CN105671350A - Aluminum alloy refiner, preparation method therefor and use thereof - Google Patents

Aluminum alloy refiner, preparation method therefor and use thereof Download PDF

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Publication number
CN105671350A
CN105671350A CN201610131543.6A CN201610131543A CN105671350A CN 105671350 A CN105671350 A CN 105671350A CN 201610131543 A CN201610131543 A CN 201610131543A CN 105671350 A CN105671350 A CN 105671350A
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China
Prior art keywords
aluminium alloy
parts
fining agent
weight
alloy fining
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CN201610131543.6A
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Chinese (zh)
Inventor
王永宁
朱志华
刘春海
李昌海
阿拉腾
王立生
张振栋
白帮伟
方正
赵维民
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Hebei University of Technology
CITIC Dicastal Co Ltd
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Hebei University of Technology
CITIC Dicastal Co Ltd
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Publication of CN105671350A publication Critical patent/CN105671350A/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/06Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D1/00Treatment of fused masses in the ladle or the supply runners before casting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D1/00Treatment of fused masses in the ladle or the supply runners before casting
    • B22D1/002Treatment with gases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/02Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
    • B22D21/04Casting aluminium or magnesium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/20Measures not previously mentioned for influencing the grain structure or texture; Selection of compositions therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D7/00Casting ingots, e.g. from ferrous metals
    • B22D7/005Casting ingots, e.g. from ferrous metals from non-ferrous metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00Obtaining aluminium
    • C22B21/06Obtaining aluminium refining
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/026Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/02Alloys based on aluminium with silicon as the next major constituent

Abstract

The invention provides an aluminum alloy refiner. The aluminum alloy refiner is characterized by comprising 7-10 parts by weight of Ti, 2-3 parts by weight of B and the balance of Al, for example, 8 parts by weight of Ti, 3 parts by weight of B and 89 parts by weight of Al. The aluminum alloy refiner is prepared through rapid solidification. By adding the refiner into an A356.2 aluminum alloy, the grain size of the alloy is remarkably reduced compared with that of the aluminum alloy treated by a conventional refiner. In addition, rapid solidification further can increase the solubility of metal in a liquid, so that the refiner is easily absorbed by an aluminum alloy melt when being added into the aluminum alloy.

