CN102554504B - Self-soldering silver solder containing praseodymium, zirconium and gallium - Google Patents
Self-soldering silver solder containing praseodymium, zirconium and gallium Download PDFInfo
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- CN102554504B CN102554504B CN 201110445597 CN201110445597A CN102554504B CN 102554504 B CN102554504 B CN 102554504B CN 201110445597 CN201110445597 CN 201110445597 CN 201110445597 A CN201110445597 A CN 201110445597A CN 102554504 B CN102554504 B CN 102554504B
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Abstract
The invention discloses a self-soldering silver solder containing praseodymium, zirconium and gallium, and belongs to the technical field of soldering materials of metal materials. The solder is characterized by comprising the following components in percentage by mass: 45.0 to 62.0 percent of Ag, 9.0 to 13.0 percent of Zn, 1.0 to 3.0 percent of P, 0.001 to 0.01 percent of Pr, 0.001 to 0.01 percent of Zr, 0.001 to 0.01 percent of Ga, and the balance of Cu. The solder has the characteristics of good flowability, good wetting property, high soldered point strength and the like, has excellent 'self-soldering' property, is particularly suitable for 'solder-free' soldering of micro contacts of micro electrical appliance assemblies, and solves the problem that the soldered points of the complex electrical appliance assemblies are difficult to clean.
Description
Technical field
the invention belongs to the technical field of soldering materials of class of metal materials, be specifically related to a kind of self-fluxing silver solder containing praseodymium, zirconium and gallium, this self-fluxing silver solder has good mobility and wetability, Joint Strength is high and the solders such as alternative BAg65CuZn and BAg60CuZn, be applicable to the welding to the microminiature contact of microminiature electric appliance component, use without using brazing flux and embody the self-fluxing performance.
Background technology
the BAg65CuZn used in prior art, the BAg60CuZn solder, owing to only containing Ag, Cu, Zn element in its chemical composition, although when coordinating scaling powder (as the FB102 brazing flux), brazing property is good, can not meet the soldering requirement to the contact of the microminiature as the microminiature electric appliance component such as special braze-welded structure, special shape and special size.Because this type of " encapsulation " device after soldering completes, residues in " brazing flux residue " inside in packaging at solder joint position, can't be cleaned or be removed." brazing flux residue " if do not remove, and can cause the even solder joint short circuit that descends of the electrical property of solder joint.Therefore, must adopt the silver solder with " self-fluxing performance ", when soldering, not use brazing flux, rely on " the striping performance " of silver solder self to remove the oxide-film at soldering position, thereby realize brazing.
the applicant has carried out literature search, although be seen in the technical information of self-drill brazing filler in published Chinese patent literature, " high volume fraction grain enhanced aluminum-base compound material brazing filler metal and preparation method thereof " that " self-drill brazing filler of antimony alloy and antimony based composites and the preparation method " who slightly provides with " self-drill brazing filler of aluminium alloy and acieral composite and the preparation method ", the CN102079018A that recommend as CN1215918C exemplified and CN101722380A disclose, etc.But, being not limited to the disclosed self-drill brazing filler of these documents is not all the copper base solder category, therefore more particularly all do not belong to CNS GB/T6418-2008 " copper base solder " category, do not there is referential meaning for what improve copper base solder from haptotaxis.For this reason, the applicant has done positive lasting and useful experiment, and technical scheme described below produces under this background.
