CN105274405A - Rare earth aluminum alloy and preparation method thereof - Google Patents
Rare earth aluminum alloy and preparation method thereof Download PDFInfo
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- CN105274405A CN105274405A CN201510741878.5A CN201510741878A CN105274405A CN 105274405 A CN105274405 A CN 105274405A CN 201510741878 A CN201510741878 A CN 201510741878A CN 105274405 A CN105274405 A CN 105274405A
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Abstract
The invention relates to a rare earth aluminum alloy and a preparation method thereof, and belongs to the technical field of alloy synthesis. The rare earth aluminum alloy is prepared through vacuum suction casting of an aluminum basal body and a rare earth source; and the rare earth aluminum alloy is obtained by performing primary smelting on the aluminum basal body, refining, adding the rare earth source into a refined product, and performing impurity removal for vacuum suction casting molding. The rare earth aluminum alloy is applied to the processing of rare earth aluminum alloys and radiator section bars, and has such advantages as high compactness, good wear resistance, good weldability and high heat conductivity.
Description
Technical field
The present invention relates to a kind of rare earth aluminium alloy and preparation method thereof, belong to heat sink technology field.
Background technology
Each fuel-engined vehicle is all at least equipped with a scatterer, and it is the key part of the coolings such as motor car engine.Heat is passed to scatterer from engine by internal coolant flowing by it, heat is distributed, thus reduces engine temperature, ensure that it runs well by outside air flowing.
The quality of scatterer directly affects fuel automobile engine thermal diffusivity, economy and reliability, even ride safety of automobile.Passing judgment on radiator performance parameter is heat radiation heat transfer coefficient, affects the many factors of this heat transfer coefficient, but determines primarily of radiator material heat conductivility and welding quality.In a metal, heat conductivility, it is still further preferred that silver, is secondly copper and aluminium.Be difficult to large-scale production because the expensive and mechanical property of silver is not good and adapt to automotive front end locate bad working environments environment windward.Copper is compared aluminium and is had better mechanical property, antiseptic property, but the production cost of copper is higher, and in downstream, car load market competition is day by day fierce, and each car load factory is difficult to tremendous development under paying much attention to the overall situation of cost control.Aluminium has lightweight as Vehicle radiator material, low cost, the feature of high-environmental, is the excellent material of automobile radiators.But in recent years along with the development of automotive industry, had further requirement to the performance of scatterer, the distortion aluminium of traditional trade mark, at corrosion resistant, heat conduction and welding property more and more can not meet the automobile industry development requirement more and more harsh to scatterer.
Rare earth is called " industrial gold ", and research finds that adding a small amount of rare earth element can significantly improve aluminium alloy overall performance.Make this regional part excessively cold at aluminium alloy moulding process middle-weight rare earths in solid-liquid interface gathering, shorten dendrite interval reinforced aluminium alloy mechanical property; Rare earth and aluminium alloy form limit solid solution and rare earth compound second-phase strength reinforced aluminium alloy mechanical property; Remove with Impure forms after hydrogen forms rare earth hydride in rare earth and aluminium alloy, significantly suppress the aluminium alloy intergranular crack that in aluminium alloy, hydrogen causes, the defects such as loose and pin hole, improve alloy product quality and good article rate; Rare earth reduces aluminum alloy surface energy in aluminum alloy surface, improves Welded performance.
The advantages such as quality is light, raw materials cost is low although aluminium radiator has, perfect heat-dissipating, its welding usability is poor, production unit has high input and poor corrosion resistance is long-term insoluble problem, limits the widespread use of aluminium radiator.Outstanding feature for the manufacture of the distortion aluminium Mn series alloy of Aluminium Radiator is anti-corrosion, heat conduction, conducts electricity very well, there is excellent processing and the performance such as to weld, in recent years, the research of domestic and international expert to wrought Al-Mn alloy achieves a lot of achievement, but in heat sink applications, still there is the problems such as intensity is low, complex process.The many performances changing wrought Al-Mn alloy by changing local process of research in past.This makes alloy improve in certain while performance, and always make performance on the other hand decline to some extent, this is not the result desired by us.Along with the development of automotive industry, the alumal of traditional trade mark can not meet the more and more harsher performance requriements of Aluminium Radiator.Develop the active demand that a kind of new radiator aluminium alloy becomes market.Comprehensive many factors is considered, by adding trace rare-earth element, is an economy, effective, practical approach to the modification of existing alumal.