Description

A kind of aluminium alloy fining agent, Preparation Method And The Use
Technical field
The present invention relates to aluminium alloy smelting field, more particularly to a kind of aluminium alloy fining agent, its preparation method and application.
Background technology
A356.2 aluminium alloy has good fluidity, and without hot cracking tendency, linear shrinkage is little, and proportion is little, and corrosion resistance waits well good characteristic, is the main use material of automotive hub. But, the as-cast structure of the A356.2 aluminium alloy of non-fine degenerate is thick lamellar or needle shaped eutectic silicon and α-Al arborescent structure, and mechanical property is relatively low. Therefore, it is necessary to add alterant element and grain refining element, make Morphology of Eutectic Silicon in Al-Si Foundry Alloys be changed into by thick lamellar or needle-like tiny spherical or bar-shaped, make α-Al crystal grain be refined simultaneously, the serviceability of A356.2 alloy could be improved, extend its range of application. At present, the fining agent that in commercial production, A356.2 aluminium alloy is conventional has Al-Ti-B, Al-Ti-C, Al-Ti-B-C etc.
In first technology, CN102886511A discloses a kind of method preparing Al-Ti-C grain refiner. Described fining agent is added in aluminum liquid prepared by TiC. The TiC related to is nano-particle, and material cost is high, complicated process of preparation. And need to use argon or nitrogen to be distributed in melt by this nanometer powder, increase the complexity of technique and the cycle of whole technique, be unfavorable for that industrialization produces.
In first technology, CN103667759A discloses a kind of Al-Mg-Si system alloy α-Al grain refiner and preparation method thereof. The method need to be ground to 200-400 order after tri-kinds of powder mixing of Ti, Bi, Cr, increases technique duration. And powder need to use after aluminium foil tight, can use after toasting 30min at 200-250 DEG C, add complex process degree, be unfavorable for that industrialization produces.
In first technology, CN103589916A discloses a kind of Rapid solidification Al-Ti-B-Sc intermediate alloy refiner and preparation method thereof. The intermediate alloy that the method relates to contains the Ti of 3.75%~5% and the B of 0.75%~1%, and two kinds of constituent contents are relatively low, and thinning effect is limited. And the method is possibly together with the noble metal Sc element of 0.1%~0.5%, manufacturing cost is high.
In sum, aluminium alloy fining agent of the prior art or relatively costly be difficult to extensive use, or use step and process complicated, limit its application on producing.
Summary of the invention
Therefore, it is an object of the invention to develop a kind of less costly and use the simple aluminium alloy fining agent of technique.
In order to realize above goal of the invention, it is provided that embodiments below:
In one aspect of the invention, it is provided that a kind of aluminium alloy fining agent, described aluminium alloy fining agent includes the Al of the Ti of 7~10 parts by weight, B and 87~91 part of 2~3 parts, for instance the Al of the Ti of 8 parts, the B of 3 parts and 89 parts by weight.Preferably, described aluminium alloy fining agent includes the Al of the Ti of 7.5~9 parts by weight, B and 88-90 part of 2.5~3 parts; It is further preferred that described aluminium alloy fining agent includes the Ti of 8-8.5 part by weight, the Al of B and 89-90 part of 2.5~3 parts; Such as: the aluminium alloy fining agent described in (1) includes the Al of the Ti of 8 parts by weight, the B of 3 parts and 89 parts; (2) the aluminium alloy fining agent described in includes the Al of the Ti of 7 parts by weight, the B of 2 parts and 91 parts; (3) the aluminium alloy fining agent described in includes the Al of the Ti of 7.5 parts by weight, the B of 2.5 parts and 90 parts; (4) the aluminium alloy fining agent described in includes the Al of the Ti of 8.5 parts by weight, the B of 2.5 parts and 89 parts; (5) the aluminium alloy fining agent described in includes the Al of the Ti of 9 parts by weight, the B of 3 parts and 88 parts; And the aluminium alloy fining agent described in (6) includes the Al of the Ti of 10 parts by weight, the B of 3 parts and 87 parts.
In a preferred aspect of the invention, described aluminium alloy fining agent is by α-Al phase, granular TiAl3Phase and TiB2Granule phase composition.
At a preferred aspect of the invention, the granular TiAl of described aluminium alloy fining agent3The particle scale of phase is less than 1.0 μm; Preferably, it is 0.6~1.0 μm.
At a preferred aspect of the invention, the TiB of described aluminium alloy fining agent2The particle scale of granule phase is less than 60nm; Preferably, it is 30~60nm.
In a preferred aspect of the invention, described aluminium alloy fining agent is that rapid solidification prepares.
In another aspect of the present invention, it is provided that the method preparing previously described aluminium alloy fining agent, described method includes step:
(1) raw material is mixed in proportion, and put in the quartz ampoule of lower ending opening, and quartz ampoule is heated until the test block of quartz ampoule is melted completely, it is preferable that the diameter of the little sky of quartz ampoule lower ending opening is 0.3~0.6mm, it is most preferred that for 0.4mm;
(2) by the melt jet in quartz ampoule to the copper roller rotated, it is preferable that described copper roller rotates according to the rotating speed of 50~65 revolutions per seconds, it is most preferred that the rotating speed of 60 revolutions per seconds rotates.
