CN102554504A - 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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- CN102554504A CN102554504A CN2011104455977A CN201110445597A CN102554504A CN 102554504 A CN102554504 A CN 102554504A CN 2011104455977 A CN2011104455977 A CN 2011104455977A CN 201110445597 A CN201110445597 A CN 201110445597A CN 102554504 A CN102554504 A CN 102554504A
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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 contain praseodymium, zirconium and gallium from the haptotaxis silver solder; Should have good flowability and wetability, Joint Strength height and solders such as alternative BAg65CuZn and BAg60CuZn from the haptotaxis silver solder; Be applicable to welding, need not to use brazing flux and use and embody the self-fluxing performance the microminiature contact of microminiature electric appliance component
Background technology
The BAg65CuZn that uses in
prior art; The BAg60CuZn solder; Owing to only contain Ag, Cu, Zn element in its chemical composition; Though brazing property is good when cooperating scaling powder (like the FB102 brazing flux), satisfied not to soldering requirement like the microminiature contact of microminiature electric appliance component such as special braze-welded structure, special shape and special size.Because this type of " encapsulation " device is after soldering is accomplished, " the brazing flux residue " that residue in the solder joint position is in the inside of packaging, can't clean or remove." brazing flux residue " then can cause the electrical property of solder joint to descend even the solder joint short circuit if do not remove.Therefore, must adopt silver solder, promptly 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 that soldering connects with " self-fluxing performance ".
the applicant has carried out literature search; Though in disclosed Chinese patent document, be seen in the technical information of self-drill brazing filler; " self-drill brazing filler of antimony alloy and antimony based composites and preparation method " and " high volume fraction grain enhanced aluminum-base compound material brazing filler metal and preparation method thereof " of CN101722380A disclosure of slightly providing with " self-drill brazing filler of aluminium alloy and acieral composite and the preparation method ", the CN102079018A that recommend like CN1215918C that gives an example, or the like.But; Being not limited to the disclosed self-drill brazing filler of these documents all is not the copper base solder category; Therefore more particularly all do not belong to CNS GB/T6418-2008 " copper base solder " category, do not have referential meaning for what improve copper base solder from haptotaxis.For this reason, the applicant has done positive lasting and useful experiment, and the technical scheme that will introduce below produces under this background
Summary of the invention
task of the present invention be to provide a kind of performance with respect to BAg65CuZn and BAg60CuZn solder more excellent and use with the self-fluxing performance of standing out from one's fellows satisfy that microminiature contact soldering to the microminiature electric appliance component requires contain praseodymium, zirconium and gallium from the haptotaxis silver solder.
task of the present invention is accomplished like this; A kind of contain praseodymium, zirconium and gallium from the haptotaxis silver solder; It is characterized in that: composition by the mass percent proportioning is: the P of the Ag of 45.0-62.0%, the Zn of 9.0-13.0%, 1.0-3.0%, the Pr of 0.001-0.01%, the Zr of 0.001-0.01% and the Ga of 0.001-0.01%, surplus is Cu.
described contain praseodymium, zirconium and gallium from the haptotaxis silver solder, 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.
described contain praseodymium, zirconium and gallium from the haptotaxis silver solder, 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.
described contain praseodymium, zirconium and gallium from the haptotaxis silver solder, 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.
described contain praseodymium, zirconium and gallium from the haptotaxis silver solder, 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.
described contain praseodymium, zirconium and gallium from the haptotaxis silver solder, 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 BAg65CuZn in the prior art and BAg60CuZn solder; Not only have good fluidity, wetability is good; Characteristics such as Joint Strength height; But also have " the self-fluxing performance " of standing out from one's fellows, be specially adapted to " no brazing flux " welding of the microminiature contact of microminiature electric appliance component, the problem of having avoided complicated electric appliance component solder joint to be difficult to clean.Use the gas brazing mode, do not use brazing flux, brazing material is a 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 the BAg60CuZn solder cooperates scaling powder (like 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 contain praseodymium, zirconium and gallium from the haptotaxis silver solder, good fluidity during soldering, wetability are good, Joint Strength is high.Through optimizing the chemical composition of " contain praseodymium, zirconium and gallium from the haptotaxis silver solder ", make neoteric silver solder except that can being prepared as a material, also can be prepared into the strip of all thickness and width; 2) through in silver solder, adding praseodymium, zirconium and the gallium element of trace; Add an amount of 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.