Summary of the invention
task of the present invention is to provide the more excellent and self-fluxing performance that use to stand out from one's fellows of a kind of performance with respect to BAg65CuZn and BAg60CuZn solder to meet the self-fluxing silver solder containing praseodymium, zirconium and gallium that the microminiature contact soldering to the microminiature electric appliance component requires.
task of the present invention completes like this, a kind of self-fluxing silver solder containing praseodymium, zirconium and gallium, it is characterized in that: composition by the mass percent proportioning is: the Zr of Pr, the 0.001-0.01% of P, the 0.001-0.01% of the Ag of 45.0-62.0%, the Zn of 9.0-13.0%, 1.0-3.0% and the Ga of 0.001-0.01%, surplus is Cu.
the described self-fluxing silver solder containing praseodymium, zirconium and gallium, composition by the mass percent proportioning is: 45.0% Ag, 13.0% Zn, 1.0% P, 0.01% Pr, 0.01% Zr and 0.001% Ga, surplus is Cu.
the described self-fluxing silver solder containing praseodymium, zirconium and gallium, composition by the mass percent proportioning is: 62.0% Ag, 9.0% Zn, 3.0% P, 0.001% Pr, 0.001% Zr and 0.01% Ga, surplus is Cu.
the described self-fluxing silver solder containing praseodymium, zirconium and gallium, composition by the mass percent proportioning is: 50.0% Ag, 12.0% Zn, 2.0% P, 0.01% Pr, 0.005% Zr and 0.008% Ga, surplus is Cu.
the described self-fluxing silver solder containing praseodymium, zirconium and gallium, composition by the mass percent proportioning is: 60.0% Ag, 11.0% Zn, 1.5% P, 0.003% Pr, 0.008% Zr and 0.005% Ga, surplus is Cu.
the described self-fluxing silver solder containing praseodymium, zirconium and gallium, composition by the mass percent proportioning is: 58.0% Ag, 10.0% Zn, 2.5% P, 0.008% Pr, 0.003% Zr and 0.005% Ga, surplus is Cu.
technical scheme provided by the invention is for the BAg65CuZn in prior art and BAg60CuZn solder, not only there is good fluidity, wetability is good, the Joint Strength high, but also there is " the self-fluxing performance " of standing out from one's fellows, be specially adapted to " without brazing flux " welding of the microminiature contact of microminiature electric appliance component, avoided complicated electric appliance component solder joint to be difficult to the problem of cleaning.Use the gas brazing mode, do not use brazing flux, brazing material is following combination: when red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy, the soldered fitting mechanical property is respectively: σ
b
=185～365MPa, τ=180～355MPa, with BAg65CuZn, the soldered fitting mechanical property when BAg60CuZn solder coordinates scaling powder (as the FB102 brazing flux) soldering red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy is suitable.
The specific embodiment
the present invention program has mainly solved following two key technical problems: 1) develop containing the self-fluxing silver solder of praseodymium, zirconium and gallium, good fluidity during soldering, wetability are good, Joint Strength is high.By optimizing the chemical composition of " containing the self-fluxing silver solder of praseodymium, zirconium and gallium ", make neoteric silver solder except can being prepared as a material, also can be prepared into the strip of various thickness and width; 2) by add micro-praseodymium, zirconium and gallium element in silver solder, add appropriate phosphorus simultaneously, make silver solder having on red copper, brass and nickel-base alloy well " self-fluxing performance ", can also guarantee that silver solder has good plasticity and comprehensive mechanical property simultaneously.
use commercially available silver, cathode copper, phosphor copper, gallium, metal praseodymium, zirconium copper alloy, proportioning, adopt conventional intermediate frequency smelting furnace to smelt, cast on demand, then, by extruding, drawing, obtains needed solder wire material; 2), according to need of production, gallium, metal praseodymium can be smelted into respectively to alloy in advance, then add in smelting furnace smelt, casting, then, by extruding, drawing, obtain needed solder wire material; Or, by the multiple tracks rolling process, be prepared into the strip of desired thickness, width.
with former studies, compare, the achievement part of technical scheme provided by the invention is:
1, the praseodymium, zirconium, gallium element of trace in the silver solder rule that affects on " low phosphorus content " silver solder " from haptotaxis " has been found in research---be praseodymium in silver solder, zirconium, gallium element content while being controlled at respectively in 0.001%～0.01% scope, can make 1.0%～3.0% the P there is good " self-fluxing performance ".
