CN109048114A - Sn-Cu-Ni lead-free brazing containing Ga and Nd - Google Patents
Sn-Cu-Ni lead-free brazing containing Ga and Nd Download PDFInfo
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- CN109048114A CN109048114A CN201811097247.4A CN201811097247A CN109048114A CN 109048114 A CN109048114 A CN 109048114A CN 201811097247 A CN201811097247 A CN 201811097247A CN 109048114 A CN109048114 A CN 109048114A
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- Prior art keywords
- lead
- free brazing
- solder
- brazing
- free
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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
- B23K35/22—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
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
The invention discloses a kind of Sn-Cu-Ni lead-free brazings containing Ga and Nd, belong to the brazing material field of class of metal materials.The Sn-Cu-Ni lead-free brazing includes 0.45~1.1% Cu by mass percentage, 0.05~0.5% Ni, 0.003~0.008% As, 0.014~0.020% Sb, 0.4~0.6% Ga, 0.04~0.06% Nd, surplus Sn, wherein the mass ratio of Ga and Nd meets Ga ︰ Nd=10 ︰ 1.Solder of the invention has good wettability, can effectively inhibit the growth of soldered fitting tin palpus, greatly increase the reliability of soldered fitting, can be used for the wave-soldering and reflow welding of electronics industry component.
Description
Technical field
The present invention relates to a kind of Sn-Cu-Ni lead-free brazings containing Ga and Nd, belong to the pricker of class of metal materials and field of metallurgy
Weld field of material technology.
Background technique
Traditional Sn-Pb solder is due to having the advantages that good wetability, at low cost, fusing point is low etc. is widely used in electricity
Subgroup dress and encapsulation field, but because Pb element is harmful to environment and human body, in the WEEE instruction and RoHS instruction that European Union promulgates
And under the stringent limitation of " No. 39 portions enable " of Chinese Government, have on many electronic products using lead-free brazing.Now
The Sn base leadless solder of research mainly has Sn-Ag, Sn-Ag-Cu, Sn-Zn, Sn-Cu, Sn-Bi etc..Sn-Cu alloy brazing filler metal because
Its low in cost, good thermal fatigue resistance and be widely used, especially in wave-soldering, eutectic melting point reaches
227 DEG C, but its wetability, mechanical property are not so good as other lead-free brazings.There is researcher to add W metal member in Sn-Cu solder
Element, discovery Sn-Cu-Ni composite soldering performance ratio Sn-Cu solder is superior, in order to further increase the comprehensive of Sn-Cu-Ni solder
Can, researcher adds rare earth element wherein.
Sn-Cu, Sn-Cu-Ni brazing filler metal are moderate due to preferable comprehensive performance at present, have good answer
With prospect, application is had begun on wave-soldering.By retrieval, in Sn-Cu, Sn-Cu-Ni system of Intellectual Property Right in China office application
Solder lead-free brazing patent of invention has reached more than 280 parts.But find in use, with the extension of time, addition
The thickness of compound has the tendency that gradually increasing, thicken between the brazed seam interface metal of the Sn-Cu-Ni solder of rare earth element, especially
Be soldered fitting over time, easy germinating can cause electronic component short circuit tin must, will be greatly reduced soldering and connect
" reliability " of head.Therefore, these problems existing for the Sn-Cu-Ni solder of rare earth element are added, is badly in need of research, improves, exploitation
New high reliability Sn-Cu-Ni brazing filler metal out, to meet the needs of user.
Summary of the invention
The object of the present invention is to provide one kind to have good wettability, can effectively inhibit and change between brazed seam interface metal
It closes the growth of object thickness and the growth of soldered fitting tin palpus can be effectively inhibited, it is thus possible to greatly improve soldered fitting
" reliability " and it is suitable for electronics industry wave-soldering, takes into account the Sn-Cu-Ni containing Ga and Nd for welding methods such as reflow weldings
Lead-free brazing.
To achieve the object of the present invention, technical scheme is as follows:
Sn-Cu-Ni lead-free brazing containing Ga and Nd, includes: 0.45~1.1% Cu by mass percentage, 0.05~
0.5% Ni, 0.003~0.008% As, 0.014~0.020% Sb, 0.4~0.6% Ga, 0.04~0.06%
Nd, surplus Sn.Wherein the mass ratio of Ga and Nd is 10 ︰ 1.
