CN109082559A - A kind of low silver-colored high-reliability lead-free solder alloy of SnAgCuNiGeCe - Google Patents

A kind of low silver-colored high-reliability lead-free solder alloy of SnAgCuNiGeCe Download PDF

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Publication number
CN109082559A
CN109082559A CN201811018722.4A CN201811018722A CN109082559A CN 109082559 A CN109082559 A CN 109082559A CN 201811018722 A CN201811018722 A CN 201811018722A CN 109082559 A CN109082559 A CN 109082559A
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China
Prior art keywords
solder
alloy
lead
free solder
snagcunigece
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CN201811018722.4A
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CN109082559B (en
Inventor
白海龙
刘宝权
吕金梅
赵玲彦
严继康
甘有为
陈东东
滕媛
徐凤仙
古列东
朵云琨
顾鑫
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Yunnan Tin New Material Co ltd
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YUNNAN TIN MATERIAL CO Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C13/00Alloys based on tin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/26Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262Sn as the principal constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

A kind of low silver-colored high-reliability lead-free solder alloy of SnAgCuNiGeCe, the weight percent composition of the alloy are as follows: the Ce of Ge, 0.01-0.2% of Ni, 0.01-0.15% of Cu, 0.01-0.2% of Ag, 0.3-1.0% of 0.1-1.0%, the Sn of surplus and inevitable impurity.The present invention can substantially reduce the production cost of solder, be with a wide range of applications in the case where guaranteeing that solder has preferable brazing characteristics especially reliability and good mechanical property.

