CN106319273A - Melt purification fused salt capable of improving aluminum-based amorphous alloy forming ability and melt purification treatment method - Google Patents
Melt purification fused salt capable of improving aluminum-based amorphous alloy forming ability and melt purification treatment method Download PDFInfo
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- CN106319273A CN106319273A CN201510394516.3A CN201510394516A CN106319273A CN 106319273 A CN106319273 A CN 106319273A CN 201510394516 A CN201510394516 A CN 201510394516A CN 106319273 A CN106319273 A CN 106319273A
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Abstract
The invention discloses a melt purification fused salt capable of improving the aluminum-based amorphous alloy forming ability and a melt purification treatment method, and belongs to the technical field of aluminum-based amorphous alloy preparation. The melt purification fused salt is formed by adding additional fused salts, namely CaF2, into a basic fused salt system, namely Cl-MgCl2-CaCl2, wherein adding amount of the additional fused salts CaF2 is 10-30% of the total weight of the basic fused salt system; and during the aluminum-based amorphous alloy melt purification treatment, the adding amount of the fused salts is 0.5-2% of the total amount of aluminum-based amorphous alloy. Through the fused salt and the treatment method, oxide inclusions in the aluminum-based amorphous alloy can be removed, the effect of refining the grain of aluminum-based amorphous mother alloy is further achieved, the forming ability of the Al-TM-RE system aluminum-based amorphous alloy can be greatly improved, and the impelling function of enlarging the application range of lightweight high-strength aluminum-based amorphous alloy is achieved.
Description
Technical field
The present invention relates to al based amorphous alloy preparing technical field, be specifically related to a kind of raising al based amorphous alloy shape
The cleaning molten fused salt of one-tenth ability and cleaning molten processing method.
Background technology
At present, utilize and the needs of green ecological environment protection for the effective of non-renewable resources, automobile,
It is lighting developing material that the research and development of the vehicle such as aircraft, naval vessel, weaponry improve emphasis.Such as, closely
Over Nian, all kinds of light materials application percentage in weapon model is rapid increase trend.Wherein aluminium alloy, especially
Be high strength alumin ium alloy owing to having the advantage of light weight, high specific strength, high specific stiffness, be widely used in national economy
Build and the every field of national defense construction, used the most in a large number at aircraft industry.With traditional aluminium alloy phase
Ratio, amorphous aluminum alloy has high specific strength, good toughness and the decay resistance of excellence, and its tension is strong
Degree more than 1000MPa, can exceed the level of current high-strength steel, and specific strength can match in excellence or beauty with pottery, and keep
Good plasticity and high-temperature stability.Its development lightweight superelevation strong metal structural material that appears as provides one
The approach that bar is new.But, the principal element limiting such materials application at present is the glass of Al base noncrystal alloy
Forming ability is very poor, and currently acquired maximum amorphous critical dimension is 1mm, and still cannot meet Practical Project should
Needs.Therefore, the Forming ability improving al based amorphous alloy is the primary factor expanding its range of application.
Utilize cleaning molten processing method improve amorphous formation ability be at present research uses more method it
One, in a lot of strong glass former systems, obtained preferable application.Universal in strong non-crystaline amorphous metal system at present
The melt treatment used is under pure argon gas is protected, and high pure metal component is melted in electric arc furnace, system
Become cylindrical ingot, and used the B of low melting point2O3Oxide wraps up, and obtains amorphous state in water of quenching
Sample.The parcel of oxide acts on of both playing: one is used to absorb the impurity particle in alloy melt,
Make alloy purify further, be similar to slag making during steel-making；Two is to be environmentally isolated with preparation by alloy melt, keeps away
When exempting from fusing, alloy mother metal is in direct contact with it.After cleaning molten, can avoid to greatest extent heterogeneous nucleation and
Oxidation.Japanese scholars A.Inoue and China Liling Sun etc. apply this approach to the base amorphous conjunction of Pd
Gold, successfully prepares the cylindrical sample of a diameter of 72mm, and size improves by about one time when not using the method.