But conduct a preliminary study the influence research of rare earth element to aluminium alloy capability both at home and abroad, but the research of rare earth element to wrought Al-Mn alloy is also in the starting stage.This project by adding different rare earth elements in the alumal of certain ingredients, is sought the affecting laws of rare earth element to aspects such as alumal tissue, corrosion-resistant, intensity, is developed a kind of novel aluminum alloy with independent intellectual property right, technology.
Based on this, make subject application.
Summary of the invention
In order to overcome the above-mentioned defect existing for existing scatterer alloy, first the present invention there is provided the rare earth aluminium alloy that a kind of density is high, rotproofness good, weldability is good and thermal conductivity is high, solves the technical barrier that aluminum alloy heat exchange radiator improves welding property, antiseptic property, heat conductivility.
For achieving the above object, the technical scheme taked of the present invention is as follows:
A kind of rare earth aluminium alloy, formed by aluminum substrate and rare earth source suction pouring, rare earth source content is 0.01-0.5%, and described aluminum substrate is made up of each composition of following mass percentage content:
Further, as preferably:
Described rare earth source is one or more in La, Nd, Pr, Ce, Sc, Yb, Sm, Eu, Y, and it adds form is alloy, oxide compound or elemental metals.
The object of second aspect present invention is to provide a kind of preparation method with above-mentioned Characteristic rare earth aluminium alloy, comprises the steps:
(1) incipient melting: aluminum substrate is warming up to abundant melting; Wherein, aluminum substrate adds (industrial volumes Raw size is irregular, and due to cost, the reasons such as operation do not have strict differentiation) with powder or block material form.
(2) concise: continue to heat up or insulation, in the incipient melting product of step (1), add refining agent carry out refining, refining temperature is 700 ± 40 DEG C; Wherein, the addition of refining agent is 0.2-0.7%, and refining agent is silicate or villaumite.Preferred, described refining agent adds several times, and with each equivalent addition manner for optimum.
(3) rare earth source is added: insulation or continuation heat up, and add rare earth source in the refined products of step (2), continue melting, and the temperature continuing melting is 710 ± 30 DEG C.
(4) removal of impurities, suction pouring: under keeping warm mode, after removal of impurities, vacuum suction casting forming at 710 ± 30 DEG C, removal of impurities adopts porous ceramics to carry out removal of impurities degasification, to remove floating solid matter.Preferred, described porous ceramics is aluminum oxide, zirconium white or titanium oxide.
Simultaneously, the object of third aspect present invention is to provide a kind of purposes with above-mentioned Characteristic rare earth aluminium alloy, this rare earth aluminium alloy can be used as plate material for heat exchanger, its relative density is 99.3-99.4%, thermal conductivity is 180-210w/ (mk), corrosion potential is-0.89 ~-0.84V, welding strength 350-380MPa.
Further, as preferably:
Principle of work of the present invention and beneficial effect as follows:
Rare earth element has the characteristics such as unique 4f electronic structure, large nonmagnetic atom distance, very strong Quantum geometrical phase, and when forming rare earth compounding, ligancy changes between 3 ~ 12, and the crystalline structure of rare earth compound is also diversified.The physics of rare earth element uniqueness, chemical property, determine the potential use that it is wide.The interpolation of trace rare-earth element, will have a significant impact the structure and properties of aluminium alloy.
The present invention is by design alloy constituent element and proportioning, rare earth kind and addition are added in design, a kind of new radiator rare earth aluminum alloy material and section bar production technique thereof are invented, compared with conventional aluminum mangal, there is the thermal conductivity of higher metal compaction degree, larger welding strength, better rotproofness and Geng Gao.
1) comprehensive mechanical property such as the intensity of alloy, hardness, elongation, fracture toughness property and wear resisting property improves.This mainly has benefited from the strong precipitation strengthening effect etc. of the rare earth compound of the improvement of rare earth element alloy tissue and disperse.Rare earth has metamorphism, at alloy graining stage rare-earth enrichment and grain boundaries, causes this place's constitutional supercooling, reduces the secondary dendrite arm spacing of alloy, thus improve the hardness of aluminium alloy; Simultaneously add rare earth source effectively reduce void content in aluminium alloy preparation process, aluminium alloy density can be improve, thus improve the thermal conductivity of aluminium alloy, improve the heat dispersion of scatterer, refining agent and porous ceramics degasification removal of impurities, obtain finer and close metal construction, with the increase of content of rare earth in therefore prepared aluminium alloy, tensile strength, hardness improve, and unit elongation slightly declines.