Description

A kind of low silver-colored high-reliability lead-free solder alloy of SnAgCuNiGeCe
Technical field
The invention belongs to electronic welding field of material technology, and in particular to a kind of low silver-colored high reliability solder alloy.
Background technique
As electronic product develops to miniaturization, portable, lightweight, high-precision and high reliability direction, circuit integration Degree increases substantially, so that number of welds becomes more, size becomes smaller, the reliability requirement of butt welding point is higher and higher.Due to SnAgCu lead-free solder possesses the advantages that relatively good brazing characteristics and good mechanical property, and can be with existing electricity Subcomponent matches, therefore the lead-free solder has become the leading alloy system in reflow soldering process.German Max Plank is ground Study carefully announced Sn4.0Ag0.5The Sn that Cu, U.S. NEMI recommend3.9Ag0.6The Sn that Cu, Europe SOLDERTEC recommend3.8Ag0.7Cu with And Japan thousand live/Panasonic recommend Sn3.0Ag0.5Cu solder alloy can substitute traditional SnPb eutectic solder alloy.But In these lead-free solders composition, silver-colored cost is accounted between 40%~50%.In recent years, silver-colored price increased rapidly, made The cost of raw material of the SnAgCu solder hierarchy of high silver content considerably increases again, becomes the heavy burden of Electronic Assemblies industry.This Outside, due to higher silver content, solder tissue Ag3Sn intermetallic compound, which increases, leads to the reduction of solder reliability, and wetability becomes Difference, service life are reduced, and limit its application in actual production.Therefore it is inevitable for developing low silver-colored high-reliability lead-free solder Trend.
Summary of the invention
Present invention seek to address that deficiency existing for existing SnAgCu system solder alloy, brazing filler metal alloy can be reduced by providing one kind Production cost and the SnAgCuNiGeCe low-temperature lead-free solder for improving solder wetting.
The technical solution adopted by the present invention is as follows:
A kind of low silver-colored high-reliability lead-free solder alloy of SnAgCuNiGeCe, the weight percent group of the leadless welding alloy Become: Ge, 0.01-0.2%'s of Ni, 0.01-0.15% of Cu, 0.01-0.2% of Ag, 0.3-1.0% of 0.1-1.0% The Sn and inevitable impurity of Ce, surplus.
During the preparation process, Ag, Cu, Ni, Ge, Ce are respectively with intermediate alloy for low temperature lead-free solder alloy of the invention Sn3Ag、Sn10Cu、Sn4Ni、Sn1Ge、Sn1.8Ce form is added, and insufficient Sn is added with pure Sn.
Leadless welding alloy of the invention is that progress ingredient levelling and supplement are perfect on the basis of the solder of SnAgCu system, Ni, Ge and Ce element is added after reducing silver-colored dosage.Ni element can form Ni with Sn3Sn、Ni3Sn2、Ni3Sn4Change between three kinds of metals Object is closed, to inhibit Cu6Sn5The growth of intermetallic compound, and the addition of Ni can also inhibit Cu matrix to molten state solder Dissolution, significantly reduce wetting time of the solder on substrate, be effectively improved the spreading ability of solder, the content control of Ni exists 0.01-0.2%.Ce is rare earth metal, and atomic radius is bigger, play the role of refine crystal grain improve tissue, and due to Ce element is surface active element, and when liquid is gathered in solder surface and positive absorption is presented, and reduces the surface free energy of liquid solder, Reduce its surface tension, promotes wetting ability of the solder on copper-based base material, improve the wettability of solder.But when containing When amount is slowly increased to a certain extent, the oxidation of rare earth element ce is occupied an leading position, and the surface tension of solder can be made to increase Greatly, to reduce wetability.Advantage is provided to improve the reliability of solder, Ce content of the invention is controlled in 0.01- 0.2%.Ge element has high-intensitive oxyphie kelvin effect, forms one layer of barrier layer in solder surface, can hinder solder into The oxidation of one step, the addition of Ge element can prevent a large amount of Sn2O and SnO oxidizing slag generate, improve the spreading ratio of solder, at that time when When Ge constituent content is excessively high, a large amount of GeO2The surface tension increase for equally also resulting in solder is generated, the wetting of solder is reduced Property.Ge constituent content of the invention is controlled in 0.01-0.15%.
The present invention on the basis of most widely used SnAgCu brazing filler metal alloy at present, addition minor metallic element Ni, Ge, Ce is compounded, and the additive amount of Ag is further decreased, and greatly reduces the cost of solder.
SnAgCuNiGeCe series lead-free solder alloy of the invention, alloying level is high, and solder crystalline structure is uniformly thin Change, wetability, weldability, the mechanical property of solder are obviously improved, and at low cost, and the use for being able to satisfy solder wave process is wanted It asks, has broad application prospects.It can be applied to a variety of welding material products, low-silver lead-free solder powder, low silver such as soldering paste Unleaded welding rod, low-silver lead-free solder stick.
Detailed description of the invention
Fig. 1 is the solder alloy angle of wetting metallographic microscope of embodiment 2;
Fig. 2 is the solder alloy metallographic structure figure of embodiment 4;
Fig. 3 is the solder alloy metallographic structure figure of embodiment 5;
Fig. 4 is the solder alloy solder joint figure of embodiment 6.
Specific embodiment
Hereinafter, further the present invention is described in detail.Below in explanation, about " % " of solder alloy composition, only It is exactly " mass percent " without being particularly limited to.
Embodiment 1
