RE, Bi and other alloy elements makes solder alloy wettability, mechanical property better, fusing point is suitable, low price, can overcome the weakness of Sn-Zn alloy, can satisfy electronic industry, especially the unleaded demand of household electrical appliance.
Description of drawings
Fig. 1 is Sn-9Zn alloy microscopic structure figure.
β-Sn white crystal grain thick among the figure can reach 100 μ m.
Fig. 2 is Sn-9Zn-0.05RE alloy microscopic structure figure.
β among the figure-Sn crystal grain has only several microns sizes.
Fig. 3 is that trace rare-earth element significantly improves Sn-Zn alloy wettability synoptic diagram.
Abscissa represents temperature among the figure, and ordinate represents wetting power. Data are to utilize wetability Tester ST50 adopts the wettability equilibrium method to record. The brazing flux that uses is RA rosin activity Brazing flux, the wetting power that records are corresponding experiment values in 10 seconds in the experiment. Article three, broken line That representative is Sn-9Zn-0.05RE from top to bottom, Sn-9Zn-0.1RE, the Sn-9Zn alloy The wetting power variation with temperature. At 245 ℃, 260 ℃, under 290 ℃ of three different temperature, Containing trace rare-earth element Sn-9Zn Alloy Wetting can be better.
Embodiment
The chemical ingredients (%) that tin zinc-base of the present invention contains the lead-free brazing of rare earth element is as follows: (5~10) Zn; (0.05~1) RE; (0~6) Bi, (0~3) Cu, (0~3) In, (0~1) Al, (0~1) Ni, (0~1) P; Surplus is that Sn and unavoidable impurities are formed.
Above-mentioned raw material of proportionately distributing is put into the vacuum for industrial use induction furnace smelt, vacuum tightness is 10 -3Pa, under normal pressure, 500 ℃ of temperature are incubated 4~6 hours, and cast can obtain welding flux alloy.Produce solder powder by spraying, add brazing flux, just obtain soldering paste.
Below be described in detail optimum implementation of the present invention:
Choose following chemical components (%): (7~9) Zn; (0.05~0.15) RE; (0.5~3) Bi; (0.2~0.5) Al, surplus is Sn.Above-mentioned raw material of proportionately distributing is put into the vacuum for industrial use induction furnace smelt, vacuum tightness is 10 -3Pa.Under normal pressure, 500 ℃ of temperature are incubated 4~6 hours, and cast can obtain welding flux alloy, produces solder powder by spraying, adds brazing flux, just obtains soldering paste.Can be used for reflow welding.

Claims (4)

1, a kind of tin zinc-base contains the lead-free solder alloy of rare earth element, it is characterized in that solder alloy is grouped into by following one-tenth:
The Zn of 5~10 weight %; 0.05 the rare earth element of~1 weight % (comprising La at least, Ce, Pr, one or more elements among the Nd); The Bi of 0~6 weight %; The C of 0~3 weight %; The In of 0~3 weight %; The Al of 0~1 weight %; The Ni of 0~1 weight %; The P of 0~1 weight %; All the other are Sn.
2, lead-free solder alloy according to claim 1 is characterized in that containing the Bi of 0.2~6 weight %, one or both among the In of 0.2~3 weight %.
3, lead-free solder alloy according to claim 1 is characterized in that containing the Cu of 0.1~3 weight %, the Al of 0.1~1 weight %, the Ni of 0.01~1 weight %, one or more among the P of 0.001~1 weight %.
4, lead-free solder alloy according to claim 1 is characterized in that containing the Bi of 0.2~6 weight %, contains the Cu of 0.1~3 weight % simultaneously, the Al of 0.1~1 weight %, one or more among the P of the Ni of 0.01~1 weight %, 0.001-1 weight %.
CNB021096236A 2002-05-10 2002-05-10 Leadfree SnZn-base alloy solder containing rare-earth elements Expired - Fee Related CN1175956C (en)