Sn-Cu-Ni lead-free brazing containing Ga and Nd of the invention using conventional method prepare, i.e., using commercially available tin slab,
Tough cathode, nickel plate, antimony slab, blocky arsenic, gallium, neodymium metal, various elements raw material match as needed, and when smelting is added through excellent
Change screening determining commercially available " coverture " or smelted, cast using " inert gas " protection, can be obtained " strip solder " or
Bar.By squeezing, drawing be to get to silk material (can also be added scaling powder, " flux-cored wire " is made).Pb element as tin slab,
" impurity element " in the raw material such as tough cathode, overall control meet the Chinese people within the scope of Pb≤0.07wt.%, to meet
Republic's standard GB/T/T 20422-2018 " lead-free brazing " regulation (provides Pb≤0.07wt.%) in standard.
In view of neodymium metal fusing point is high and easily aoxidizes, metal praseodymium can also be smelted into advance to intermediate conjunction according to production needs
Gold is added, to guarantee the accuracy of neodymium metal ingredient in solder in the form of Sn-Nd.
Solder brazing performance (such as wettability) of the invention is good, solder joint (brazed seam) good mechanical performance, can be effectively
Inhibit soldered fitting tin must growth, environmentally protective, even tissue is easily processed into various shape, such as strip, rodlike, Filamentous
Deng assembling and encapsulation to adapt to the needs of different working conditions, suitable for electronics industry component.
Detailed description of the invention
Fig. 1 is Sn-0.7Cu-0.05Ni-0.5Ga-xNd difference Nd content wetting power figure of changing.
Fig. 2 is Sn-0.7Cu-0.05Ni-0.5Ga-xNd difference Nd content wetting time figure of changing.
Fig. 3 is soldered fitting " interface " shape appearance figure after room-temperature aging 30 days.
Specific embodiment
Compared with previous research, creativeness of the invention is:
1) it finds and demonstrates the synergistic effect of Ga, Nd in this element combinations, Ga, Nd element mass ratio meet Ga ︰ Nd
When=10 ︰ 1, compound thickness increases and can effectively inhibit soldered fitting tin palpus between capable of effectively inhibiting brazed seam interface metal
Growth.
During test of the invention, the study found that Ga, Nd are added in Sn-Cu-Ni lead-free brazing, it can be effectively
The growth rate of compound thickness between inhibition Sn-Cu-Ni lead-free brazing brazed seam interface metal.Further study show that and verify plus
Ga, Nd the element mass ratio entered meets Ga ︰ Nd=10 ︰ 1, the brazed seam interface metal chemical combination of Ga, Nd to Sn-Cu-Ni lead-free brazing
The inhibiting effect of the growth rate of object thickness is more significant, and inhibit soldered fitting tin must germinating, growth effect also ten
Divide significant.
Existing invention is pointed out, while adding Ga and Nd element, when their additive amount is at " certain particular ranges ", energy
Enough significantly improve the wettability of Sn-Ag-Cu lead-free brazing.But the negative work of rare earth element is not to be noted added in existing research
With being that can generate " tin one of the main divisions of the male role in traditional opera is long ".However, soldered fitting will be easy to cause electronics device once the germinating of tin palpus occurs, grows up
The short circuit of part is burnt.The present inventor passes through a large amount of comparative tests, screening, optimization, it is found that Ga, Nd are added to Sn-Cu-Ni simultaneously
When in lead-free brazing, the wettability of solder can not only be significantly improved, moreover it is possible to improve its antioxygenic property, in this way can not only
The needs for meeting " wave-soldering ", due to the addition of Ga, moreover it is possible to the fusion temperature of Sn-Cu-Ni solder is significantly reduced, so that it is answered
Use reflow soldering process.Test discovery, the additional amount that the additional amount of Ga reaches 0.4%, Nd reach 0.04%
When, Sn-Cu-Ni-Ga brazing filler metal melts temperature can achieve the performance of Sn-3.0Ag-0.7Cu lead-free brazing, solidus
Temperature is about at 210 DEG C, and for liquidus temperature about at 218 DEG C, 227 DEG C of liquidus temperature compared with Sn-Cu-Ni reduce 9 DEG C.