The Fe base noncrystal alloy with soft magnetism is also suitable by same this method, it is possible to improves it in various degree and is formed
Ability.Oxygen in aluminium-based amorphous alloy melt is mainly with compound Al2O3Form exists, and these oxides are oxidation folders
Miscellaneous main component.For Al base noncrystal alloy, use B2O3Coated purified treatment there will be reduction reaction,
Separate out simple substance B and oxide Al2O3, form more heterogeneous forming core core, reduce amorphous formation ability and reach not
To the requirement purified.
Visible, in aluminium-based amorphous alloy melt the existence of oxide inclusion be restrict its Forming ability promote one crucial because of
Element, but the melt treating method used in the strongest glass former system is inapplicable in Al base noncrystal alloy,
Therefore, cleaning molten molten salt composition and the processing method gesture thereof being applicable to improve aluminium-based amorphous alloy Forming ability is sought
Must go.
Summary of the invention
It is an object of the invention to provide a kind of cleaning molten fused salt improving al based amorphous alloy Forming ability and
Cleaning molten processing method, solve oxide inclusion too high levels in conventional aluminium-based amorphous alloy foundry alloy and cause non-
The problem that brilliant Forming ability is low, expands the light high-intensity aluminum base non-crystaline amorphous metal range of application as structural material.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of cleaning molten fused salt improving al based amorphous alloy Forming ability, is at basis molten salt system
KCl-MgCl2-CaCl2Middle addition additional fused salt CaF2Formed, wherein: each component in the molten salt system of described basis
Weight percentage is: KCl is 20-65%, MgCl2For 30-50%, CaCl2For 1-30%；Described attached
Add fused salt CaF2Addition based on the 10-30% of molten salt system gross weight.
When utilizing above-mentioned cleaning molten fused salt that al based amorphous alloy carries out cleaning molten process, the addition of fused salt
Account for the 0.5-2% of al based amorphous alloy gross weight；Concrete cleaning molten processing method comprises the steps:
Aluminium-based amorphous alloy foundry alloy uses vacuum arc furnace melting, carries out cleaning molten process in fusion process, tool
Body process is: be first placed in bottom al based amorphous alloy by described cleaning molten fused salt, when vacuum reaches
5×10-3During Pa, start master alloy melting, after foundry alloy is completely melt, controls mother alloy melt temperature and exist
Between 1000-1200 DEG C, open electromagnetic mixing apparatus simultaneously and carry out cleaning molten process, when cleaning molten processes
Between be 30-120s.Electromagnetic mixing apparatus electric current is 10-20A.
It is non-that the present invention above-mentioned cleaning molten fused salt and cleaning molten processing method are applicable to Al-TM-RE system aluminum base
Peritectic alloy (RE represents that rare earth element, TM represent transiting group metal elements).
Design principle of the present invention is as follows:
Oxide inclusion (Al in aluminium-based amorphous alloy melt2O3) in non-crystaline amorphous metal process of setting, can be with heterogeneous shape
Presented in epipole in melt, this is beneficial to the forming core of crystal phase, grows up and reunite, for the crystalline substance of amorphous
Change condition of providing convenience.And, melt exists oxide inclusion, the rate of heat transfer of melt can be had a strong impact on,
Make melt quickly not transfer heat away from, increase the critical cooling rate of melt, cause non-crystaline amorphous metal
The reduction of Forming ability.For Al base noncrystal alloy, use B2O3Coated purified treatment there will be reduction reaction,
Separate out simple substance B and oxide Al2O3, form more heterogeneous forming core core, reduce amorphous formation ability and reach not
To the requirement purified.
The present invention, when melting Al base amorphous master alloy, uses the molten salt system of specific components to carry out cleaning molten
After process, not only can remove the oxide slag inclusion in al based amorphous alloy, but also it is female to have refinement aluminium-based amorphous alloy
The effect of alloy grain, does not has crystal phase in sample after cleaning molten process, so that Al TM RE
The Forming ability of system al based amorphous alloy obtains bigger raising.