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Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1303236C (en) * 2005-02-07 2007-03-07 株洲冶炼集团有限责任公司 Zinc bismuth multicomponent alloy used for hot dip galvanizing of steel and iron members and hot dip galvanizing method therefor
CN100387741C (en) * 2005-08-04 2008-05-14 上海交通大学 Sn-Zn-Cr alloy lead-free solder preparation method
CN100445018C (en) * 2006-08-16 2008-12-24 东莞市普赛特电子科技有限公司 Lead-free solder
CN100453245C (en) * 2006-03-15 2009-01-21 浙江亚通焊材有限公司 Lead-free tin-radicel soft solder
CN100462183C (en) * 2006-04-30 2009-02-18 东莞市中实焊锡有限公司 Lead-free anti-oxidation rare-earth-contg. type SnZn alloy welding flux, and its prepn. method
CN101214586B (en) * 2008-01-04 2010-06-02 东南大学 Tin-zinc base lead-free solder and preparation thereof
CN101804527A (en) * 2010-04-06 2010-08-18 山东大学 Sn-Zn based unleaded brazing material with low Zn
CN1974108B (en) * 2006-08-21 2011-02-09 南昌大学 Hypoeutectic no-lead SnZn alloy brazing alloy
CN102029478A (en) * 2010-12-10 2011-04-27 株洲冶炼集团股份有限公司 Lead-free solder
CN101564803B (en) * 2008-07-15 2011-11-23 广州冶炼厂 Leadless solder of silverless Sn-Bi-Cu system and preparation method thereof
CN102489893A (en) * 2010-12-31 2012-06-13 广东中实金属有限公司 SnZn-based lead-free brazing alloy
CN102489892A (en) * 2010-12-31 2012-06-13 广东中实金属有限公司 SnZn-based lead-free brazing filler metal containing Cr
CN101585120B (en) * 2009-06-29 2012-08-22 铜陵森泰金属材料有限公司 Tin-zinc-based leadless solder alloy
CN102672367A (en) * 2011-12-12 2012-09-19 河南科技大学 ZnSn-base high-temperature lead-free soft solder and preparation method thereof
CN102825396A (en) * 2012-09-18 2012-12-19 金华市双环钎焊材料有限公司 Sn-Zn leadless brazing filler metal containing Pr, Ga and Te
CN102848096A (en) * 2012-09-18 2013-01-02 南京航空航天大学 Sn-Zn lead-free solder containing Pr, Ga and Se
CN102862000A (en) * 2012-09-18 2013-01-09 常熟市华银焊料有限公司 Sn-Zn lead-free brazing filler metal containing Nd, Ga and Te
CN102922164A (en) * 2012-11-01 2013-02-13 青岛英太克锡业科技有限公司 Sn-Zn solder for soft-soldering tin wires and preparation method thereof
CN103192194A (en) * 2013-03-28 2013-07-10 天津市恒固科技有限公司 Solder wire for aluminum and aluminum alloy soldering and preparation method thereof
CN103240541A (en) * 2013-05-13 2013-08-14 金封焊宝有限责任公司 Tin zinc multi-element alloy solder for soldering copper and aluminum and preparation method thereof
CN103317255A (en) * 2013-06-03 2013-09-25 北京科技大学 Zinc-based solder for aluminum/copper brazing and preparing method thereof
CN103706962A (en) * 2013-12-30 2014-04-09 大连理工大学 Sn-Zn-Ni lead-free solder alloy for aluminum copper soldering
CN103737195A (en) * 2013-12-30 2014-04-23 大连理工大学 Sn-Zn-Bi-base lead-free solder alloy for soft soldering of aluminum and copper
CN104588911A (en) * 2014-12-11 2015-05-06 徐国华 Lead-free solder and preparation method thereof
CN104588910A (en) * 2014-12-11 2015-05-06 徐国华 Lead-free solder with praseodymium, cesium, zinc and tin and preparation method thereof
CN104588908A (en) * 2014-12-11 2015-05-06 徐国华 Lead-free solder with lanthanum, rubidium and zinc and preparation method thereof
CN105479030A (en) * 2016-01-07 2016-04-13 哈尔滨工业大学 Active anti-corrosion SnZn base brazing filler metal, manufacturing method thereof and low-temperature ultrasonic brazing method of ceramic and/or composite material and aluminum and magnesium alloy
CN105499830A (en) * 2016-03-04 2016-04-20 保定爱廸新能源股份有限公司 Sn-Zn system lead-free multi-element alloy for photovoltaic welding strips and method for preparing Sn-Zn system lead-free multi-element alloy
CN106676321A (en) * 2016-12-07 2017-05-17 北京态金科技有限公司 Low-melting-point metal and preparation method and application thereof
CN108203776A (en) * 2017-12-21 2018-06-26 柳州智臻智能机械有限公司 A kind of high-strength tin spelter soldering alloy and preparation method thereof
CN108296668A (en) * 2017-12-21 2018-07-20 柳州智臻智能机械有限公司 A kind of leadless welding alloy and preparation method thereof
CN108465971A (en) * 2018-02-28 2018-08-31 西安理工大学 A kind of preparation method of low melting point Sn-Zn-Bi brazing filler metal alloys
CN114990381A (en) * 2021-03-01 2022-09-02 北京理工大学 Low-melting-point alloy for safe ammunition slow-release structure and preparation method and application thereof