Sn-Cu-Ni lead-free brazing containing Ga and Nd its with good wettability, show that its wetting power significantly increases
Add, " wetting time " is significantly less than 1s as defined in internationally recognized IPC standard (referring to attached drawing 1, Fig. 2).Moreover, from Fig. 3
As can be seen that being added to the Sn-Cu-Ni lead-free brazing of Ga, Nd element, brazed seam interface sample is in aging time after 30 days
(in test, generally acknowledge carry out analog component using the time with aging time in the industry), compound thickness is not sent out between brazed seam interface metal
Raw significant change (having no that its thickness increases), and have no the germinating of tin palpus, growth, illustrate that Ga, Nd synergistic effect inhibit soldering to connect
Head tin must germinate, the effect that grows is very significant, so as to reduce cause because of growing up for intermetallic compound crack initiation,
The risk grown up, solder joint (brazed seam) is finally made to crack；It is short electronic device caused by must germinating, grow up because of tin has been suppressed or eliminated
Road, failure risk, improve the reliability of soldered fitting.
2) invigoration effect of research discovery As, the Sb to Sn-Cu-Ni lead-free brazing, and verification experimental verification, preferably As and Sb
Add range.
Existing research shows that arsenic is used as alloy addition production lead bullet, type metal, brass (condenser), electric power storage
Pond screen, antifriction alloy, high strength construction steel and corrosion-resisting steel etc..Dezincification can be prevented when containing weight arsenic in brass.High purity arsenic is system
Take the raw material of gaas compound semiconductor, indium arsenide etc. and the doped chemical of semiconductor material germanium and silicon, these materials wide
It is general to be used as diode, light emitting diode, RF transmitter, laser etc..The compound of arsenic is also used to manufacture pesticide, anti-corrosion
Agent, dyestuff and medicine etc..Expensive White brass alloy is exactly to be closed to refine with copper and arsenic.Arsenic is also used to manufacture hard alloy, in brass
Dezincification etc. can be prevented when containing micro amount of arsenic.About the effect of antimony element, according to the literature, it is available that alloy is made in antimony and lead and tin
Welding material, bullet and the performance of bearing are promoted, antimony also has its extensive use in emerging microelectric technique.
The application, which uses, adds YS/T 68-2014 " arsenic " moderate purity as 99.95% arsenic, GB/T 1599-2014 " antimony
Ingot " moderate purity be 99.90% antimony slab add arsenic and antimony.Have found that As, Sb are added to Sn- by " Sequential designed experiment " method
In Cu-Ni lead-free brazing, between inhibit brazed seam interface metal compound thickness increase affecting laws, and primarily determined As with
The addition range of Sb.
Although As is significant for the invigoration effect of copper alloy, Sb also has in Sn-Pb solder adjusts tin-lead pricker well
Expect the effect of performance, still, based on the invention aims to invent a kind of Sn-Cu-Ni brazing filler metal of high reliability, so,
Be intended to reach " effectively inhibit the growth of compound thickness between brazed seam interface metal and can effectively inhibit soldered fitting tin must life
It is long " purpose, in this element combinations, the additional amount of As with 0.003~0.008% range, the additional amount of Sb with 0.014~
0.020% range is preferred.
3) optimization has determined the addition range of Ga, Nd, As, Sb.
Compared with the lead-free brazing of existing addition rare earth element, in alloy system of the present invention, rare element Ga
" advantageous " addition range it is very narrow, only in 0.4~0.6% range；Although as shown in attached drawing 1, attached drawing 2, the additive amount of Nd from
0.01% to 0.25%, can Beneficial Effect be generated to the wettability of Sn-Cu-Ni-Ga solder, still, strengthen in addition
After elements A s, Sb, solder performance becomes very " to lack rule ".Collateral security solder performance and soldered fitting reliability angle
Degree considers, while by the addition scope control of Ga 0.4~0.6%, the addition range of Nd is determined 0.04~
0.06%, and Ga ︰ Nd=10 ︰ 1 is controlled, to ensure that solder while with good wettability, can effectively inhibit pricker
The growth of compound thickness increased and soldered fitting tin palpus can be effectively inhibited between seam interface metal.
The quality proportioning of " the Sn-Cu-Ni lead-free brazing containing Ga and Nd " according to the present invention, describes specific reality of the invention
It is as follows to apply mode.