A kind of low silver-colored high-reliability lead-free solder alloy of SnAgCuNiGeCe, the weight percent composition of the lead-free solder Are as follows: 0.3% Ag, 0.7% Cu, 0.03% Ni, 0.03% Ge, 0.01% Ce remaining for Sn and inevitably it is miscellaneous Matter, 219 DEG C, tensile strength 59Mpa of the fusing point of the lead-free solder, elongation percentage 47%, wetting time 0.53s, maximum profit Wet power is 0.94mN, and angle of wetting is 21.2 °, and solder joint spreading ratio is 77.2%, and product form is leadless welding powder.
Embodiment 2
A kind of low silver-colored high-reliability lead-free solder alloy of SnAgCuNiGeCe, the weight percent composition of the lead-free solder Are as follows: 0.1% Ag, 0.5% Cu, 0.2% Ni, 0.05% Ge, 0.05% Ce remaining for Sn and inevitably it is miscellaneous Matter, 221 DEG C, tensile strength 57Mpa of the fusing point of the lead-free solder, elongation percentage 49%, wetting time 0.58s, maximum profit Wet power is 0.93mN, and angle of wetting is 22.1 °, and solder joint spreading ratio is 73.9%, and product form is unleaded welding rod.Fig. 1 is this implementation The solder alloy angle of wetting metallographic microscope of example.
Embodiment 3
A kind of low silver-colored high-reliability lead-free solder alloy of SnAgCuNiGeCe, the weight percent composition of the lead-free solder Are as follows: 0.5% Ag, 1.0% Cu, 0.05% Ni, 0.07% Ge, 0.1% Ce remaining for Sn and inevitably it is miscellaneous Matter, 222 DEG C, tensile strength 60Mpa of the fusing point of the lead-free solder, elongation percentage 47%, wetting time 0.46s, maximum profit Wet power is 0.98mN, and angle of wetting is 21.5 °, and solder joint spreading ratio is 77.4%, and product form is lead-free soldering wire.
Embodiment 4
A kind of low silver-colored high-reliability lead-free solder alloy of SnAgCuNiGeCe, the weight percent composition of the lead-free solder Are as follows: 0.7% Ag, 0.3% Cu, 0.09% Ni, 0.01% Ge, 0.07% Ce remaining for Sn and inevitably it is miscellaneous Matter, 219 DEG C, tensile strength 63Mpa of the fusing point of the lead-free solder, elongation percentage 50%, wetting time 0.55s, maximum profit Wet power is 0.97mN, and angle of wetting is 22.5 °, and solder joint spreading ratio is 74.9%, and product form is unleaded welding rod.Fig. 2 is this implementation The solder alloy metallographic structure figure of example.
Embodiment 5
A kind of SnAgCuNiGeCe lead-free solder alloy in low silver, the weight percent composition of the lead-free solder are as follows: 1.0% Remaining is Sn and inevitable impurity by Ag, 0.8% Cu, 0.01% Ni, 0.09% Ge, 0.2% Ce, the Pb-free coating 220 DEG C, tensile strength 65Mpa of the fusing point of material, elongation percentage 48%, wetting time 0.53s, maximum wetting power is 1.1mN, Angle of wetting is 19.1 °, and solder joint spreading ratio is 76.8%, and product form is leadless welding powder.Fig. 3 is the solder alloy gold of the present embodiment Phase constitution figure.
Embodiment 6
A kind of low silver-colored high-reliability lead-free solder alloy of SnAgCuNiGeCe, the weight percent composition of the lead-free solder Are as follows: 0.3% Ag, 0.7% Cu, 0.07% Ni, 0.05% Ge, 0.05% Ce remaining for Sn and inevitably it is miscellaneous Matter, 219 DEG C, tensile strength 60Mpa of the fusing point of the lead-free solder, elongation percentage 52%, wetting time 0.56s, maximum profit Wet power is 1.0mN, and angle of wetting is 20.7 °, and solder joint spreading ratio is 75.2%, and product form is lead-free soldering wire.Fig. 4 is this implementation The alloy solder joint figure of example solder.
Embodiment 7
A kind of low silver-colored high-reliability lead-free solder alloy of SnAgCuNiGeCe, the weight percent composition of the lead-free solder Are as follows: 0.5% Ag, 0.9% Cu, 0.12% Ni, 0.09% Ge, 0.05% Ce remaining for Sn and inevitably it is miscellaneous Matter, 221 DEG C, tensile strength 61Mpa of the fusing point of the lead-free solder, elongation percentage 49%, wetting time 0.47s, maximum profit Wet power is 0.99mN, and angle of wetting is 20.6 °, and solder joint spreading ratio is 78.8%, and product form is leadless welding powder.
Embodiment 8
A kind of low silver-colored high-reliability lead-free solder alloy of SnAgCuNiGeCe, the weight percent composition of the lead-free solder Are as follows: 0.8% Ag, 0.7% Cu, 0.03% Ni, 0.15% Ge, 0.1% Ce remaining for Sn and inevitably it is miscellaneous Matter, 220 DEG C, tensile strength 61Mpa of the fusing point of the lead-free solder, elongation percentage 46%, wetting time 0.49s, maximum profit Wet power is 0.99mN, and angle of wetting is 21.2 °, and solder joint spreading ratio is 77.9%, and product form is unleaded welding rod.
During the preparation process, Ag is with intermediate alloy Sn for the low temperature lead-free solder alloy of above embodiments3Ag form is added, C With intermediate alloy Sn10Cu form is added, and Ni is with intermediate alloy Sn4Ni form is added, and Ge is with intermediate alloy Sn1Ge form is added, Ce is with intermediate alloy Sn1.8Ce form is added, and insufficient Sn is added with pure Sn.According to the component ratio of alloy, required for calculating The quality of intermediate alloy, then weighed intermediate alloy and pure tin, are melted in smelting furnace, and smelting temperature is 270~300 DEG C temperature keeps the temperature 20 minutes after the completion of melting, in fusion process, for the oxidization burning loss for preventing alloy part, in the table of melt Face covers one layer of anti-oxidation solvent, after melting is uniform, casts in molding die.The Pb-free coating of the be classified as Examples 1 to 8 of table 1 Expect the performance data of alloy.
The leadless welding alloy performance data of 1 Examples 1 to 8 of table
Lead-free solder alloy in low silver of the invention is guaranteeing that SnAgCu alloy is excellent by the compound addition of polynary alloy Solder characteristic under the premise of greatly improve the wettability of SnAgCu lead-free solder, reduce production cost.Fusing point is on 219 DEG C of left sides The right side, tensile strength reach 60MPa, and elongation percentage is up to 48%.Wetting time is 0.50s, and maximum wetting power is 0.99mN, and angle of wetting is 21 °, for spreading ratio up to 77%, performance indexes shows that low-silver lead-free solder of the invention can be widely applied to electronic welding neck Domain.