Commercially available silver, cathode copper, phosphor copper, gallium, metal praseodymium, zirconium copper alloy are used in
; Proportioning on demand; Adopt conventional intermediate frequency smelting furnace to smelt, cast, through extruding, drawing, promptly obtain needed solder wire material then; 2), according to the production needs, can gallium, metal praseodymium be smelted into alloy respectively in advance, add then in the smelting furnace smelt, casting, through extruding, drawing, promptly obtain needed solder wire material again; Or, be prepared into the strip of desired thickness, width through the multiple tracks rolling process.
Compare with former studies, the achievement part of technical scheme provided by the invention is:
1, the praseodymium of having discovered trace in the silver solder, zirconium, gallium element are to the rule that influences of " low phosphorus content " silver solder " from haptotaxis "---and be praseodymium in the silver solder, zirconium, gallium element content when being controlled in 0.001%～0.01% the scope respectively, can make 1.0%～3.0% the P have good " self-fluxing performance ".
can be known by version GB/T 6418-2008 prevailing for the time being in force " copper base solder " table 4: P content is 4.8%～8.1% o'clock in the copper base solder; Be that Cu-P series solder has " from haptotaxis " when the soldering red copper; Need not use scaling powder (being brazing flux), be less than or equal to the report of 3% silver solder in P content with " from haptotaxis " but still have nothing to do at present both at home and abroad.
inventor has found when praseodymium, zirconium, gallium element acting in conjunction; Be that to add composition range simultaneously be 45.0%～62.0% Ag for praseodymium, zirconium, gallium element; 9.0%～13.0% Zn; 1.0%～3.0% P, when all the other were the silver solder of Cu, silver solder had well " self-fluxing performance ".Discover that further it is best that the content of P should be controlled at 1.0%～3.0% scope in the Ag-Cu-Zn solder.Be lower than 1.0% or be higher than 3.0% and all can the mechanical property of soldered fitting be had a negative impact, Joint Strength is reduced.Therefore, the content of P is one of key point of the present invention program in 1.0%～3.0% scope in the control Ag-Cu-Zn solder.
When
, praseodymium, zirconium, the gallium element content of having discovered trace in the silver solder must be controlled in 0.001%～0.01% the scope respectively; Just can make the Ag-Cu-Zn solder is 1.0%～3.0% o'clock at P content; Have good " self-fluxing performance ", this and existing result of study have significant difference.Existing research all is to think that the upper content limit of rare earth element can reach more than 0.1% even higher; But; As to improve the result of study discovery that " silver solder is from haptotaxis " is purpose,, " silver solder is from haptotaxis " reduced rapidly if rare earth element surpasses 0.01%.
, discovered in the silver solder, when having only simultaneously the praseodymium that adds trace, zirconium, gallium element, be that 1.0%～3.0% Ag-Cu-Zn solder " self-fluxing performance " could produce good effect to P content.
are discovered, when adopting the Ce close with the Pr element, Nd element substitution Pr, neoteric silver solder " self-fluxing performance " descends rapidly, descends 15%～30% when the brazed seam strength of joint adds the Pr element; When adopting, self-fluxing performance with the Ti of Zr " of the same clan " or Hf element substitution Zr " descending causes that neoteric silver solder is mobile, the wetability variation, reduces more than 30% when average " spreading area " adds the Zr element; When adopting In element substitution Ga, " self-fluxing performance " descends and causes neoteric silver solder flowability, wetability variation, reduces more than 45% when average " spreading area " adds the Ga element.Therefore, through a large amount of " screening ", " optimization " test, the Ag-Cu-Zn-P-Pr-Zr-Ga silver solder of having confirmed to have " good self-fluxing performance " at last.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 need not to add scaling powder (like the FB102 brazing flux), can obtain the soldered fitting of function admirable.
As use the gas brazing mode; Use neoteric " contain praseodymium, zirconium and gallium from the haptotaxis silver solder "; Do not use brazing flux, soldering combination material: 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 the BAg60CuZn solder cooperates scaling powder (like the FB102 brazing flux) soldering red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy is suitable.
Above-mentioned technique effect is embodied in
, and the concrete embodiment from the haptotaxis silver solder that contains praseodymium, zirconium and gallium of the present invention is following.
Embodiment 1:
The Ag of
45.0%, 13.0% Zn, 1.0% P, 0.01% Pr, 0.01% Zr, 0.001% Ga, all the other are Cu.Use the gas brazing mode " contain praseodymium, zirconium and gallium from the haptotaxis silver solder " that the mentioned component proportioning obtains, and do not use brazing flux, and the brazed seam intensity when the soldering mother metal is combination is seen data in the 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 the BAg60CuZn solder cooperates scaling powder (like the FB102 brazing flux) soldering red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy is suitable.
