CN104694789B - 4004 aluminium alloys and its production method of soldering bismuth-containing and tellurium - Google Patents
4004 aluminium alloys and its production method of soldering bismuth-containing and tellurium Download PDFInfo
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Abstract
The present invention relates to a kind of soldering bismuth-containing and 4004 aluminium alloys and its production method of tellurium, it is characterised in that its chemical constituent is by mass percentage：Si：9.0~10.5%, Mg：1.0~2.0%, Fe≤0.8%, Cu≤0.25%, Mn≤0.1%, Zn≤0.20%, Sr：0.02~0.2%, Bi：0.02~2.0%, Te：0.01~1.0%, single content≤0.05% of other impurity elements, other impurity element total content≤0.15%, balance of Al；The production method of the aluminium alloy is smelting, degasification removes the gred, cast, destressing and sawing are obtained.The present invention reduces the surface tension of 4004 alloys by adding micro Bi and Te elements, the mobility and wetability of 4004 alloys when improving soldering, reduces welding point fraction defective, reduces welding leak source incidence.
Description
Technical field
The present invention relates to a kind of manufacture field of aluminium alloy, and in particular to 4004 aluminium alloys of a kind of soldering bismuth-containing and tellurium
And its production method.
Background technology
4004 as Al-Si alloys one kind, often and 3003 aluminium alloys are rolled into Al alloy composite together, 4004 make
It is clad, in vacuum brazing, soldering effect is played in clad fusing.Al alloy composite is widely used in automobile, sky
On the radiator or heat exchanger of tune, oxygenerator and deep freeze refrigeration plant.Large-scale changed especially for what the air separation plants such as oxygenerator were used
Hot device, it is necessary to work, the quality requirement for heat exchanger is stricter, this is required in vacuum brazing under pressure
The brazing quality of heat exchanging device proposes requirements at the higher level.Welded when causing the underproof main cause of radiator to be exactly soldering at present
Weld is bad, and this caused by the solder fluidity of clad 4004 deficiency, is particularly connect with strip of paper used for sealing in dividing plate when soldering
Contact portion position is easier leak source occur, causes finished product to be scrapped.
At present in vacuum brazing, in order to obtain preferable welding quality, mainly there is following several method：One is current master
If alloying technology aspect is improved, vacuum higher such as being ensured, carrying out alloy surface cleaning, optimization uses suitable brazing flux etc.
Measure so that metal oxide film is easily broken during soldering, increases solder fluidity and wetability, reaches preferable Product jointing matter
Amount；Two is to use magnesium powder or other suitable brazing fluxes, destroys oxide-film, improves solder wetting；Three be Optimum Temperature Raising speed and
Cooling velocity；Four is the Pressure Rise Rate for reducing vacuum brazing furnace as far as possible, it is ensured that sufficiently low vacuum.
But in actual production, if magnesium powder does not have the effect of destruction oxide-film using very few；Magnesium powder is excessive to drop again
Low solder flowing velocity, is difficult to control.Magnesium powder meeting contaminated vacuum system is, it is necessary to timely clean vacuum system simultaneously.In addition, vacuum
The Pressure Rise Rate of soldering oven, mainly soldering oven seal an index of gas leakage performance, and in general Pressure Rise Rate ＜ 0.3Pa/h can be with
Preferable brazing quality is obtained, this proposes requirement very high to equipment performance.Heating too fast alloy surface in heating can oxygen
Change, part is easily deformed；Programming rate is slow, and the volatilization of solder low melting point composition is serious, and remaining brazing filler metal compositions useful fusing point will be raised,
Cause not weld.Accurate temperature control also has direct relation except technological design with the temperature control ability of equipment, and this is same right
Soldering oven proposes high requirement.