2) improve the castability of aluminium alloy, improve the mobility of liquid metal, reduce casting shrinking hole, pore, segregation and surface crack.This is because iron is impurity very harmful in aluminum substrate, ten thousand/several iron just can form Al+FeAl
3eutectic, the crystal structure of most of Copper component is all very thick, directly affects the mechanical property of alloy, falls low-alloyed mobility, increases inhomogeneity of structure, adds rare earth source, then can change the existing forms of iron phase, improves the castability of aluminium alloy.
3) reduce the proneness that weld crack is formed, improve the weldability of aluminium alloy.For 3003 alloys, Pa Teqi welding test is carried out to 3003 alloys, adopt such scheme of the present invention, rare earth element is by being adsorbed in alloy surface, effectively can reduce the surface energy of aluminium alloy, realize improving aluminum alloy heat sink high welding performance, prepared rare earth aluminum alloy material does not then observe crack, strength of welded joint can reach more than 350MPa, comparatively Conventional alloys can increase 30-40%, weldment, along base fracture, in addition, adds wetting property and the luminance brightness that appropriate rare earth can improve welding zone in welding Al-Si alloy.
4) alloy monolithic corrosion potential is just becoming, and increases the resistance of electrochemical reaction, improves the solidity to corrosion of aluminium alloy.Aluminum alloy machinery intensity is high, and density is little, is widely applied in a lot of fields, but particularly has Cl in its environment for use
-deposit in case, very easily suffer the destruction of pitting corrosion, crevice corrosion, stress corrosion and corrosion fatigue etc.In order to improve the corrosion resistance nature of aluminium alloy further, people have attempted a variety of way, and conventional method has anodic oxidation, chromate oxidations and organic coating etc.Although these methods can play certain protective effect to aluminum alloy surface, also all there is certain drawback.The present invention, by the interpolation in rare earth source, makes corrosion of aluminium alloy current potential in operating mode just become, effectively increases electrochemical reaction resistance, improve corrosive protection of aluminium alloy performance.Wherein, the addition of rare earth is particularly evident on solidity to corrosion impact: in aluminium alloy, when the add-on in rare earth source is at 0.1% ~ 0.25wt%, improve its solidity to corrosion effect best, when content of rare earth is more than 0.3%, above-mentioned effect has reached maximum, and continuing to increase rare earth source content will destroy the stability of overall current potential, and corrosion resisting property degenerates raising alloy corrosion resistance on the contrary.
The present invention take aluminum substrate as raw material, its melting is also added suitable elite rare earth source, improve alloy microstructure, alloy grain is made obviously to obtain refinement, first villaumite or silicate are applied to as refining agent the alloy processing that aluminum substrate is raw material, add refining agent in batches, abundant adsorbing contaminant step by step, avoid the alloy structure defect caused by impurity existence, and be aided with vacuum suction casting forming technique, improve tensile strength and the corrosion resistance nature of alloy significantly, when using as sheet materials such as scatterers, its relative density is 99.3-99.4%, thermal conductivity is 180-210w/ (mk), corrosion potential is-0.89-0.84v, welding strength 350-380MPa.
Embodiment
Fig. 1 is the relative density (under identical casting level different embodiment sample contrast) of aluminium alloy of the present invention;
Fig. 2 is the thermal conductivity of aluminium alloy of the present invention;
Fig. 3 is the corrosion potential (according to Corrosion standards ASTMG69, and adopting mercurous chloride electrode as reference electrode) of aluminium alloy of the present invention;
Fig. 4 is the strength of welded joint of aluminium alloy of the present invention.
Embodiment
Embodiment 1
Rare earth aluminium alloy prepared by the present embodiment is made up of each composition of following mass percent: Si:0.1, Fe :≤0.2, Cu:0.1, Mn:1.3, Zn:4, Cr:0.5, Ni:0.25, Ti:0.22, Zr:0.7, La:0.13, Ce:0.1, Y:0.05, surplus is Al.