it is known by version GB/T 6418-2008 prevailing for the time being in force " copper base solder " table 4: when in copper base solder, P content is 4.8%～8.1%, be that Cu-P series solder has " from haptotaxis " when the soldering red copper, do not need to use scaling powder (being brazing flux), but there is no at present the report that is less than or equal to 3% the silver solder with " from haptotaxis " about P content both at home and abroad.
the inventor has found when praseodymium, zirconium, gallium element acting in conjunction, be the Ag that praseodymium, zirconium, gallium element add composition range to be 45.0%～62.0% simultaneously, 9.0%～13.0% Zn, 1.0%～3.0% P, during silver solder that all the other are Cu, silver solder has well " self-fluxing performance ".Further research is found, in the Ag-Cu-Zn solder, the content of P should be controlled at 1.0%～3.0% scope the best.Lower than 1.0% or all can the mechanical property of soldered fitting be had a negative impact higher than 3.0%, can make Joint Strength reduce.Therefore, controlling the content of P in the Ag-Cu-Zn solder in 1.0%～3.0% scope, is one of key point of the present invention program.
, research has been while having found that praseodymium, zirconium, the gallium element content of trace in the silver solder must be controlled at respectively in 0.001%～0.01% scope, just can make the Ag-Cu-Zn solder when P content is 1.0%～3.0%, have good " self-fluxing performance ", this and existing result of study have significant difference.Existing research is all to think that the upper content limit of rare earth element can reach even higher more than 0.1%, but, find as take the result of study that raising " silver solder is from haptotaxis " is purpose, if rare earth element surpasses 0.01%, will make " silver solder is from haptotaxis " to reduce rapidly.
, research found in silver solder to only have while adding micro-praseodymium, zirconium, gallium element simultaneously, the Ag-Cu-Zn solder that is 1.0%～3.0% to P content " self-fluxing performance " could produce good effect.
the research discovery, while adopting the Ce close with the Pr element, Nd element substitution Pr, neoteric silver solder " self-fluxing performance " descends rapidly, when the brazed seam strength of joint adds the Pr element, descends 15%～30%; When adopting with the Ti of Zr " of the same clan " or Hf element substitution Zr, the self-fluxing performance " descending causes neoteric silver solder mobility, wetability variation, when average " spreading area " adds the Zr element, reduces more than 30%; When adopting In element substitution Ga, " self-fluxing performance " descends and causes neoteric silver solder mobility, wetability variation, when average " spreading area " adds the Ga element, reduces more than 45%.Therefore, by a large amount of " screening ", " optimization " test, finally determined the Ag-Cu-Zn-P-Pr-Zr-Ga silver solder with " good self-fluxing performance ".Through actual soldering evidence, solder of the present invention is applicable to combined materials such as mode soldering red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy such as gas brazing, resistance brazing, induction brazings, and without adding scaling powder (as the FB102 brazing flux), the soldered fitting that available can be good.
as use the gas brazing mode, use neoteric " containing the self-fluxing silver solder of praseodymium, zirconium and gallium ", do not use brazing flux, the following combined material of soldering: when red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy, the soldered fitting mechanical property is respectively: σ
b
=185～365MPa, τ=180～355MPa, with BAg65CuZn, the soldered fitting mechanical property when BAg60CuZn solder coordinates scaling powder (as the FB102 brazing flux) soldering red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy is suitable.
the specific embodiment of the self-fluxing silver solder containing praseodymium, zirconium and gallium of the present invention that embodies above-mentioned technique effect is as follows.