4004 aluminium alloys of relevant soldering, we retrieve documents below：
1st, Chinese patent, title：A kind of 4004 aluminium alloys of soldering, application（Patent）Number:CN 201310276733.3,
It is open（Bulletin）Number:The A of CN 103343267, the applying date：2013.07.03, apply（Patent right）People:Silver-colored nation's Metals composite
Material limited company, address:New District, Wuxi City, Jiangsu Province Hong Shan streets Hou Zhai, invention（Design）People:Lv Jinming, Zhou De
Respect, make a summary:A kind of 4004 aluminium alloys of soldering, its mobility that can effectively improve solder aluminium alloy, improve product soldering into
Material rate.It is characterized in that：It includes the following material that gross mass number is 100 parts, silicon（Si）For 10.2 parts~11.2 parts, iron
（Fe）≤ 0.3 part, copper（Cu）≤ 0.2 part, manganese（Mn）≤ 0.05 part, magnesium（Mg）It is 0.5~1.0 part, zinc（Zn）≤0.1
Part, remaining is aluminium（Al）And inevitable impurity element.
4004 aluminium alloys of soldering disclosed in above-mentioned document 1 are over oxidations when preventing soldering by reducing content of magnesium, this
The wetability of alloy when the method for kind cannot also dramatically increase soldering simultaneously, does not have the effect of destruction oxide-film, and content of magnesium
The wetability of solder is poor when reduction causes vacuum brazing, increases welding leak source incidence, causes heat exchanger after vacuum brazing
Qualification rate is low.
The content of the invention
The invention aims to overcome the deficiencies in the prior art, there is provided 4004 aluminium of a kind of soldering bismuth-containing and tellurium are closed
Gold and its production method, 4004 aluminium alloy reduce the surface tension of 4004 alloys by adding bismuth and tellurium element, significantly improve
The mobility and wetability of 4004 alloys, greatly reduce weld fraction defective during soldering.
What the present invention was realized in：
A kind of soldering bismuth-containing and the aluminium alloy of tellurium 4004, it is characterised in that its chemical constituent is by mass percentage：Si：
9.0~10.5%, Mg：1.0~2.0%, Fe≤0.8%, Cu≤0.25%, Mn≤0.1%, Zn≤0.20%, Sr：0.02~0.2%,
Bi：0.02~2.0%, Te：0.01~1.0%, single content≤0.05% of other impurity elements, other impurity element total contents≤
0.15%, balance of Al.
The production method of soldering bismuth-containing of the present invention and the aluminium alloy of tellurium 4004, it is characterised in that：Removed including melting, degasification
Slag, casting, destressing and sawing operation, detailed process are as follows：
（1）Melting：During purity is put into smelting furnace up to the aluminium ingot of 99.75% and the above, and alloying element is weighed by proportioning
Melting is carried out at a temperature of 720~770 DEG C after good shove charge, speed of melting is accelerated with electromagnetic agitation in fusion process, and with taking off
The slag car carries out taking off slag operation to aluminium liquid slag inclusion, and aluminium liquid is in melting in-furnace time≤8h；
（2）Degasification removes the gred：Smelting aluminium alloy melt carries out furnace refining and online degasification, slagging-off；Online degasification is adopted
It is argon gas as blanketing gas, prevents the aluminium liquid after purification from secondary oxidation occurring, gas flow is 2~5m3/ h, degasification
Temperature of aluminum liquid is maintained between 700~740 DEG C in journey, last filter cleaner, and the aluminum melt after filtering can directly be cast；
（3）Casting：The casting of aluminium alloy controls temperature for 670~720 DEG C, and casting speed is 20-70mm/min, cooling water
It is 40-190 m3/ h, obtains ingot casting；
（4）Destressing：The destressing of ingot casting controls temperature for 420~500 DEG C, in 120T homogenizing annealing stoves inside holding 8
~18 hours；
（5）Sawing：Aluminium alloy cast ingot after destressing is processed carries out crop end, is then sawed aluminium alloy using plane
Ingot casting is sawed into the aluminum alloy plate materials of required thickness, obtains 4004 aluminium alloys.