(1) incipient melting: take plumbago crucible as container, temperature is increased to the abundant melting of aluminum substrate, adduction stirs.
(2) refining: above-mentioned system is warming up to 720 DEG C, utilizes bell jar to add 0.4wt%C to 2/3 place under alloy liquid level
2cl
6(point 3 equivalent add), slowly in crucible, rotate 20min.
(4) rare earth source is added: by above-mentioned architecture heat preservation, and add Titd-CuLa, Mg-Ce30, Al-Y5 by bell jar and fully turn round and mobile 10min, the rare earth source of adding with Titd-CuLa, Mg-Ce30, Al-Y5 form, can avoid the generation of impurity.
(5) removal of impurities: utilize skimming ladle, by the floating impurity removing in above-mentioned system.
(6) shaping: the vacuum die cavity being transferred to the subsidiary porous alumina ceramic of pouring gate after above-mentioned metallic solution is warming up to 740 DEG C, by the further removal of impurities degasification of porous ceramics, by vacuum suction casting forming, after leaving standstill 20min, obtain rare earth aluminium alloy shaped material of radiator.
Embodiment 2
Composition and each Ingredient percent of rare earth aluminium alloy prepared by the present embodiment are: Si:0.15, Fe:0.5, Cu:0.05, Mn:1.2, Zn:3.5, Zr:0.05, La:0.04, Ce:0.12, Nd:0.04, Pr:0.02, and surplus is Al.
(1) incipient melting: take plumbago crucible as container, temperature is increased to the abundant melting of aluminum substrate, adduction stirs.
(2) refining: above-mentioned system is warming up to 710 DEG C, utilizes bell jar to add 0.6wt% refining agent F to 2/3 place under alloy liquid level
6na
2si (point 5 equivalent add), slowly rotates 30min in crucible.
(3) rare earth source is added: above-mentioned system heated up 730 DEG C, add rare earth source praseodymium neodymium hybrid metal (Nd of the Ce+4-10%Pr+14-18% of the La+40-55% of 25-35%), and fully stir.
(4) removal of impurities: utilize skimming ladle, by the floating impurity removing in above-mentioned system.
(6) shaping: the vacuum die cavity above-mentioned metallic solution being transferred to the subsidiary porous oxidation zircon ceramic of pouring gate, by the further removal of impurities degasification of porous ceramics, obtains rare earth aluminium alloy radiator element by suction pouring.
Embodiment 3-6
In embodiment 3-6, in aluminum substrate, except aluminium, the content of each element is as shown in table 1.
In table 1 aluminum substrate except aluminium the content (mass percent, unit: %) of each composition
| Embodiment | Si | Fe | Cu | Mn | Zn | Cr | Ni | Ti | Zr | Re |
| 3 | 0.2 | 0.3 | 0.2 | 1 | 3 | 0.2 | 0.2 | 0.1 | 0.5 | 0.5 |
| 4 | 2.3 | 0.4 | 0.5 | 1.2 | 5 | 0.7 | 0.5 | - | - | - |
| 5 | 0.15 | 0.5 | 0.1 | 1.2 | 3.5 | 0.1 | 0.1 | 0.15 | - | - |
| 6 | 0.1 | ≤0.2 | 3 | 1.2 | 4 | 0.2 | 0.1 | 0.3 | 0.8 | 0.2 |
Wherein, in table 1 ,-expression does not contain this composition or this composition addition is 0.
Remaining operations step is identical with embodiment 2, and difference optimum configurations is as shown in table 2.
The processing condition of the different preparation method of table 2
Effect detection part
Aluminium alloy prepared by above-described embodiment and 3003 alloys with regard to thermal conductivity, welding strength, corrosion potential and relative density four aspect compare, be alumal mother metal material as a comparison by 3003, compare with the rare earth aluminum alloy material of system.Mother metal tensile strength 165MPa, rare earth aluminum alloy material tensile strength 189MPa.Sample is produced respectively, at 3.5%NaCl+1%H by 50 × 50 × 2
2o
2soak the change of 120 hours rate of weight loss.After soaking, rare earth aluminum alloy material corrosion resistance nature improves 22%.
