CN102513722A - Medium temperature Zn-Al solder containing Sr, Si, Ti, Ni and P and having high air tightness - Google Patents
Medium temperature Zn-Al solder containing Sr, Si, Ti, Ni and P and having high air tightness Download PDFInfo
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- CN102513722A CN102513722A CN2012100046453A CN201210004645A CN102513722A CN 102513722 A CN102513722 A CN 102513722A CN 2012100046453 A CN2012100046453 A CN 2012100046453A CN 201210004645 A CN201210004645 A CN 201210004645A CN 102513722 A CN102513722 A CN 102513722A
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Abstract
The invention discloses a medium temperature Zn-Al solder containing Sr, Si, Ti, Ni and P and having high air tightness and belongs to a soldering material of metal materials. The solder comprises the following chemical components in percentage by mass: 0.01 to 0.1 percent of Sr, 1.5 to 6.5 percent of Si, 0.001 to 0.01 percent of Ti, 0.001 to 0.01 percent of Ni, 0.0001 to 0.001 percent of P, 36.0 to 65.0 percent of Zn and the balance of Al. The melting point of the solder is at about 480-520 DEG C, the solder has excellent wetting property and permeability on the surface of a high-strength aluminum alloy and a copper-aluminum alloy; a soldering seam has good mechanical property and good air tightness; and the solder is a novel medium temperature aluminum solder which can be applied to soldering of aluminum alloy and aluminum-aluminum pipeline structural parts of multiple brands.
Description
One, technical field
A kind of middle temperature Zn-Al solder that contains the high-air-tightness of Sr, Si, Ti, Ni, P cooperates commercially available CsF-AlF
3Brazing flux or KF-AlF
3Brazing flux is used for the soldering of aluminium-constructed of aluminium spare, belongs to the welding material of class of metal materials.
Two,
Background technology
At present; At household electric appliances, refrigeration industry, hardware industry; Because the use amount of copper is huge; Raising up of cathode copper price makes the demand of household electric appliances refrigerator, air-conditioner industry parts, system maker merchant " with aluminium for copper " along with the aggravation of household electric appliances " production capacity surplus " and the continuous upgrading of " product price war ", and be more and more urgent.In addition, in many industries, adopting 3 to be that (like 3003 aluminium alloys), 6 are (like 6061 aluminium alloys) high strength alumin ium alloy, make the all-aluminium construction parts, to substitute copper structure, also is the whole world manufacturing industry developing direction.But the welding difficult problem of high strength alumin ium alloy is more and more, presses for the new welding material of research and development and goes to solve.
Because the heat exchange effect and the copper of aluminium are very approaching, the processing characteristics of high strength alumin ium alloy, working ability have all had very big improvement, so the field that the aluminium instead of copper is used more and more widely.In recent years; At home and abroad in the evolution of domestic air conditioning, refrigerator, air conditioning for automobiles, automobile radiators; The lesson of many successful experience, failure, difficulty and demand to the high-strength aluminum alloy welding have caused various equivalent modifications and enterpriser's attention.The automotive air-conditioning system service condition is abominable more than domestic air conditioning, in air conditioning for automobiles, and the employing of the heat exchanger of high-efficiency compact (parallel flow type, stacked); Basically all adopt aluminium from compressor, heat exchanger, valve body to pipeline in the automotive air-conditioning system; This just requires intensity of aluminum alloy enough high; Weight is also light, corrosion resistance and good, therefore; Be the Welding Problems of the novel aluminum alloy that satisfies above-mentioned requirements and research and develop, adopt, also become one of restriction novel aluminum alloy material, novel aluminum alloy structure applications " key technology " simultaneously.In addition; When " pipe-pipe connections " of a large amount of heat exchangers that use aluminium alloys, because when working, the cold-producing medium of pipeline inside is generation " vapour-liquid conversion " under the situation of " pressure is arranged "; Therefore, to the particularly higher requirement of " air-tightness " proposition of aluminium alloy brazed seam of aluminium alloy pipeline.Because existing Al-Si brazing filler metal (as 4047,4043 etc.); Though its air-tightness meets the demands, the fusing point of himself higher (577 ℃ of solidus temperatures, liquidus temperature is more than 600 ℃); With 3 be, the fusing point of 6 series high-strength aluminum alloys is very approaching, soldering is difficulty very.(solidus temperature like 98Zn-2Al is 381 ℃ about 400 ℃ though its fusing point of Zn-Al solder can be low to moderate; Liquidus temperature is about 410 ℃); But the air-tightness of Zn-Al solder brazed seam is relatively poor; Breadboard " slip " can't satisfy the large-scale production requirement of a heat exchanger factory hundreds of thousands every day soldered fitting just up to 16% at all.This invention has the middle temperature almit of high-air-tightness, promptly under this technical background, accomplishes.