Above-described online degasification be furnace refining after the completion of, standing furnace exit using online hydrogen meter determine aluminium
The liquid hydrogen content of melt, depassing unit is gone to by aluminium liquid, depassing unit argon gas is stirred by rotor to be formed it is small more
Scattered bubble, adsorbs the free hydrogen and harmful substance in aluminium liquid during bubble floating, temperature of aluminum liquid is maintained in degassing procedure
Between 700~740 DEG C.
Above-described online degasification is that, using argon gas degasification, flow is 2~5m3/ t aluminum melts, rotor speed be 350~
580rpm。
It is above-described to be filtered into first with 30PPI type filter plates, Rose Box filtering is then imported again.
Utstanding substantial characteristics and significant improvement of the present invention are：
1st, the present invention reduces by 4004 alloys by 4004 solder alloy composition adjustments, adding micro Bi and Te elements
Surface tension, increased its wetability and spreadability, reduce welding leak source incidence.Low-alloyed table can substantially drop in addition Bi
Face tension force, and Bi can be effectively improved the form of α-Al dendrite nets and eutectic Si；Te is easy to be enriched with alloy surface layer, reduces
Surface tension, increases the wettability of Al-Si soldering fillers, and Te has very strong dehydrogenation, can make containing for aluminium liquid
Hydrogen amount is further reduced, and suppresses the formation of stomata or pin hole；Bi and Te can very well improve the wetability of 4004 alloys, particularly
There is the spreadability that material can be more efficiently improved in the presence of Te.
2nd, 4004 aluminium alloy of the invention verifies by actual production, under same process, uses the 4004 of bismuth-containing and tellurium
/ 3003 compared with conventional 4004/3003 brazing material, and heat exchanger leak source quantity in soldering is substantially reduced, and is changed after vacuum brazing
The qualification rate of hot device improves 5%, and maximum pressure improves about 20% during hydraulic pressure test, and effect is obvious.
3rd, the oxygen during 4004 aluminium alloy melt of the invention removes aluminum melt in preparation process by degasification slag removing system
Compound, non-metallic inclusion and other harmful metal impurities so that the H content in ingot casting is controlled in below 0.15ml/100gAl,
Degassing efficiency and degasification quality can be significantly improved, the casting flaw aluminium alloy such as flawless, loose, pinhole is obtained, be mingled with
Ingot casting, makes ingot casting yield rate reach more than 95%.
Specific embodiment
Embodiment 1
（One）Raw material and weight：
Its chemical constituent is by mass percentage：Si：9.0%、Mg：1.0%、Fe≤0.8%、Cu≤0.25%、Mn≤0.1%、
Zn≤0.20%、Sr：0.02%、Bi：0.02%、Te：0.01%th, single content≤0.05% of other impurity elements, other impurity elements
Total content≤0.15%, balance of Al.
（Two）Production method：
（1）Melting：During purity is put into smelting furnace up to the aluminium ingot of 99.75% and the above, and alloying element is weighed by proportioning
Melting is carried out at a temperature of 720 DEG C after good shove charge, speed of melting is accelerated with electromagnetic agitation in fusion process, and with forklift for slag pair
Aluminium liquid slag inclusion carries out taking off slag operation, and aluminium liquid is in melting in-furnace time 8h；
（2）Degasification removes the gred：Smelting aluminium alloy melt carries out furnace refining and online degasification, slagging-off；Online degasification is adopted
It is argon gas as blanketing gas, prevents the aluminium liquid after purification from secondary oxidation occurring, gas flow is 2m3/ h, degassing procedure
Middle temperature of aluminum liquid is maintained between 700 DEG C, last filter cleaner, and the aluminum melt after filtering can directly be cast；
（3）Casting：The casting of aluminium alloy controls temperature for 670 DEG C, and casting speed is 20-70mm/min, and cooling water is
40-190 m3/ h, obtains ingot casting；
（4）Destressing：The destressing of ingot casting controlled temperature for 420 DEG C, in 120T homogenizing annealing stoves inside holding 18 hours；
（5）Sawing：Aluminium alloy cast ingot after destressing is processed carries out crop end, is then sawed aluminium alloy using plane
Ingot casting is sawed into the aluminum alloy plate materials of required thickness, obtains 4004 aluminium alloys.