Claims (2)

1. a kind of low silver-colored high-reliability lead-free solder alloy of SnAgCuNiGeCe, which is characterized in that the weight of the leadless welding alloy Measure percentage composition are as follows: the Ge of Ni, 0.01-0.15% of Cu, 0.01-0.2% of Ag, 0.3-1.0% of 0.1-1.0%, The Ce of 0.01-0.2%, the Sn of surplus and inevitable impurity.
2. the low highly reliable leadless welding alloy of silver of a kind of SnAgCuNiGeCe as described in claim 1, which is characterized in that described During the preparation process, Ag, Cu, Ni, Ge, Ce are respectively with intermediate alloy Sn for low temperature lead-free solder alloy3Ag、Sn10Cu、Sn4Ni、 Sn1Ge、Sn1.8Ce form is added, and insufficient Sn is added with pure Sn.
CN201811018722.4A 2018-09-03 2018-09-03 SnAgCuNiGeCe low-silver high-reliability lead-free solder alloy Active CN109082559B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112775583A (en) * 2021-01-14 2021-05-11 深圳市兴鸿泰锡业有限公司 Solder alloy for automatic tin soldering machine and preparation method thereof

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CN1570166A (en) * 2004-05-09 2005-01-26 邓和升 Lead free solder alloy and its preparation method
US20070071634A1 (en) * 2005-09-26 2007-03-29 Indium Corporation Of America Low melting temperature compliant solders
US20070092396A1 (en) * 2005-10-24 2007-04-26 Indium Corporation Of America Technique For Increasing The Compliance Of Lead-Free Solders Containing Silver
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CN101585119A (en) * 2009-02-26 2009-11-25 郴州金箭焊料有限公司 Oxidation resistant low silver lead-free solder alloy
CN101671784A (en) * 2008-09-12 2010-03-17 深圳市亿铖达工业有限公司 Sn-Ag-Cu lead-free brazing alloy
CN103028863A (en) * 2011-09-29 2013-04-10 郴州金箭焊料有限公司 High-anti-oxidation lead-free solder
KR20160139585A (en) * 2015-05-28 2016-12-07 덕산하이메탈(주) Solder alloy, solder ball and manufacturing method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1570166A (en) * 2004-05-09 2005-01-26 邓和升 Lead free solder alloy and its preparation method
US20070071634A1 (en) * 2005-09-26 2007-03-29 Indium Corporation Of America Low melting temperature compliant solders
US20070092396A1 (en) * 2005-10-24 2007-04-26 Indium Corporation Of America Technique For Increasing The Compliance Of Lead-Free Solders Containing Silver
CN101028673A (en) * 2006-03-03 2007-09-05 天津市宏远电子有限公司 Lead-free solder alloy
CN101157162A (en) * 2007-11-23 2008-04-09 北京工业大学 SnAgCu leadless brazing filler metal with antioxygenic performance
CN101671784A (en) * 2008-09-12 2010-03-17 深圳市亿铖达工业有限公司 Sn-Ag-Cu lead-free brazing alloy
CN101585119A (en) * 2009-02-26 2009-11-25 郴州金箭焊料有限公司 Oxidation resistant low silver lead-free solder alloy
CN103028863A (en) * 2011-09-29 2013-04-10 郴州金箭焊料有限公司 High-anti-oxidation lead-free solder
KR20160139585A (en) * 2015-05-28 2016-12-07 덕산하이메탈(주) Solder alloy, solder ball and manufacturing method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112775583A (en) * 2021-01-14 2021-05-11 深圳市兴鸿泰锡业有限公司 Solder alloy for automatic tin soldering machine and preparation method thereof

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Address after: 650501 No.2, Yunjing Road, information industry base, Kunming Economic and Technological Development Zone, Yunnan Province

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Address before: 650501 No.2, Yunjing Road, information industry base, Kunming Economic and Technological Development Zone, Yunnan Province

Patentee before: YUNNAN TIN MATERIAL Co.,Ltd.