embodiment 1:
45.0% Ag, 13.0% Zn, 1.0% P, 0.01% Pr, 0.01% Zr, 0.001% Ga, all the other are Cu." containing the self-fluxing silver solder of praseodymium, zirconium and gallium " that the mentioned component proportioning obtains used the gas brazing mode, do not use brazing flux, and the Joint intensity when soldering mother metal is following combination is shown in data in bracket: red copper-brass (σ
b
=210 ± 25MPa, τ=200 ± 30MPa), red copper-nickel-base alloy (σ
b
=210 ± 25MPa, τ=200 ± 30MPa), brass-nickel-base alloy (σ
b
=330 ± 25MPa, τ=325 ± 30MPa), with BAg65CuZn, the soldered fitting mechanical property when BAg60CuZn solder coordinates scaling powder (as the FB102 brazing flux) soldering red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy is suitable.
embodiment 2:
62.0% Ag, 9.0% Zn, 3.0% P, 0.001% Pr, 0.001% Zr, 0.01% Ga, all the other are Cu." containing the self-fluxing silver solder of praseodymium, zirconium and gallium " that the mentioned component proportioning obtains used the gas brazing mode, do not use brazing flux, and the Joint intensity when soldering mother metal is following combination is shown in data in bracket: red copper-brass (σ
b
=210 ± 25MPa, τ=200 ± 30MPa), red copper-nickel-base alloy (σ
b
=210 ± 25MPa, τ=200 ± 30MPa), brass-nickel-base alloy (σ
b
=330 ± 25MPa, τ=325 ± 30MPa), with BAg65CuZn, the soldered fitting mechanical property when BAg60CuZn solder coordinates scaling powder (as the FB102 brazing flux) soldering red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy is suitable.
embodiment 3:
50.0% Ag, 12.0% Zn, 2.0% P, 0.01% Pr, 0.005% Zr, 0.008% Ga, all the other are Cu." containing the self-fluxing silver solder of praseodymium, zirconium and gallium " that the mentioned component proportioning obtains used the gas brazing mode, do not use brazing flux, and the Joint intensity when soldering mother metal is following combination is shown in data in bracket: red copper-brass (σ
b
=210 ± 25MPa, τ=200 ± 30MPa), red copper-nickel-base alloy (σ
b
=210 ± 25MPa, τ=200 ± 30MPa), brass-nickel-base alloy (σ
b
=330 ± 25MPa, τ=325 ± 30MPa), with BAg65CuZn, the soldered fitting mechanical property when BAg60CuZn solder coordinates scaling powder (as the FB102 brazing flux) soldering red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy is suitable.
embodiment 4:
60.0% Ag, 11.0% Zn, 1.5% P, 0.003% Pr, 0.008% Zr, 0.005% Ga, all the other are Cu." containing the self-fluxing silver solder of praseodymium, zirconium and gallium " that the mentioned component proportioning obtains used the gas brazing mode, do not use brazing flux, and the Joint intensity when soldering mother metal is following combination is shown in data in bracket: red copper-brass (σ
b
=210 ± 25MPa, τ=200 ± 30MPa), red copper-nickel-base alloy (σ
b
=210 ± 25MPa, τ=200 ± 30MPa), brass-nickel-base alloy (σ
b
=330 ± 25MPa, τ=325 ± 30MPa), with BAg65CuZn, the soldered fitting mechanical property when BAg60CuZn solder coordinates scaling powder (as the FB102 brazing flux) soldering red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy is suitable.
embodiment 5:
58.0% Ag, 10.0% Zn, 2.5% P, 0.008% Pr, 0.003% Zr, 0.005% Ga, all the other are Cu." containing the self-fluxing silver solder of praseodymium, zirconium and gallium " that the mentioned component proportioning obtains used the gas brazing mode, do not use brazing flux, and the Joint intensity when soldering mother metal is following combination is shown in data in bracket: red copper-brass (σ b =210 ± 25MPa, τ=200 ± 30MPa), red copper-nickel-base alloy (σ b =210 ± 25MPa, τ=200 ± 30MPa), brass-nickel-base alloy (σ b =330 ± 25MPa, τ=325 ± 30MPa), with BAg65CuZn, the soldered fitting mechanical property when BAg60CuZn solder coordinates scaling powder (as the FB102 brazing flux) soldering red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy is suitable.