Three, summary of the invention
It is good that the purpose of this invention provides a kind of fusing point good mechanical properties, brazed seam air-tightness of wetability, superior permeability, brazed seam about 480 ℃ ~ 520 ℃, on high-strength aluminum alloy surface and on copper-aluminium alloy, goes for warm almit in welding novel of multiple grade aluminium alloy aluminium-aluminum pipe line structure spare.
For this reason, a kind of Zn-Al solder that contains Sr, Si, Ti, Ni, P of this invention, its chemical composition by mass percent is: 0.01% ~ 0.1% Sr; 1.5% ~ 6.5% Si, 0.001% ~ 0.01% Ti, 0.001% ~ 0.01% Ni; 0.0001% ~ 0.001% P; 36.0% ~ 65.0% Zn, surplus is the middle temperature almit with high-air-tightness of Al, has promptly satisfied above-mentioned requirements.
" middle temperature almit " of the present invention with high-air-tightness; Use commercially available zinc ingot metal, aluminium ingot, metal Ti, industrial silicon, al-sr alloy, nickel-phosphorus alloy; Adopt conventional smelting mode by the design mix proportioning; Add during smelting through optimizing and screen " coverture " confirmed or adopt " inert gas " protection to smelt, cast, 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.Add brazing flux, can be made into " flux-cored wire ".Product of the present invention can cooperate commercially available CsF-AlF
3Brazing flux or KF-AlF
3Brazing flux can be used for the soldering of multiple grade aluminium alloy aluminium-constructed of aluminium spare.
Though be generally 380 ℃～420 ℃ than the low melting temperature interval in order to reach the existing Zn-Al alloy solder fusing point of improvement), poor air-tightness; Al-Si brazing filler metal (as 4047,4043 etc.), though its air-tightness is good, higher (577 ℃ of the solidus temperatures of fusing point; Liquidus temperature is more than 600 ℃) a difficult problem; Through a large amount of " screening test ", confirmed that at last with the Zn-Al solder be matrix, add in a subtle way Sr, Si, Ti, Ni, the P element of (fitting) amount; Thereby neoteric solder molten temperature region is controlled at 480 ℃～520 ℃ scopes; Be lower than about 80 ℃ of the fusion temperatures of Al-Si brazing filler metal, utilize " microalloying " effect of more trace elements, improve the air-tightness of new invention solder.Through " optimizing components " and analysis of experiments, confirmed the best in quality percentage proportioning of " middle temperature almit " with high-air-tightness.Adopt oxy-propane flame brazing mode soldering 3003 aluminium-alloy pipes-tubular construction (socket), use " flux-cored wire " or brazing wire to cooperate CsF-AlF
3Brazing flux, soldered fitting is through the water pressure test (hydraulic pressure is 18MPa, pressurize 30 minutes), brazed seam does not have leakage.Soldered fitting maximum in the water pressure test is born pressure can reach 21 MPa (cracking at the aluminum pipe position).
Four, description of drawings
Fig. 1 brazed seam water pressure test correction data.
Five, specific embodiments
This invention has mainly solved following critical problem:
1) existing research shows: though the fusing point of Zn-Al alloy is low (generally at 380 ℃～420 ℃; Individual other fusing point can reach 450 ℃～460 ℃), but its " air-tightness " is poor, when " aluminum pipe-aluminum pipe " soldering connects; The brazed seam slip is higher, can't be in the heat exchanger sector application.Therefore, utilize " microalloying " effect of Sr, Si, Ti, Ni, P more trace elements, improved the air-tightness of new invention solder.