Described online degasification is that flow is 2m using argon gas degasification3/ t aluminum melts, rotor speed is 350rpm.
Described is filtered into first with 30PPI type filter plates, and Rose Box filtering is then imported again.
Embodiment 2
（One）Raw material and weight：
Its chemical constituent is by mass percentage：Si：9.5%、Mg：1.5%、Fe≤0.8%、Cu≤0.25%、Mn≤0.1%、
Zn≤0.20%、Sr：0.1%、Bi：0.1%、Te：0.1%th, single content≤0.05% of other impurity elements, other impurity elements are total
Content≤0.15%, balance of Al.
（Two）Production method：
（1）Melting：During purity is put into smelting furnace up to the aluminium ingot of 99.75% and the above, and alloying element is weighed by proportioning
Melting is carried out at a temperature of 740 DEG C after good shove charge, speed of melting is accelerated with electromagnetic agitation in fusion process, and with forklift for slag pair
Aluminium liquid slag inclusion carries out taking off slag operation, and aluminium liquid is in melting in-furnace time 7.5h；
（2）Degasification removes the gred：Smelting aluminium alloy melt carries out furnace refining and online degasification, slagging-off；Online degasification is adopted
It is argon gas as blanketing gas, prevents the aluminium liquid after purification from secondary oxidation occurring, gas flow is 3m3/ h, degassing procedure
Middle temperature of aluminum liquid is maintained between 710 DEG C, last filter cleaner, and the aluminum melt after filtering can directly be cast；
（3）Casting：The casting of aluminium alloy controls temperature for 690 DEG C, and casting speed is 20-70mm/min, and cooling water is
40-190 m3/ h, obtains ingot casting；
（4）Destressing：The destressing of ingot casting controlled temperature for 440 DEG C, in 120T homogenizing annealing stoves inside holding 16 hours；
（5）Sawing：Aluminium alloy cast ingot after destressing is processed carries out crop end, is then sawed aluminium alloy using plane
Ingot casting is sawed into the aluminum alloy plate materials of required thickness, obtains 4004 aluminium alloys.
Described online degasification is that flow is 3m using argon gas degasification3/ t aluminum melts, rotor speed is 400rpm.
Described is filtered into first with 30PPI type filter plates, and Rose Box filtering is then imported again.
Embodiment 3
（One）Raw material and weight：
Its chemical constituent is by mass percentage：Si：10.0%、Mg：1.8%、Fe≤0.8%、Cu≤0.25%、Mn≤
0.1%、Zn≤0.20%、Sr：0.15%、Bi：1.0%、Te：0.5%th, single content≤0.05% of other impurity elements, other impurity
Element total content≤0.15%, balance of Al.
（Two）Production method：
（1）Melting：During purity is put into smelting furnace up to the aluminium ingot of 99.75% and the above, and alloying element is weighed by proportioning
Melting is carried out at a temperature of 760 DEG C after good shove charge, speed of melting is accelerated with electromagnetic agitation in fusion process, and with forklift for slag pair
Aluminium liquid slag inclusion carries out taking off slag operation, and aluminium liquid is in melting in-furnace time 7h；
（2）Degasification removes the gred：Smelting aluminium alloy melt carries out furnace refining and online degasification, slagging-off；Online degasification is adopted
It is argon gas as blanketing gas, prevents the aluminium liquid after purification from secondary oxidation occurring, gas flow is 4m3/ h, degassing procedure
Middle temperature of aluminum liquid is maintained between 730 DEG C, last filter cleaner, and the aluminum melt after filtering can directly be cast；
（3）Casting：The casting of aluminium alloy controls temperature for 700 DEG C, and casting speed is 20-70mm/min, and cooling water is
40-190 m3/ h, obtains ingot casting；
（4）Destressing：The destressing of ingot casting controlled temperature for 480 DEG C, in 120T homogenizing annealing stoves inside holding 14 hours；
（5）Sawing：Aluminium alloy cast ingot after destressing is processed carries out crop end, is then sawed aluminium alloy using plane
Ingot casting is sawed into the aluminum alloy plate materials of required thickness, obtains 4004 aluminium alloys.