In a preferred aspect of the invention, described raw material is industrial Al-Ti-B intermediate alloy, simple substance Ti granule and simple substance B granule.
In another aspect of the present invention, provide the method using previously described aluminium alloy fining agent or the aluminium alloy fining agent prepared according to previously described method to carry out refining aluminum alloy, it is characterized in that, described method includes step: after aluminium alloy cast ingot is added heat fusing by (1), stirring at low speed, stands and skims surface scum; (2) the aluminium alloy fining agent that in aluminum alloy melt prepared by addition aluminium alloy fining agent according to any one of claim 1-5 or the method according to any one of claim 6-7, addition is the 0.15-0.30% of molten aluminium alloy mass fraction, treat that fining agent is completely melt, after melt insulation 10min, skim surface scum. Being slowly introducing high-purity argon gas in melt and carry out refine, refining temperature 720 DEG C, ventilation limit, limit is slowly stirred, and refine removes surface scum again after terminating; (3), after the melt of 720 DEG C being stood, slowly it is poured in the cast iron die of preheating. Preferably, described aluminium alloy is A356.2 aluminium alloy; Preferably, addition is the 0.20% of molten aluminium alloy mass fraction.
In another aspect of the present invention, provide the method using previously described aluminium alloy fining agent or the aluminium alloy fining agent prepared according to previously described method to carry out refining aluminum alloy, it is characterized in that, described method includes step: A356.2 aluminium alloy cast ingot is heated to 740 DEG C with stove by (1), after alloy melting, to the artificial stirring at low speed 0.5min of melt, then after standing 1min, skim surface scum;(2) adding this patent rapid solidification Al-Ti-B refiner in aluminum alloy melt, addition is the 0.2% of A356.2 molten aluminium alloy mass fraction. Treat that fining agent is completely melt, after melt insulation 10min, skim surface scum. Being slowly introducing high-purity argon gas (purity 99.99%) in melt and carry out refine, refining temperature 720 DEG C, ventilation limit, limit is slowly stirred 5min, and refine removes surface scum again after terminating; (3), after the melt of 720 DEG C being stood 1min, slowly it is poured in the cast iron die that preheating temperature is 150 DEG C.
In another aspect of the present invention, it is provided that according to the aluminium alloy of previously described method micronization processes.
In another aspect of the present invention, it is provided that process the aluminium alloy obtained or the previously described aluminium alloy purposes in casting aluminum vehicle wheel according to previously described method.
In other aspects of the present invention, it is provided that following technical scheme:
Rapid solidification Al-Ti-B refiner, the mass percent of its component is: Ti8%, B3%, Al89%, and this fining agent is mainly by α-Al phase, the yardstick granular TiAl less than 1.0 μm3Phase and the yardstick TiB less than 60nm2Granule phase composition.
The preparation method of above-mentioned rapid solidification Al-Ti-B refiner, comprises the steps:
The first step, the preparation of rapid solidification fining agent band.
By industrial Al-Ti-B intermediate alloy fritter, (length is no more than 6mm, the mass percent of component is: Ti5.0%, B1.0%, Fe, Cu, Mg, Mn sum is less than 0.15%, surplus Al, purchased from KBMAffilips company), (diameter is not more than 2mm to Ti granule, purity 99.99%) and B granule (diameter is not more than 2mm, purity 99.99%) it is made into Al-8Ti-3B composition, above-mentioned material mixing is put in the quartz ampoule that lower end has diameter 0.4mm aperture. Getting rid of the heating of band machine induction coil to WK-IIB type vacuum, the test block to quartz ampoule is completely melt, melted intermediate alloy is ejected into rotating speed and reaches on the copper roller of 60 revolutions per seconds, and prepared thickness is 8 μm, the rapid solidification Al-8Ti-3B fining agent band of wide 1.2mm.
Second step, is pressed into test block by band.
Utilize cuber by band 500MPa pressure system 5 seconds, make the cylindrical test block of φ 20mm × 10mm to take, standby.
Compared with prior art, the marked improvement of the present invention is as follows:
(1) preparation method equipment is simple, alloy melting and get rid of band process and accomplish without any letup, and operating process is simple and easy, and productivity ratio is high, the drawback such as overcome melting and preparation process complex process, process time length, thinning effect is limited, the cost of raw material is high.
(2) in the Al-Ti-B alloy that patent system of the present invention is standby, the content of Ti and B is higher than conventional alloys, and distribution is more more uniform than conventional alloys, yardstick is more tiny, considerably increases forming core particle quantity, and the thinning effect of aluminium alloy is better.
(3) patent of the present invention is without precious metal element, has saved the cost of raw material.
(4) the aluminium alloy fining agent in the present invention is prepared by quick setting method. Rapid solidification makes precipitated phase granule more tiny, disperses more uniform. After fining agent adds A356.2 aluminium alloy, the aluminium alloy that alloy grain size processes than traditional fining agent significantly reduces. Additionally, rapid solidification also can make metal dissolubility in liquid increase so that fining agent is easier to be absorbed by aluminium alloy melt when adding in aluminium alloy.