Cleaning molten molten salt composition of the present invention and cleaning molten processing method have the advantage that
1, fused salt cost is the lowest.
2, the easy easily enforcement of technical process is processed.
3, amorphous formation ability can be improved, be the Al of 1mm to existing critical dimension86Ni6Y4.5Co2La1.5Five
Unit's alloy (patent: ZL 200910010727.7), after using molten salt system of the present invention and PROCESS FOR TREATMENT, is formed
The critical dimension of amorphous can bring up to 1.5mm, is the full-size al base block that fusion casting obtains the most in the world
Body non-crystaline amorphous metal, expands the light high-intensity aluminum base non-crystaline amorphous metal range of application as structural material.
4, the present invention has progradation to the range of application expanding light high-intensity aluminum base non-crystaline amorphous metal, makes aluminum base
The preparation of amorphous becomes to be more prone to.
Accompanying drawing explanation
Fig. 1 is the outward appearance comparison diagram of ingot casting before and after cleaning molten processes；In figure: before (A) processes；(B) place
After reason.
Fig. 2 is the XRD diffraction pattern on mother alloy ingot surface before and after cleaning molten processes；
Fig. 3 is the vertical section SEM photograph of mother alloy ingot before and after cleaning molten processes；In figure: (A) processes
Before；(B) after processing.
Fig. 4 is the EDS analysis result of ingot casting section before and after cleaning molten processes；In figure: before (A) processes；
(B) after processing.
Fig. 5 is the aluminium-based amorphous alloy sample prepared by foundry alloy before and after cleaning molten processes；In figure: (A) processes
Before；(B) after processing.
Fig. 6 is the X-ray diffractogram of amorphous sample before and after cleaning molten processes；In figure: before (A) processes；
(B) after processing.
Detailed description of the invention
Below in conjunction with drawings and Examples in detail the present invention is described in detail.
Embodiment 1
The aluminium-based amorphous alloy foundry alloy chemical composition that the present embodiment selects is (at.%), Al 86%, Ni 6%, Co 2%,
Y 4.5%, La 1.5%；This composition is one of aluminum current the strongest alloy of base noncrystal alloy Forming ability, critical chi
Very little up to 1mm.Molten salt system is by KCl-MgCl2-CaCl2Basis molten salt system and additional fused salt CaF2Constitute,
The most each Ingredients Weight proportioning is: KCl:26%, MgCl2: 49%, CaCl2: 25%, additional fused salt CaF2
Account for the 20% of basis molten salt system gross weight；When al based amorphous alloy cleaning molten is processed, adding of above-mentioned fused salt
Dosage accounts for the 1.5% of al based amorphous alloy gross weight；Specific embodiment: above-mentioned fused salt is placed in aluminium-based amorphous alloy
Bottom alloy, arc melting foundry alloy is used to become circle ingot casting, when vacuum reaches 5 × 10-3During Pa, start to melt
Refining, after foundry alloy is completely melt, control foundry alloy melt liquid temperature, between 1000-1200 DEG C, opens electricity
Magnetic agitating device, electric current is 15A, and the cleaning molten time is at 120s.