The present invention take aluminum substrate as raw material, its melting is also added suitable elite rare earth source, improve alloy microstructure, alloy grain is made obviously to obtain refinement, first villaumite or silicate are applied to as refining agent the alloy processing that aluminum substrate is raw material, add refining agent in batches, abundant adsorbing contaminant step by step, avoid the alloy structure defect caused by impurity existence, and be aided with vacuum suction casting forming technique, improve tensile strength and the corrosion resistance nature of alloy significantly, specifically compare with embodiment 1, embodiment 2 with conventional 3003 alloys and analyze.
(1) relative density and thermal conductivity: the rare earth source that the application adds, at alloy graining stage rare-earth enrichment and grain boundaries, makes this place's constitutional supercooling, to reduce the secondary dendrite arm spacing of alloy, thus improves the hardness of aluminium alloy, simultaneously add rare earth source effectively reduce void content in aluminium alloy preparation process, aluminium alloy density can be improve, thus improve the thermal conductivity of aluminium alloy, improve the heat dispersion of scatterer, and be aided with and add refining agent and porous ceramics degasification removal of impurities, obtain finer and close metal construction, as can be seen from the results of comparison of Fig. 1 and Fig. 2, adopt the aluminium alloy prepared by the application's method, its relative density is 99.3-99.4%, thermal conductivity is 180-210w/ (mk), exceed conventional 3003 alloys far away, and with the increase of content of rare earth, tensile strength, hardness improves, and unit elongation slightly declines.
(2) corrosion potential and welding strength: iron is impurity very harmful in aluminum substrate, and ten thousand/several iron just can form Al+FeAl
3eutectic, the crystal structure of most of Copper component is all very thick, and this will directly affect the mechanical property of alloy, falls low-alloyed mobility, increases inhomogeneity of structure, adds rare earth source, and add villaumite or silicate as refining agent, villaumite is as C simultaneously
2cl
6, its absorption property is comparatively strong, therefore a small amount of C
2cl
6just can be complete by impurity absorption, and silicate is as F
6na
2si absorption property is relatively weak, therefore need add amount will be more; And in alloy casting process, impurity non-once produce, and added by refining agent if disposable, then excessive refining agent cannot fully contact with impurity, just cannot play refining and adsorption effect, in the application, according to its absorption property and treatment situation, refining agent is divided into and repeatedly adds, especially the best is added to equivalent, refining agent coordinates with rare earth source, can change the existing forms of iron phase, improves the castability of aluminium alloy; And rare earth element is by being adsorbed in metallic surface, effectively can reduce the surface energy of aluminium alloy, and corrosion of aluminium alloy current potential in operating mode is just being become, effective increase electrochemical reaction resistance, coordinate again and present in suction pouring mode, improve corrosive protection of aluminium alloy performance, realize improving aluminum alloy heat sink high welding performance, prepared rare earth aluminum alloy material does not then observe crack, composition graphs 3 and Fig. 4, its corrosion potential is between-0.89v and-0.84v, and welding strength then can reach 350-380MPa, and comparatively Conventional alloys can increase 30-40%.
Claims (9)
1. a rare earth aluminium alloy, is characterized in that: formed by aluminum substrate and rare earth source suction pouring, rare earth source content is 0.01-0.5%, and described aluminum substrate is made up of each composition of following mass percentage content:
Si：0.1~2.3
Fe：≤0.5
Cu：0.05~3
Mn：1~1.5
Zn：3~5
Cr：0~0.7
Ni：≤0.5
Ti：≤0.3
Zr：≤0.8
RE：≤0.5
Surplus is Al.
2. rare earth aluminium alloy as claimed in claim 1, is characterized in that: described rare earth source is containing one or more in La, Nd, Pr, Ce, Sc, Yb, Sm, Eu, Y, and it adds form is alloy, oxide compound or elemental metals.
3. a preparation method for rare earth aluminium alloy as claimed in claim 1, is characterized in that, comprise the steps:
(1) incipient melting: aluminum substrate is warming up to abundant melting;
(2) concise: continue to heat up or insulation, in the incipient melting product of step (1), add refining agent carry out refining, refining temperature is 700 ± 40 DEG C;
(3) rare earth source is added: insulation or continuation heat up, and add rare earth source in the refined products of step (2), continue melting, and the temperature continuing melting is 710 ± 30 DEG C;
(4) removal of impurities, suction pouring: under keeping warm mode, after removal of impurities, vacuum suction casting forming at 710 ± 30 DEG C.
