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 PDFInfo
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- 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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- solder
- alloy
- lead
- free solder
- snagcunigece
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- 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
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making 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
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.
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CN201811018722.4A CN109082559B (en) | 2018-09-03 | 2018-09-03 | SnAgCuNiGeCe low-silver high-reliability lead-free solder alloy |
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Cited By (1)
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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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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 |
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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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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 |
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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 Patentee after: YUNNAN TIN NEW MATERIAL Co.,Ltd. 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. |