Fig. 1 is the outward appearance comparison diagram of ingot casting before and after cleaning molten processes, and wherein Fig. 1 (A) is at cleaning molten
Ingot casting before reason, Fig. 1 (B) is the ingot casting after cleaning molten processes, as seen from the figure, at cleaning molten
After reason, ingot casting surface is brighter and cleaner, and oxide slag inclusion separates out and reduces.Fig. 2 is foundry alloy casting before and after cleaning molten processes
The XRD diffraction pattern of ingot surface, in figure, curve A is before cleaning molten processes, and curve B is that cleaning molten processes
After.As seen from the figure, before cleaning molten processes, sample surfaces is mainly by α-Al phase and Al2O3Constitute Deng oxide,
Al after melt treatment2O3Oxide is more to be separated out by fused salt parcel.Fig. 3 is foundry alloy before and after cleaning molten processes
The vertical section SEM photograph of ingot casting, before wherein Fig. 3 (A) is melt treatment, Fig. 3 (B) is melt treatment
After.Relatively concrete dynamic modulus and oxide slag inclusion distribution is there is on the section of sample before cleaning molten processes as seen from the figure,
And streaky structure is the thickest in alloy, and cleaning molten eliminates the oxide slag inclusion in sample after processing, and
Alloy structure is the most tiny.Fig. 4 is the EDS analysis result of ingot casting section before and after cleaning molten processes, wherein
Before Fig. 4 (A) is melt treatment, after Fig. 4 (B) is melt treatment.As seen from the figure, after cleaning molten processes
Oxygen content in ingot casting reduces about about 8 times.Fig. 5 is the aluminum base prepared by foundry alloy before and after cleaning molten processes
Amorphous sample, before wherein Fig. 5 (A) is melt treatment, after Fig. 5 (B) is melt treatment.As seen from the figure,
Before melt treatment, in 1.5mm sample there is relatively polycrystal phase in centre, and after cleaning molten process in sample
There is no crystal phase.Fig. 6 is the X-ray diffractogram of amorphous sample before and after cleaning molten processes, wherein
Before Fig. 6 (A) is melt treatment, after Fig. 6 (B) is melt treatment.As seen from the figure, sample after melt treatment
For completely amorphous state.
Embodiment 2
It is with the difference of embodiment 1:
Basis molten salt system KCl-MgCl2-CaCl2In each Ingredients Weight proportioning different, each Ingredients Weight proportioning is:
KCl:62%, MgCl2: 35%, CaCl2: 3%.
Result: in mother alloy ingot, the most untreated ingot casting of oxygen content substantially reduces, about reduces by 8 times, and tissue is thin
Change.
Embodiment 3
It is with the difference of embodiment 1:
Additional fused salt addition is different, additional fused salt CaF2Account for the 10% of basis molten salt system gross weight.
Result: in mother alloy ingot, the most untreated ingot casting of oxygen content substantially reduces, about reduces by 6 times, and tissue is thin
Change.
Embodiment 4
It is with the difference of embodiment 1:
Additional fused salt addition is different, additional fused salt CaF2Account for the 30% of basis molten salt system gross weight.
Result: in mother alloy ingot, oxygen content is higher than embodiment 1, but reduces about 4 times relative to untreated ingot casting,
Sample occurs smaller aperture defect.
Embodiment 5
It is with the difference of embodiment 1:
When cleaning molten processes, the addition of fused salt is different, and the addition of fused salt accounts for al based amorphous alloy total amount
2%.
Result: in mother alloy ingot, the most untreated ingot casting of oxygen content reduces about 5 times, but has unreacted in ingot casting
Fused salt remains.
Comparative example 1
It is with the difference of embodiment 1:
When cleaning molten processes, the addition of fused salt is different, and the addition of fused salt accounts for al based amorphous alloy gross weight
0.2%.
Result: in mother alloy ingot, the most untreated ingot casting of oxygen content reduces inconspicuous, has oxide slag inclusion in ingot casting
Residual.
Comparative example 2
It is with the difference of embodiment 1:
When cleaning molten processes, cleaning molten time 20s.
Result: in mother alloy ingot oxygen content reduce inconspicuous, and ingot casting has a large amount of unreacted fused salt residual and
Pore exists.
Comparative example 3
It is with the difference of embodiment 1:
When cleaning molten processes, cleaning molten time 90s.
Result: in mother alloy ingot, the most untreated ingot casting of oxygen content reduces about 6 times, but has a small amount of gas in ingot casting
Hole exists.
Comparative example 4
It is with the difference of embodiment 1:
When cleaning molten processes, cleaning molten time 130s.