Embodiment 1
Sn-Cu-Ni lead-free brazing containing Ga and Nd, includes: 0.45% Cu, 0.5% Ni by mass percentage,
0.003% As, 0.020% Sb, 0.4% Ga, 0.04% Nd, surplus Sn.Wherein the mass ratio of Ga and Nd meets
Ga ︰ Nd=10 ︰ 1.
" the Sn-Cu-Ni lead-free brazing containing Ga and Nd " solidus temperature that mentioned component matches at 210 DEG C or so,
Liquidus temperature is 218 DEG C or so (considering test error).Cooperate commercially available RMA brazing flux that there is excellent profit on copper plate
Wet performance, brazed seam tensile strength reach 45MPa ± 5MPa.
Fig. 3 is shown, after timeliness 720 hours (30 days), is added to the Sn-Cu-Ni lead-free brazing brazed seam interface containing Ga and Nd
Intermetallic compound is without significant change and Wuxi must germinate, and illustrates that the reliability of solder joint (brazed seam) is significantly improved.
Embodiment 2
Sn-Cu-Ni lead-free brazing containing Ga and Nd, includes: 1.1% Cu, 0.05% Ni by mass percentage,
0.008% As, 0.014% Sb, 0.6% Ga, 0.06% Nd, surplus Sn.Wherein the mass ratio of Ga and Nd meets
Ga ︰ Nd=10 ︰ 1.
" the Sn-Cu-Ni lead-free brazing containing Ga and Nd " solidus temperature that mentioned component matches at 210 DEG C or so,
Liquidus temperature is 218 DEG C or so (considering test error).Cooperate commercially available RMA brazing flux that there is excellent profit on copper plate
Wet performance, brazed seam tensile strength reach 45MPa ± 5MPa.
Fig. 3 is shown, after timeliness 720 hours (30 days), is added to the Sn-Cu-Ni lead-free brazing brazed seam interface containing Ga and Nd
Intermetallic compound is without significant change and Wuxi must germinate, and illustrates that the reliability of solder joint (brazed seam) is significantly improved.
Embodiment 3
Sn-Cu-Ni lead-free brazing containing Ga and Nd, includes: 0.7% Cu, 0.15% Ni by mass percentage,
0.005% As, 0.016% Sb, 0.5% Ga, 0.05% Nd, surplus Sn.Wherein the mass ratio of Ga and Nd meets
Ga ︰ Nd=10 ︰ 1.
" the Sn-Cu-Ni lead-free brazing containing Ga and Nd " solidus temperature that mentioned component matches at 210 DEG C or so,
Liquidus temperature is 218 DEG C or so (considering test error).Cooperate commercially available RMA brazing flux that there is excellent profit on copper plate
Wet performance, brazed seam tensile strength reach 45MPa ± 5MPa.
Fig. 3 is shown, after timeliness 720 hours (30 days), is added to the Sn-Cu-Ni lead-free brazing brazed seam interface containing Ga and Nd
Intermetallic compound is without significant change and Wuxi must germinate, and illustrates that the reliability of solder joint (brazed seam) is significantly improved.
Embodiment 4
Sn-Cu-Ni lead-free brazing containing Ga and Nd, includes: 0.85% Cu, 0.35% Ni by mass percentage,
0.006% As, 0.018% Sb, 0.46% Ga, 0.046% Nd, surplus Sn.Wherein the mass ratio of Ga and Nd is full
Sufficient Ga ︰ Nd=10 ︰ 1.
" the Sn-Cu-Ni lead-free brazing containing Ga and Nd " solidus temperature that mentioned component matches at 210 DEG C or so,
Liquidus temperature is 218 DEG C or so (considering test error).Cooperate commercially available RMA brazing flux that there is excellent profit on copper plate
Wet performance, brazed seam tensile strength reach 45MPa ± 5MPa.
Fig. 3 is shown, after timeliness 720 hours (30 days), is added to the Sn-Cu-Ni lead-free brazing brazed seam interface containing Ga and Nd
Intermetallic compound is without significant change and Wuxi must germinate, and illustrates that the reliability of solder joint (brazed seam) is significantly improved.
Embodiment 5
Sn-Cu-Ni lead-free brazing containing Ga and Nd, includes: 0.65% Cu, 0.3% Ni by mass percentage,
0.004% As, 0.017% Sb, 0.55% Ga, 0.055% Nd, surplus Sn.Wherein the mass ratio of Ga and Nd is full
Sufficient Ga ︰ Nd=10 ︰ 1.