2) find through 15 groups of about 150 alloy formula experimental studies; The Sr, Si, Ti, Ni, P element that add the amount of (fitting) in a subtle way be in the bubble-tight while of improving Zn-Al alloy, also have improve Zn-Al alloy in high-strength aluminum alloy wetting of surfaces property, infiltrative effect.Simultaneously; Through optimizing the content range of Sr, Si, Ti, Ni, P element; The molten temperature region of neoteric solder is controlled at 480 ℃～520 ℃ scopes; About 80 ℃ of fusion temperatures that are lower than the Al-Si brazing filler metal are (like 577 ℃ of solidus temperatures such as 4047,4043; Liquidus temperature is more than 600 ℃), thus " middle temperature almit " (temperature is for 577 ℃～600 ℃ of fusing points of 4047 in this) obtained with high-air-tightness, and the soldering that can realize " aluminum pipe-aluminum pipe " at an easy rate connects and does not have the danger of aluminium alloy element " burning ", " subsiding ".Adopt oxy-propane flame brazing mode soldering 3003 aluminium-alloy pipes-tubular construction (socket), use " flux-cored wire " or brazing wire to cooperate CsF-AlF
3Brazing flux, soldered fitting is through the water pressure test (hydraulic pressure is 18MPa, pressurize 30 minutes), brazed seam does not have leakage.Soldered fitting maximum in the water pressure test is born pressure can reach 21 MPa (cracking at the aluminum pipe position).
Compare with former studies, creativeness of the present invention is:
One, found " raising air-tightness " effect of P element.
As everyone knows, in copper alloy, P has deoxidation, like " phosphorized copper " TP1 (referring to http://baike.baidu.com/view/3059316.htm).In " tin-lead solder " old edition national standard, the P of adding 0.001% ~ 0.004% and 0.001% ~ 0.004% Ga are referred to as " anti-oxidant tin-lead solder " (referring to GB 3131-88 " tin-lead solder " table 6).Through more than 10 years; P has " antioxidation " for after the known in tin-lead solder, lead-free brazing; In new edition (version prevailing for the time being in force) GB/T 3131-2001 " tin-lead solder " table 3, table 4; Though also listed two kinds of solders that contain P0.001% ~ 0.004% in, no longer indicating has been " anti-oxidant tin-lead solder ".And it is found that, only add P merely and get final product, needn't add the Ga element of equivalent simultaneously.But, in the present invention, find, verified through overtesting to be the adding of P not deoxidation, oxidation resistant effect, but to have the effect of " raising air-tightness ".
Two, the interpolation scope of verification experimental verification and preferred Sr, Si, Ti, Ni, P element.
Research in the past, in the research and development of new metallic material, the interpolation scope of Sr, Si, Ti, Ni, P is generally all very wide in range.Originally discover to have the Zn-Al base alloy of good " air-tightness ", good brazing property (like solder wetting property, permeability, brazed seam mechanical property), the addition of Sr can not surpass 0.01% ~ 0.1% scope; The addition of Si can not surpass 1.5% ~ 6.5% scope; The addition of Ti can not surpass 0.001% ~ 0.01% scope; The addition of Ni can not surpass 0.001% ~ 0.01% scope; The addition of P can not surpass 0.0001% ~ 0.001% scope.Special needs to be pointed out is: P adds in the solder (like lead-free brazing, tin-lead solder); Mainly be to play a part " anti-oxidant "; Its addition is 0.001% ~ 0.004% (referring to GB/T 3131-2001 " tin-lead solder " table 3); But in the present invention, the addition of P must be controlled at 0.0001% ~ 0.001% scope.
Lot of test is found, in Zn-Al base alloy, after adding elements such as Sr, Si, Ti, Ni, adds the P of trace again, promptly adds 0.0001% ~ 0.001% P, and is very big to the brazed seam air-tightness effect that improves the Zn-Al-Sr-Si-Ti-Ni-P solder.This breadboard test data shows; After adding the P element, the slip of brazed seam 6/100000ths has been dropped to and has added 2/100000ths of P, the heat exchanger of average 1000 groups of 100 passages of soldering by what do not add P; Have only two solder joints to need repair welding, slip has reduced by 66.7% (referring to table 1).