Result: in mother alloy ingot, the most untreated ingot casting of oxygen content reduces about 2 times, but ingot casting has the most not
Reaction fused salt residual and pore exist.
Claims (6)
1. the cleaning molten fused salt improving al based amorphous alloy Forming ability, it is characterised in that: this melt
Purifying fused salt is at basis molten salt system KCl-MgCl2-CaCl2Middle addition additional fused salt CaF2Formed, wherein:
Described additional fused salt CaF2Addition based on the 10-30% of molten salt system gross weight.
The cleaning molten fused salt of raising al based amorphous alloy Forming ability the most according to claim 1, its
Being characterised by: according to weight, in the molten salt system of described basis, each constituent content is as follows:
KCl 20-65%；
MgCl230-50%；
CaCl21-30%.
3. utilize cleaning molten fused salt described in claim 1 to carry out improving the molten of al based amorphous alloy Forming ability
Body purifying treatment method, it is characterised in that: use vacuum arc furnace melting aluminium-based amorphous alloy foundry alloy, in melting
Utilizing cleaning molten fused salt to carry out cleaning molten process in journey, the usage amount of fused salt accounts for al based amorphous alloy gross weight
0.5-2%.
The cleaning molten processing method of raising al based amorphous alloy Forming ability the most according to claim 3,
It is characterized in that: this processing method detailed process is: first described cleaning molten fused salt is placed in aluminium-based amorphous alloy and closes
Bottom gold, when vacuum reaches 5 × 10-3During Pa, start master alloy melting, after foundry alloy is completely melt, control
Mother alloy melt temperature processed, between 1000-1200 DEG C, is opened electromagnetic mixing apparatus simultaneously and is carried out at cleaning molten
Reason, the cleaning molten process time is 30-120s.
The cleaning molten processing method of raising al based amorphous alloy Forming ability the most according to claim 4,
It is characterized in that: described electromagnetic mixing apparatus electric current is 10-20A.
The cleaning molten processing method of raising al based amorphous alloy Forming ability the most according to claim 1,
It is characterized in that: described al based amorphous alloy is Al TM RE system al based amorphous alloy.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109604547A (en) * | 2019-02-01 | 2019-04-12 | 中国科学院金属研究所 | A method of improving Al-Y-TM system al based amorphous alloy corrosion resistance |
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| RU2203337C1 (en) * | 2001-10-31 | 2003-04-27 | ООО "Промтрейдинтелл" | Flux for aluminum and its alloys |
| CN101338391A (en) * | 2008-08-11 | 2009-01-07 | 北京航空航天大学 | Quick setting block aluminum alloy with high strength and high ductibility and toughness and method for preparing same |
| CN103468976A (en) * | 2013-10-12 | 2013-12-25 | 青海三工镁业有限公司 | No-pollution green environment-friendly fluxing agent for magnesium and magnesium alloy and preparation method thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5751230A (en) * | 1980-09-12 | 1982-03-26 | Aikoorosuborou Kk | Flux for treating molten aluminum or aluminum alloy by blowing |
| CN1073486A (en) * | 1991-12-16 | 1993-06-23 | 东北工学院 | The aluminum or aluminum alloy slag remover for refining |
| RU2203337C1 (en) * | 2001-10-31 | 2003-04-27 | ООО "Промтрейдинтелл" | Flux for aluminum and its alloys |
| CN1362531A (en) * | 2001-12-27 | 2002-08-07 | 上海交通大学 | Filtering process of eliminating non-metallic foreign impurity ion aluminium melt |
| CN101338391A (en) * | 2008-08-11 | 2009-01-07 | 北京航空航天大学 | Quick setting block aluminum alloy with high strength and high ductibility and toughness and method for preparing same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109604547A (en) * | 2019-02-01 | 2019-04-12 | 中国科学院金属研究所 | A method of improving Al-Y-TM system al based amorphous alloy corrosion resistance |
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