4. the preparation method of a kind of rare earth aluminium alloy as claimed in claim 3, is characterized in that: in step (1), and aluminum substrate adds with powder or block material form.
5. the preparation method of a kind of rare earth aluminium alloy as claimed in claim 3, is characterized in that: in step (2), and the addition of refining agent is 0.2-0.7%, and refining agent is silicate or villaumite.
6. the preparation method of a kind of rare earth aluminium alloy as described in claim 3 or 5, is characterized in that: described refining agent several times equivalent adds.
7. the preparation method of a kind of rare earth aluminium alloy as claimed in claim 3, is characterized in that: in step (4), and removal of impurities adopts porous ceramics to carry out removal of impurities degasification, to remove floating solid matter.
8. the preparation method of a kind of rare earth aluminium alloy as claimed in claim 7, is characterized in that: described porous ceramics is aluminum oxide, zirconium white or titanium oxide.
9. a rare earth aluminium alloy as claimed in claim 1, it is characterized in that: this rare earth aluminium alloy can be used as plate material for heat exchanger, its relative density is 99.3-99.4%, and thermal conductivity is 180-210w/mk, corrosion potential is-0.89-0.84v, welding strength 350-380MPa.
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| CN105714020A (en) * | 2016-04-06 | 2016-06-29 | 北京科技大学 | Rare earth aluminum-base alloy for steelmaking deoxidization and preparation method thereof |
| CN108398320A (en) * | 2018-01-24 | 2018-08-14 | 航天科工防御技术研究试验中心 | A kind of measurement method of wrought aluminium alloy tensile stress etching |
| CN108950316A (en) * | 2018-07-23 | 2018-12-07 | 武汉理工大学 | A kind of rare earth modified aluminium alloy automobile wagon sheet and preparation method thereof |
| CN109158792A (en) * | 2018-10-15 | 2019-01-08 | 广东美的制冷设备有限公司 | Weld-ring, workpiece, heat exchanger and air conditioner |
| CN109234578A (en) * | 2018-09-25 | 2019-01-18 | 广东美的制冷设备有限公司 | Aluminium alloy, tubing, heat exchanger, air-conditioning and refrigeration equipment |
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| CN109402468A (en) * | 2018-09-11 | 2019-03-01 | 湖南工业大学 | A kind of light-weighted aluminum alloy materials and its application in terms of preparing shell case |
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| CN110777274A (en) * | 2019-11-06 | 2020-02-11 | 山东钢铁集团有限公司 | Metallurgical rare earth aluminum alloy apparatus for producing |
| CN113897521A (en) * | 2020-07-06 | 2022-01-07 | 济南科为达新材料科技有限公司 | Aluminum alloy material suitable for manufacturing sliding bearing |
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| CN109402468A (en) * | 2018-09-11 | 2019-03-01 | 湖南工业大学 | A kind of light-weighted aluminum alloy materials and its application in terms of preparing shell case |
| CN109402469A (en) * | 2018-09-11 | 2019-03-01 | 湖南工业大学 | A kind of aluminum alloy materials and its application in terms of preparing shell case |
| CN109234578A (en) * | 2018-09-25 | 2019-01-18 | 广东美的制冷设备有限公司 | Aluminium alloy, tubing, heat exchanger, air-conditioning and refrigeration equipment |
| CN109158792A (en) * | 2018-10-15 | 2019-01-08 | 广东美的制冷设备有限公司 | Weld-ring, workpiece, heat exchanger and air conditioner |
| CN110777274A (en) * | 2019-11-06 | 2020-02-11 | 山东钢铁集团有限公司 | Metallurgical rare earth aluminum alloy apparatus for producing |
| CN113897521A (en) * | 2020-07-06 | 2022-01-07 | 济南科为达新材料科技有限公司 | Aluminum alloy material suitable for manufacturing sliding bearing |
| WO2022237073A1 (en) * | 2021-05-08 | 2022-11-17 | 上海中天铝线有限公司 | Aluminum alloy material, and aluminum alloy wire and preparation method therefor |
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