Claims (6)
1.
a kind of self-fluxing silver solder containing praseodymium, zirconium and gallium, it is characterized in that composition by the mass percent proportioning is: the Zr of Pr, the 0.001-0.01% of P, the 0.001-0.01% of the Ag of 45.0-62.0%, the Zn of 9.0-13.0%, 1.0-3.0% and the Ga of 0.001-0.01%, surplus is Cu.
2.
self-fluxing silver solder containing praseodymium, zirconium and gallium according to claim 1 is characterized in that composition by the mass percent proportioning is: 45.0% Ag, 13.0% Zn, 1.0% P, 0.01% Pr, 0.01% Zr and 0.001% Ga, surplus is Cu.
3.
self-fluxing silver solder containing praseodymium, zirconium and gallium according to claim 1 is characterized in that composition by the mass percent proportioning is: 62.0% Ag, 9.0% Zn, 3.0% P, 0.001% Pr, 0.001% Zr and 0.01% Ga, surplus is Cu.
4.
self-fluxing silver solder containing praseodymium, zirconium and gallium according to claim 1 is characterized in that composition by the mass percent proportioning is: 50.0% Ag, 12.0% Zn, 2.0% P, 0.01% Pr, 0.005% Zr and 0.008% Ga, surplus is Cu.
5.
self-fluxing silver solder containing praseodymium, zirconium and gallium according to claim 1 is characterized in that composition by the mass percent proportioning is: 60.0% Ag, 11.0% Zn, 1.5% P, 0.003% Pr, 0.008% Zr and 0.005% Ga, surplus is Cu.
6.
self-fluxing silver solder containing praseodymium, zirconium and gallium according to claim 1 is characterized in that composition by the mass percent proportioning is: 58.0% Ag, 10.0% Zn, 2.5% P, 0.008% Pr, 0.003% Zr and 0.005% Ga, surplus is Cu.
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|---|---|---|---|
| CN 201110445597 CN102554504B (en) | 2011-12-28 | 2011-12-28 | Self-soldering silver solder containing praseodymium, zirconium and gallium |
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| CN102554504B true CN102554504B (en) | 2013-11-06 |
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| CN105081607B (en) * | 2015-09-15 | 2017-05-03 | 江苏师范大学 | Self-fluxing silver solder containing Yb, Ge and nano Nb |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007023288A3 (en) * | 2005-08-24 | 2007-07-12 | Fry Metals Inc | Solder alloy |
| CN101132881A (en) * | 2004-12-01 | 2008-02-27 | 爱尔发加热有限公司 | Solder alloy |
| CN101537546A (en) * | 2009-04-17 | 2009-09-23 | 南京航空航天大学 | Sn-Ag-Cu lead-free solder containing Pr, Ni and Ga |
| 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 |
| CN102240870A (en) * | 2011-05-20 | 2011-11-16 | 杭州华光焊接新材料股份有限公司 | Multielement rare-earth silver solder |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200720005A (en) * | 2005-11-28 | 2007-06-01 | Univ Nat Central | Solder composition and soldering structure |
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2011
- 2011-12-28 CN CN 201110445597 patent/CN102554504B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101132881A (en) * | 2004-12-01 | 2008-02-27 | 爱尔发加热有限公司 | Solder alloy |
| WO2007023288A3 (en) * | 2005-08-24 | 2007-07-12 | Fry Metals Inc | Solder alloy |
| CN101537546A (en) * | 2009-04-17 | 2009-09-23 | 南京航空航天大学 | Sn-Ag-Cu lead-free solder containing Pr, Ni and Ga |
| 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 |
| CN102240870A (en) * | 2011-05-20 | 2011-11-16 | 杭州华光焊接新材料股份有限公司 | Multielement rare-earth silver solder |
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