Three, discovered alterant element Sr and Si, Ti, Ni, P " cooperative effect ".
Existing research shows, in the Al-Si alloy, adds the reciprocation of element, particularly Sr such as Sr and B, Sr and Ti, has a large amount of bibliographical informations.But, Zn content is up to 36.0% ~ 65.0% solder of the present invention, and obviously the character with the Al-Si alloy has marked difference, adopts the method and element " processing of going bad " poor of existing bibliographical information.Therefore; The present invention is in test, research process; Found on the basis of adding Sr and Si, Ti, to add Ni, P element again, promptly when Ni, P element and Sr and Si, Ti coexistence are arranged; Have the bubble-tight effect of significant raising, and solder wetting property, permeability, brazed seam mechanical property are not had " negative Effect.Through adopting " sequential experiment design " method that Sr, Si, Ti, Ni, P are carried out further " preferably ", obtained the composition range of this claim 1.Adopt oxy-propane flame brazing mode soldering 3003 aluminium-alloy pipes-tubular construction (socket), use " flux-cored wire " or brazing wire to cooperate CsF-AlF
3Brazing flux, soldered fitting is through the water pressure test (hydraulic pressure is 18MPa, pressurize 30 minutes), brazed seam does not have leakage.Soldered fitting maximum in the water pressure test is born pressure can reach 21 MPa (cracking at the aluminum pipe position).
According to the quality prescription ratio of " middle temperature almit " of the present invention with high-air-tightness, associative list 1, it is following to narrate the specific embodiment of the present invention.
Embodiment one
A kind of middle temperature almit with high-air-tightness, its chemical composition by mass percent is: 0.01% Sr, 6.5% Si, 0.001% Ti, 0.01% Ni, 0.0001% P, 65.0% Zn, surplus is Al.
" the middle temperature almit with high-air-tightness " that the mentioned component proportioning obtains cooperates commercially available CsF-AlF
3Brazing flux or KF-AlF
3Brazing flux is, the good mechanical performance of wetability, superior permeability, brazed seam on the 6 series high strength aluminum alloy surface that air-tightness is good 3.Soldered fitting is through the water pressure test (hydraulic pressure is 18MPa, pressurize 30 minutes), and brazed seam does not have leakage, and soldered fitting maximum in the water pressure test is born pressure can reach 21 MPa (cracking at the aluminum pipe position).
Embodiment two
A kind of middle temperature almit with high-air-tightness, its chemical composition by mass percent is: 0.1% Sr, 1.5% Si, 0.01% Ti, 0.001% Ni, 0.001% P, 36.0% Zn, surplus is Al.
" the middle temperature almit with high-air-tightness " that the mentioned component proportioning obtains cooperates commercially available CsF-AlF
3Brazing flux or KF-AlF
3Brazing flux is, the good mechanical performance of wetability, superior permeability, brazed seam on the 6 series high strength aluminum alloy surface that air-tightness is good 3.Soldered fitting is through the water pressure test (hydraulic pressure is 18MPa, pressurize 30 minutes), and brazed seam does not have leakage, and soldered fitting maximum in the water pressure test is born pressure can reach 21 MPa (cracking at the aluminum pipe position).
Embodiment three
A kind of middle temperature almit with high-air-tightness, its chemical composition by mass percent is: 0.05% Sr, 4.5% Si, 0.005% Ti, 0.005% Ni, 0.0005% P, 46.0% Zn, surplus is Al.
" the middle temperature almit with high-air-tightness " that the mentioned component proportioning obtains cooperates commercially available CsF-AlF
3Brazing flux or KF-AlF
3Brazing flux is, the good mechanical performance of wetability, superior permeability, brazed seam on the 6 series high strength aluminum alloy surface that air-tightness is good 3.Soldered fitting is through the water pressure test (hydraulic pressure is 18MPa, pressurize 30 minutes), and brazed seam does not have leakage, and soldered fitting maximum in the water pressure test is born pressure can reach 21 MPa (cracking at the aluminum pipe position).