Embodiment 2:
The Ag of
62.0%, 9.0% Zn, 3.0% P, 0.001% Pr, 0.001% Zr, 0.01% Ga, all the other are Cu.Use the gas brazing mode " contain praseodymium, zirconium and gallium from the haptotaxis silver solder " that the mentioned component proportioning obtains, and do not use brazing flux, and the brazed seam intensity when the soldering mother metal is combination is seen data in the 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 the BAg60CuZn solder cooperates scaling powder (like the FB102 brazing flux) soldering red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy is suitable.
Embodiment 3:
The Ag of
50.0%, 12.0% Zn, 2.0% P, 0.01% Pr, 0.005% Zr, 0.008% Ga, all the other are Cu.Use the gas brazing mode " contain praseodymium, zirconium and gallium from the haptotaxis silver solder " that the mentioned component proportioning obtains, and do not use brazing flux, and the brazed seam intensity when the soldering mother metal is combination is seen data in the 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 the BAg60CuZn solder cooperates scaling powder (like the FB102 brazing flux) soldering red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy is suitable.
Embodiment 4:
The Ag of
60.0%, 11.0% Zn, 1.5% P, 0.003% Pr, 0.008% Zr, 0.005% Ga, all the other are Cu.Use the gas brazing mode " contain praseodymium, zirconium and gallium from the haptotaxis silver solder " that the mentioned component proportioning obtains, and do not use brazing flux, and the brazed seam intensity when the soldering mother metal is combination is seen data in the 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 the BAg60CuZn solder cooperates scaling powder (like the FB102 brazing flux) soldering red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy is suitable.
Embodiment 5:
The Ag of
58.0%, 10.0% Zn, 2.5% P, 0.008% Pr, 0.003% Zr, 0.005% Ga, all the other are Cu.Use the gas brazing mode " contain praseodymium, zirconium and gallium from the haptotaxis silver solder " that the mentioned component proportioning obtains, and do not use brazing flux, and the brazed seam intensity when the soldering mother metal is combination is seen data in the 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 the BAg60CuZn solder cooperates scaling powder (like the FB102 brazing flux) soldering red copper-brass, red copper-nickel-base alloy, brass-nickel-base alloy is suitable
Claims (6)
- a kind of contain praseodymium, zirconium and gallium from the haptotaxis silver solder; It is characterized in that composition by the mass percent proportioning is: the P of the Ag of 45.0-62.0%, the Zn of 9.0-13.0%, 1.0-3.0%, the Pr of 0.001-0.01%, the Zr of 0.001-0.01% and the Ga of 0.001-0.01%, surplus is Cu.
- according to claim 1 contain praseodymium, zirconium and gallium from the haptotaxis silver solder; It 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.
- according to claim 1 contain praseodymium, zirconium and gallium from the haptotaxis silver solder; It 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.
- according to claim 1 contain praseodymium, zirconium and gallium from the haptotaxis silver solder; It 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.
- according to claim 1 contain praseodymium, zirconium and gallium from the haptotaxis silver solder; It 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. According to claim 1 contain praseodymium, zirconium and gallium from the haptotaxis silver solder, it 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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| Application Number | Priority Date | Filing Date | Title |
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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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110445597 CN102554504B (en) | 2011-12-28 | 2011-12-28 | Self-soldering silver solder containing praseodymium, zirconium and gallium |
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| CN102554504B CN102554504B (en) | 2013-11-06 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105081607A (en) * | 2015-09-15 | 2015-11-25 | 江苏师范大学 | Self-fluxing silver solder containing Yb, Ge and nano Nb |
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| 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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2011
- 2011-12-28 CN CN 201110445597 patent/CN102554504B/en active Active
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|---|---|---|---|---|
| CN101132881A (en) * | 2004-12-01 | 2008-02-27 | 爱尔发加热有限公司 | Solder alloy |
| WO2007023288A2 (en) * | 2005-08-24 | 2007-03-01 | Fry's Metals Inc. | Solder alloy |
| WO2007023288A3 (en) * | 2005-08-24 | 2007-07-12 | Fry Metals Inc | Solder alloy |
| US20070122646A1 (en) * | 2005-11-28 | 2007-05-31 | Cheng-Yi Liu | Solder composition and soldering structure |
| 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 |
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| CN105081607A (en) * | 2015-09-15 | 2015-11-25 | 江苏师范大学 | Self-fluxing silver solder containing Yb, Ge and nano Nb |
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