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CN1303236C (en) * 2005-02-07 2007-03-07 株洲冶炼集团有限责任公司 Zinc bismuth multicomponent alloy used for hot dip galvanizing of steel and iron members and hot dip galvanizing method therefor
CN100387741C (en) * 2005-08-04 2008-05-14 上海交通大学 Sn-Zn-Cr alloy lead-free solder preparation method
CN100453245C (en) * 2006-03-15 2009-01-21 浙江亚通焊材有限公司 Lead-free tin-radicel soft solder
CN100462183C (en) * 2006-04-30 2009-02-18 东莞市中实焊锡有限公司 Lead-free anti-oxidation rare-earth-contg. type SnZn alloy welding flux, and its prepn. method
CN100445018C (en) * 2006-08-16 2008-12-24 东莞市普赛特电子科技有限公司 Lead-free solder
CN1974108B (en) * 2006-08-21 2011-02-09 南昌大学 Hypoeutectic no-lead SnZn alloy brazing alloy
CN101214586B (en) * 2008-01-04 2010-06-02 东南大学 Tin-zinc base lead-free solder and preparation thereof
CN101564803B (en) * 2008-07-15 2011-11-23 广州冶炼厂 Leadless solder of silverless Sn-Bi-Cu system and preparation method thereof
CN101585120B (en) * 2009-06-29 2012-08-22 铜陵森泰金属材料有限公司 Tin-zinc-based leadless solder alloy
CN101804527A (en) * 2010-04-06 2010-08-18 山东大学 Sn-Zn based unleaded brazing material with low Zn
CN102029478A (en) * 2010-12-10 2011-04-27 株洲冶炼集团股份有限公司 Lead-free solder
CN102489893A (en) * 2010-12-31 2012-06-13 广东中实金属有限公司 SnZn-based lead-free brazing alloy
CN102489892A (en) * 2010-12-31 2012-06-13 广东中实金属有限公司 SnZn-based lead-free brazing filler metal containing Cr
CN102672367B (en) * 2011-12-12 2015-05-13 河南科技大学 ZnSn-base high-temperature lead-free soft solder and preparation method thereof
CN102672367A (en) * 2011-12-12 2012-09-19 河南科技大学 ZnSn-base high-temperature lead-free soft solder and preparation method thereof
CN102825396B (en) * 2012-09-18 2015-06-03 金华市双环钎焊材料有限公司 Sn-Zn leadless brazing filler metal containing Pr, Ga and Te
CN102848096A (en) * 2012-09-18 2013-01-02 南京航空航天大学 Sn-Zn lead-free solder containing Pr, Ga and Se
CN102862000A (en) * 2012-09-18 2013-01-09 常熟市华银焊料有限公司 Sn-Zn lead-free brazing filler metal containing Nd, Ga and Te
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CN102825396A (en) * 2012-09-18 2012-12-19 金华市双环钎焊材料有限公司 Sn-Zn leadless brazing filler metal containing Pr, Ga and Te
CN102848096B (en) * 2012-09-18 2015-05-20 南京航空航天大学 Sn-Zn lead-free solder containing Pr, Ga and Se
CN102922164A (en) * 2012-11-01 2013-02-13 青岛英太克锡业科技有限公司 Sn-Zn solder for soft-soldering tin wires and preparation method thereof
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CN103240541B (en) * 2013-05-13 2014-08-13 金封焊宝有限责任公司 Tin zinc multi-element alloy solder for soldering copper and aluminum and preparation method thereof
CN103317255A (en) * 2013-06-03 2013-09-25 北京科技大学 Zinc-based solder for aluminum/copper brazing and preparing method thereof
CN103317255B (en) * 2013-06-03 2015-07-22 北京科技大学 Zinc-based solder for aluminum/copper brazing and preparing method thereof
CN103737195A (en) * 2013-12-30 2014-04-23 大连理工大学 Sn-Zn-Bi-base lead-free solder alloy for soft soldering of aluminum and copper
CN103706962B (en) * 2013-12-30 2015-12-30 大连理工大学 A kind of Sn-Zn-Ni lead-free solder alloy for aluminum bronze solder
CN103706962A (en) * 2013-12-30 2014-04-09 大连理工大学 Sn-Zn-Ni lead-free solder alloy for aluminum copper soldering
CN104588908A (en) * 2014-12-11 2015-05-06 徐国华 Lead-free solder with lanthanum, rubidium and zinc and preparation method thereof
CN104588910A (en) * 2014-12-11 2015-05-06 徐国华 Lead-free solder with praseodymium, cesium, zinc and tin and preparation method thereof
CN104588911A (en) * 2014-12-11 2015-05-06 徐国华 Lead-free solder and preparation method thereof
CN105479030A (en) * 2016-01-07 2016-04-13 哈尔滨工业大学 Active anti-corrosion SnZn base brazing filler metal, manufacturing method thereof and low-temperature ultrasonic brazing method of ceramic and/or composite material and aluminum and magnesium alloy
CN105499830A (en) * 2016-03-04 2016-04-20 保定爱廸新能源股份有限公司 Sn-Zn system lead-free multi-element alloy for photovoltaic welding strips and method for preparing Sn-Zn system lead-free multi-element alloy
CN106676321A (en) * 2016-12-07 2017-05-17 北京态金科技有限公司 Low-melting-point metal and preparation method and application thereof
CN108203776A (en) * 2017-12-21 2018-06-26 柳州智臻智能机械有限公司 A kind of high-strength tin spelter soldering alloy and preparation method thereof
CN108296668A (en) * 2017-12-21 2018-07-20 柳州智臻智能机械有限公司 A kind of leadless welding alloy and preparation method thereof
CN108465971A (en) * 2018-02-28 2018-08-31 西安理工大学 A kind of preparation method of low melting point Sn-Zn-Bi brazing filler metal alloys
CN114990381A (en) * 2021-03-01 2022-09-02 北京理工大学 Low-melting-point alloy for safe ammunition slow-release structure and preparation method and application thereof

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