Accompanying drawing explanation
Hereinafter, describe embodiment of the present invention in detail in conjunction with accompanying drawing, wherein:
Fig. 1 is the metallographic structure photo of as cast condition Al-Ti-B refiner;
Fig. 2 is the stereoscan photograph of rapid solidification Al-Ti-B refiner band;
Fig. 3 is the transmission electron microscope photo of rapid solidification Al-Ti-B refiner band;
Fig. 4 is metallographic microstructure photo after A356.2 alloy heat treatment;
Fig. 5 is A356.2 alloy after tradition Al-Ti-B refiner processes then through heat treated metallographic structure photo;
Fig. 6 be in embodiment 1 A356.2 alloy after rapid solidification Al-Ti-B refiner bar tape handling then through heat treated metallographic structure photo.
Detailed description of the invention
The first step, the preparation of rapid solidification fining agent band.
By industrial Al-Ti-B intermediate alloy fritter, (length is no more than 6mm, the mass percent of component is: Ti5.0%, B1.0%, Fe, Cu, Mg, Mn sum is less than 0.15%, surplus Al, purchased from KBMAffilips company), (diameter is not more than 2mm to Ti granule, purity 99.99%) and B granule (diameter is not more than 2mm, purity 99.99%) be made into Al-8Ti-3B composition, by above-mentioned material mix (make Ti, B and Al element wt number as shown in table 1) put in the quartz ampoule that lower end has diameter 0.4mm aperture. Getting rid of the heating of band machine induction coil to WK-IIB type vacuum, the test block to quartz ampoule is completely melt, melted intermediate alloy is ejected into rotating speed and reaches on the copper roller of 60 revolutions per seconds, and prepared thickness is 8 μm, the rapid solidification Al-8Ti-3B fining agent band of wide 1.2mm.
Table 1:Ti, B and Al element wt number
Group number The element wt number of Ti The element wt number of B The element wt number of Al
1 8 3 89
2 7 2 91
3 7.5 2.5 90
4 8.5 2.5 89
5 9 3 88
6 10 3 87
Second step, is pressed into test block by band.
Utilize cuber by band 500MPa pressure system 5 seconds, makeThe cylindrical test block of × 10mm is to take, standby.
Fig. 1 show the metallographic structure photo of as cast condition Al-5Ti-1B fining agent, and as seen from the figure, as cast condition Al-5Ti-1B fining agent is by α-Al phase, the yardstick block TiAl less than 40 μm3Mutually with the Dispersed precipitate yardstick TiB less than 9 μm2Phase composition.
The microscopic structure of the 1st group of the rapid solidification Al-8Ti-3B fining agent band that the present embodiment prepares as shown in Figures 2 and 3, respectively show the TiAl formed3Phase and TiB2The pattern of phase and size. As seen from the figure, rapid solidification Al-8Ti-3B fining agent band is by α-Al phase, the yardstick granular TiAl less than 1.0 μm3Phase and the yardstick granular TiB less than 60nm2Phase composition, it is seen that after rapid solidification processes, in alloy, precipitate particle dispersion is more uniform, and the yardstick of precipitated phase is greatly reduced, and forming core particle is greatly improved. The sample of 2-6 group has carried out microstructure observation too, and it also shows rapid solidification Al-8Ti-3B fining agent band by α-Al phase, the yardstick granular TiAl less than 1.0 μm3Phase and the yardstick granular TiB less than 60nm2Phase composition (experimental result does not show).
Fig. 4 show A356.2 aluminium alloy (6.83%Si, 0.34%Mg, 0.07%Fe, 0.11%Ti, 0.024%Sr, 0.0008%B, surplus Al, purchased from Binzhou Meng Weilianxin new material company limited) metallographic microstructure after heat treatment, Technology for Heating Processing is 540 DEG C × 2h+150 DEG C × 12h. From fig. 4, it can be seen that α-Al crystal grain is thicker after A356.2 aluminum alloy heat processes, its average grain size is 136.5 μm.
Fig. 5 show in A356.2 aluminium alloy to add after traditional as cast condition Al-5Ti-1B fining agent of mass fraction 0.1%Ti (converting according to the addition of Ti) metallographic microstructure after heat treatment again, and Technology for Heating Processing is 540 DEG C × 2h+150 DEG C × 12h.As seen from Figure 5, so treated α-Al crystal grain is refined, and its average grain size is 98.4 μm.
After Fig. 6 show the Al-8Ti-3B fining agent cylindrical band test block of the present embodiment the 1st group that in A356.2 aluminium alloy, addition comprises mass fraction 0.1%Ti (converting according to the addition of Ti), metallographic microstructure after heat treatment again, Technology for Heating Processing is 540 DEG C × 2h+150 DEG C × 12h. As seen from Figure 6, so treated α-Al crystal grain is refined further, and its average grain size is 56.8 μm, and the thinning effect of more traditional fining agent significantly improves. The made rapid solidification fining agent cylindrical band test block of visible the present embodiment, when Ti addition is identical, joins the thinning effect after A356.2 alloy more excellent than traditional as cast condition fining agent. The sample of 2-6 group has carried out above test too, it is shown that so treated α-Al crystal grain is refined further, its average grain size is less than 65 μm, and the thinning effect of more traditional fining agent significantly improves.
Raw material used in above-described embodiment and equipment obtain each through known approach, and operating procedure used is that those skilled in the art can grasp.