Described online degasification is that flow is 4m using argon gas degasification3/ t aluminum melts, rotor speed is 500rpm.
Described is filtered into first with 30PPI type filter plates, and Rose Box filtering is then imported again.
Embodiment 4
（One）Raw material and weight：
Its chemical constituent is by mass percentage：Si：10.5%、Mg：2.0%、Fe≤0.8%、Cu≤0.25%、Mn≤
0.1%、Zn≤0.20%、Sr：0.2%、Bi：2.0%、Te：1.0%th, single content≤0.05% of other impurity elements, other impurity unit
Plain total content≤0.15%, balance of Al.
（Two）Production method：
（1）Melting：During purity is put into smelting furnace up to the aluminium ingot of 99.75% and the above, and alloying element is weighed by proportioning
Melting is carried out at a temperature of 770 DEG C after good shove charge, speed of melting is accelerated with electromagnetic agitation in fusion process, and with forklift for slag pair
Aluminium liquid slag inclusion carries out taking off slag operation, and aluminium liquid is in melting in-furnace time 6.8h；
（2）Degasification removes the gred：Smelting aluminium alloy melt carries out furnace refining and online degasification, slagging-off；Online degasification is adopted
It is argon gas as blanketing gas, prevents the aluminium liquid after purification from secondary oxidation occurring, gas flow is 5m3/ h, degassing procedure
Middle temperature of aluminum liquid is maintained between 740 DEG C, last filter cleaner, and the aluminum melt after filtering can directly be cast；
（3）Casting：The casting of aluminium alloy controls temperature for 720 DEG C, and casting speed is 20-70mm/min, and cooling water is
40-190 m3/ h, obtains ingot casting；
（4）Destressing：The destressing of ingot casting controlled temperature for 500 DEG C, in 120T homogenizing annealing stoves inside holding 8 hours；
（5）Sawing：Aluminium alloy cast ingot after destressing is processed carries out crop end, is then sawed aluminium alloy using plane
Ingot casting is sawed into the aluminum alloy plate materials of required thickness, obtains 4004 aluminium alloys.
Described online degasification is that flow is 5m using argon gas degasification3/ t aluminum melts, rotor speed is 580rpm.
Described is filtered into first with 30PPI type filter plates, and Rose Box filtering is then imported again.
Following table is the result of hydraulic test using heat exchanger after brazing material vacuum brazing of the invention, wherein contrast product
It is 4004/3003/4004 conventional brazing material heat exchanger, product 1, product 2 are using the product obtained by the technology of the present invention.
As seen from the above table, under same process, after adding Bi and Te elements in 4004 alloys, the voltage endurance capability of heat exchanger is carried
High by about 20%, weld strength is significantly improved.