" the Sn-Cu-Ni lead-free brazing containing Ga and Nd " solidus temperature that mentioned component matches at 210 DEG C or so,
Liquidus temperature is 218 DEG C or so (considering test error).Cooperate commercially available RMA brazing flux that there is excellent profit on copper plate
Wet performance, brazed seam tensile strength reach 45MPa ± 5MPa.
Fig. 3 is shown, after timeliness 720 hours (30 days), is added to the Sn-Cu-Ni lead-free brazing brazed seam interface containing Ga and Nd
Intermetallic compound is without significant change and Wuxi must germinate, and illustrates that the reliability of solder joint (brazed seam) is significantly improved.
Claims (1)
1. the Sn-Cu-Ni lead-free brazing containing Ga and Nd, which is characterized in that by mass percentage include: 0.45~1.1%
Cu, 0.05~0.5% Ni, 0.003~0.008% As, 0.014~0.020% Sb, 0.4~0.6% Ga, 0.04
~0.06% Nd, surplus Sn；Wherein the mass ratio of Ga and Nd is 10 ︰ 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811097247.4A CN109048114B (en) | 2018-09-20 | 2018-09-20 | Sn-Cu-Ni lead-free solder containing Ga and Nd |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811097247.4A CN109048114B (en) | 2018-09-20 | 2018-09-20 | Sn-Cu-Ni lead-free solder containing Ga and Nd |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109048114A true CN109048114A (en) | 2018-12-21 |
| CN109048114B CN109048114B (en) | 2021-02-12 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007023288A2 (en) * | 2005-08-24 | 2007-03-01 | Fry's Metals Inc. | Solder alloy |
| US20070122646A1 (en) * | 2005-11-28 | 2007-05-31 | Cheng-Yi Liu | Solder composition and soldering structure |
| CN101456103A (en) * | 2008-11-18 | 2009-06-17 | 高新锡业（惠州）有限公司 | Leadless soft soldering material and manufacture method thereof |
| CN101862921A (en) * | 2010-06-25 | 2010-10-20 | 南京航空航天大学 | Sn-Cu-Ni lead-free solder containing Pr, Sr and Ga |
| CN101885119A (en) * | 2010-06-25 | 2010-11-17 | 常熟市华银焊料有限公司 | Sn-Cu-Ni lead-free solder containing V, Nd and Ge |
| CN102848100A (en) * | 2012-10-10 | 2013-01-02 | 南京航空航天大学 | Low-silver Sn-Ag-Cu lead-free brazing filler metal containing Nd and Ga |
-
2018
- 2018-09-20 CN CN201811097247.4A patent/CN109048114B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007023288A2 (en) * | 2005-08-24 | 2007-03-01 | Fry's Metals Inc. | Solder alloy |
| US20070122646A1 (en) * | 2005-11-28 | 2007-05-31 | Cheng-Yi Liu | Solder composition and soldering structure |
| CN101456103A (en) * | 2008-11-18 | 2009-06-17 | 高新锡业（惠州）有限公司 | Leadless soft soldering material and manufacture method thereof |
| CN101862921A (en) * | 2010-06-25 | 2010-10-20 | 南京航空航天大学 | Sn-Cu-Ni lead-free solder containing Pr, Sr and Ga |
| CN101885119A (en) * | 2010-06-25 | 2010-11-17 | 常熟市华银焊料有限公司 | Sn-Cu-Ni lead-free solder containing V, Nd and Ge |
| CN102848100A (en) * | 2012-10-10 | 2013-01-02 | 南京航空航天大学 | Low-silver Sn-Ag-Cu lead-free brazing filler metal containing Nd and Ga |
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| Publication number | Publication date |
|---|---|
| CN109048114B (en) | 2021-02-12 |
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Application publication date: 20181221 Assignee: YANGZHOU GUANGMING CABLE Co.,Ltd. Assignor: NANJING University OF SCIENCE AND TECHNOLOGY Contract record no.: X2023980032350 Denomination of invention: Sn-Cu-Ni lead-free solder containing Ga and Nd Granted publication date: 20210212 License type: Common License Record date: 20230221 |