Claims (10)

1. an aluminium alloy fining agent, it is characterised in that described aluminium alloy fining agent includes the Al of the Ti of 7~10 parts by weight, B and 87~91 part of 2~3 parts;
Preferably, described aluminium alloy fining agent includes the Al of the Ti of 7.5~9 parts by weight, B and 88-90 part of 2.5~3 parts;
It is further preferred that described aluminium alloy fining agent includes the Ti of 8-8.5 part by weight, the Al of B and 89-90 part of 2.5~3 parts;
Such as:
(1) the aluminium alloy fining agent described in includes the Al of the Ti of 8 parts by weight, the B of 3 parts and 89 parts;
(2) the aluminium alloy fining agent described in includes the Al of the Ti of 7 parts by weight, the B of 2 parts and 91 parts;
(3) the aluminium alloy fining agent described in includes the Al of the Ti of 7.5 parts by weight, the B of 2.5 parts and 90 parts;
(4) the aluminium alloy fining agent described in includes the Al of the Ti of 8.5 parts by weight, the B of 2.5 parts and 89 parts;
(5) the aluminium alloy fining agent described in includes the Al of the Ti of 9 parts by weight, the B of 3 parts and 88 parts; And
(6) the aluminium alloy fining agent described in includes the Al of the Ti of 10 parts by weight, the B of 3 parts and 87 parts.
2. the aluminium alloy fining agent described in claim 1, it is characterised in that described aluminium alloy fining agent is by α-Al phase, granular TiAl3Phase and TiB2Granule phase composition.
3. the aluminium alloy fining agent described in claim 1, it is characterised in that the granular TiAl of described aluminium alloy fining agent3The yardstick of phase is less than 1.0 μm; Preferably, it is 0.6~1.0 μm.
4. the aluminium alloy fining agent described in claim 1, it is characterised in that the TiB of described aluminium alloy fining agent2The yardstick of granule phase is less than 60nm; Preferably, it is 30~60nm.
5. the aluminium alloy fining agent according to any one of claim 1-4, it is characterised in that described aluminium alloy fining agent is that rapid solidification prepares.
6. the method for preparation aluminium alloy fining agent according to any one of claim 1-5, it is characterised in that described method includes step:
(1) raw material is mixed in proportion, and put in the quartz ampoule of lower ending opening, and quartz ampoule is heated until the test block of quartz ampoule is melted completely, it is preferable that the diameter of the little sky of quartz ampoule lower ending opening is 0.3~0.6mm, it is most preferred that for 0.4mm;
(2) by the melt jet in quartz ampoule to the copper roller rotated, it is preferable that described copper roller rotates according to the rotating speed of 50~65 revolutions per seconds, it is most preferred that the rotating speed of 60 revolutions per seconds rotates.
7. the method described in claim 6, it is characterised in that described raw material is industrial Al-Ti-B intermediate alloy, simple substance Ti granule and simple substance B granule.
8. use the method that aluminium alloy fining agent prepared by the aluminium alloy fining agent according to any one of claim 1-5 or the method according to any one of claim 6-7 carrys out refining aluminum alloy, it is characterised in that described method includes step:
(1) after aluminium alloy cast ingot being added heat fusing, stirring at low speed, stand and skim surface scum;
(2) the aluminium alloy fining agent that in aluminum alloy melt prepared by addition aluminium alloy fining agent according to any one of claim 1-5 or the method according to any one of claim 6-7, addition is the 0.15-0.30% of molten aluminium alloy mass fraction, treat that fining agent is completely melt, after melt insulation 10min, skim surface scum. Being slowly introducing high-purity argon gas in melt and carry out refine, refining temperature 720 DEG C, ventilation limit, limit is slowly stirred, and refine removes surface scum again after terminating;
(3), after the melt of 720 DEG C being stood, slowly it is poured in the cast iron die of preheating;
Preferably, described aluminium alloy is A356.2 aluminium alloy;
Preferably, addition is the 0.20% of molten aluminium alloy mass fraction.
9. the aluminium alloy of micronization processes in accordance with the method for claim 8.
10. the method described in claim 8 processes the aluminium alloy described in aluminium alloy or claim 9 obtained purposes in casting aluminum vehicle wheel.
CN201610131543.6A 2015-03-19 2016-03-09 Aluminum alloy refiner, preparation method therefor and use thereof Pending CN105671350A (en)

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