Claims (4)
1. a kind of soldering bismuth-containing and the aluminium alloy of tellurium 4004, it is characterised in that its chemical constituent is by mass percentage：Si：
9.0~10.5%, Mg：1.0~2.0%, Fe≤0.8%, Cu≤0.25%, Mn≤0.1%, Zn≤0.20%, Sr：0.02~0.2%,
Bi：0.02~2.0%, Te：0.01~1.0%, single content≤0.05% of other impurity elements, other impurity element total contents≤
0.15%, balance of Al；
Described soldering bismuth-containing and the production method of the aluminium alloy of tellurium 4004, including melting, degasification slagging-off, casting, destressing and
Sawing operation, detailed process is as follows：
（1）Melting：By purity up to 99.75% and the above aluminium ingot input smelting furnace in, and by proportioning by the weighted dress of alloying element
Melting is carried out after stove at a temperature of 720~770 DEG C, accelerates speed of melting with electromagnetic agitation in fusion process, and use forklift for slag
Aluminium liquid slag inclusion is carried out to take off slag operation, aluminium liquid is in melting in-furnace time≤8h；
（2）Degasification removes the gred：Smelting aluminium alloy melt carries out furnace refining and online degasification, slagging-off；What online degasification was used
It is argon gas as blanketing gas, prevents the aluminium liquid after purification from secondary oxidation occurring, gas flow is 2~5m3/ h, in degassing procedure
Temperature of aluminum liquid is maintained between 700~740 DEG C, and last filter cleaner, the aluminum melt after filtering is directly cast；
（3）Casting：The casting of aluminium alloy controls temperature for 670~720 DEG C, and casting speed is 20-70mm/min, and cooling water is
40-190 m3/ h, obtains ingot casting；
（4）Destressing：The destressing of ingot casting controls temperature for 420~500 DEG C, in 120T homogenizing annealing stoves inside holding 8~18
Hour；
（5）Sawing：Aluminium alloy cast ingot after destressing is processed carries out crop end, is then sawed aluminium alloy cast ingot using plane
The aluminum alloy plate materials of required thickness are sawed into, 4004 aluminium alloys are obtained.
2. soldering bismuth-containing according to claim 1 and the aluminium alloy of tellurium 4004, it is characterised in that：Described online degasification is
After the completion of furnace refining, the liquid hydrogen content of aluminum melt is determined using online hydrogen meter in standing furnace exit, aluminium liquid is gone to
Argon gas is stirred depassing unit, depassing unit the bubble to form small disperse by rotor, is adsorbed during bubble floating
Free hydrogen and harmful substance in aluminium liquid, temperature of aluminum liquid is maintained between 700~740 DEG C in degassing procedure.
3. soldering bismuth-containing according to claim 2 and the aluminium alloy of tellurium 4004, it is characterised in that：Described online degasification is
Using argon gas degasification, flow is 2~5m3/ t aluminum melts, rotor speed is 350~580rpm.
4. soldering bismuth-containing according to claim 1 and the aluminium alloy of tellurium 4004, it is characterised in that：Described being filtered into first is used
30PPI type filter plates, then import Rose Box filtering again.
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| CN112605554A (en) * | 2020-12-17 | 2021-04-06 | 东北轻合金有限责任公司 | Bismuth-containing 4-series aluminum alloy suitable for brazing flux-free brazing and preparation method thereof |
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|---|---|---|---|---|
| JPS5417349A (en) * | 1977-07-11 | 1979-02-08 | Mitsubishi Aluminium | Aluminum alloy brazing material for brazing used for fluxxfree brazing in high vacuum or nonoxidizable atomosphere |
| CN85102454A (en) * | 1985-04-01 | 1986-04-10 | 陕西机械学院 | Aluminium alloy for casting piston of eatectic silicon, copper, magnesium, manganese and tellurium series |
| CN102152024A (en) * | 2011-04-28 | 2011-08-17 | 浙江大学 | High-strength aluminum alloy brazing filler metal with melting point being lower than 500 DEG C and preparation method thereof |
| CN104372207A (en) * | 2013-08-12 | 2015-02-25 | 大力神铝业股份有限公司 | 4004 aluminum alloy for soldering |
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2015
- 2015-03-09 CN CN201510101944.2A patent/CN104694789B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5417349A (en) * | 1977-07-11 | 1979-02-08 | Mitsubishi Aluminium | Aluminum alloy brazing material for brazing used for fluxxfree brazing in high vacuum or nonoxidizable atomosphere |
| CN85102454A (en) * | 1985-04-01 | 1986-04-10 | 陕西机械学院 | Aluminium alloy for casting piston of eatectic silicon, copper, magnesium, manganese and tellurium series |
| CN102152024A (en) * | 2011-04-28 | 2011-08-17 | 浙江大学 | High-strength aluminum alloy brazing filler metal with melting point being lower than 500 DEG C and preparation method thereof |
| CN104372207A (en) * | 2013-08-12 | 2015-02-25 | 大力神铝业股份有限公司 | 4004 aluminum alloy for soldering |
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