Embodiment four
A kind of middle temperature almit with high-air-tightness, its chemical composition by mass percent is: 0.09% Sr, 6.1% Si, 0.001% Ti, 0.002% Ni, 0.0002% P, 60.0% Zn, surplus is Al.
" the middle temperature almit with high-air-tightness " that the mentioned component proportioning obtains cooperates commercially available CsF-AlF
3Brazing flux or KF-AlF
3Brazing flux is, the good mechanical performance of wetability, superior permeability, brazed seam on the 6 series high strength aluminum alloy surface that air-tightness is good 3.Soldered fitting is through the water pressure test (hydraulic pressure is 18MPa, pressurize 30 minutes), and brazed seam does not have leakage, and soldered fitting maximum in the water pressure test is born pressure can reach 21 MPa (cracking at the aluminum pipe position).
Embodiment five
A kind of middle temperature almit with high-air-tightness, its chemical composition by mass percent is: 0.03% Sr, 6.1% Si, 0.01% Ti, 0.002% Ni, 0.0008% P, 56.0% Zn, surplus is Al.
" the middle temperature almit with high-air-tightness " that the mentioned component proportioning obtains cooperates commercially available CsF-AlF
3Brazing flux or KF-AlF
3Brazing flux is, the good mechanical performance of wetability, superior permeability, brazed seam on the 6 series high strength aluminum alloy surface that air-tightness is good 3.Soldered fitting is through the water pressure test (hydraulic pressure is 18MPa, pressurize 30 minutes), and brazed seam does not have leakage, and soldered fitting maximum in the water pressure test is born pressure can reach 21 MPa (cracking at the aluminum pipe position).
Claims (1)
1. middle temperature Zn-Al solder that contains the high-air-tightness of Sr, Si, Ti, Ni, P; Its chemical composition by mass percent is: 0.01% ~ 0.1% Sr, 1.5% ~ 6.5% Si, 0.001% ~ 0.01% Ti; 0.001% ~ 0.01% Ni; 0.0001% ~ 0.001% P, 36.0% ~ 65.0% Zn, surplus is Al.
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| CN103302417A (en) * | 2013-06-03 | 2013-09-18 | 北京科技大学 | Zn-Al-Cu-based brazing material and preparation method thereof |
| CN103317253A (en) * | 2013-06-03 | 2013-09-25 | 北京科技大学 | Zn-Al-Cu-based solder for aluminum/copper brazing and preparing method thereof |
| CN104070304A (en) * | 2013-03-28 | 2014-10-01 | 株式会社神户制钢所 | Aluminum alloy brazing filler metal and brazing plate |
| CN113579547A (en) * | 2021-08-12 | 2021-11-02 | 郑州机械研究所有限公司 | Brazing filler metal paste for copper-aluminum dissimilar metal brazing flux-free brazing and brazing method |
| CN113909734A (en) * | 2021-11-11 | 2022-01-11 | 烟台精创力合科技有限公司 | High-conductivity flux-cored soldering sheet |
| CN115106676A (en) * | 2022-05-23 | 2022-09-27 | 航天科工防御技术研究试验中心 | Aluminum alloy brazing filler metal wire and preparation method thereof |
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| CN113909734A (en) * | 2021-11-11 | 2022-01-11 | 烟台精创力合科技有限公司 | High-conductivity flux-cored soldering sheet |
| CN115106676A (en) * | 2022-05-23 | 2022-09-27 | 航天科工防御技术研究试验中心 | Aluminum alloy brazing filler metal wire and preparation method thereof |
| CN115106676B (en) * | 2022-05-23 | 2023-09-01 | 航天科工防御技术研究试验中心 | Aluminum alloy solder wire and preparation method thereof |
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Effective date of registration: 20210918 Address after: 321016 building A5, No. 3188, south 2nd Ring West Road, qiubin street, Wucheng District, Jinhua City, Zhejiang Province Patentee after: ZHEJIANG YONGWANG WELDING MATERIAL MANUFACTURING Co.,Ltd. Address before: Yudaojie Baixia District of Nanjing City, Jiangsu Province, No. 29 210016 Patentee before: Nanjing University of Aeronautics and Astronautics |