CN105154725B - High-end Al-Zr intermediate alloy and industrial preparation method - Google Patents
High-end Al-Zr intermediate alloy and industrial preparation method Download PDFInfo
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Abstract
The invention discloses a high-end Al-Zr intermediate alloy and an industrial preparation method. The method is simple, practical and beneficial to realization of industrialization. The mass percent of Zr in the prepared Al-Zr intermediate alloy is 3-20%. The second phase (Al3Zr) in the alloy is evenly distributed and dispersed, and the purification degree is high. The preparation technology comprises the steps of raw material pretreatment and prefabrication, aluminum ingot melting or molten aluminum transferring in, adding of a material containing Zr, alloying refinement treatment and casting; and particularly, one or more of potassium fluozirconate, zirconium sponge, zirconium alloy scraps and zirconium scraps are evenly mixed in proportion, an aluminum ingot is placed into an electric furnace crucible to be molten or a molten aluminum transfer bag is used for transferring aluminum molten in advance into an electric furnace, a bell jar or an adding machine is utilized for adding the prepared raw material into the molten body for alloying when the temperature of the molten aluminum reaches 700-900 DEG C, the molten body is constantly and sufficiently stirred and refined in the reaction process, finally, casing is performed at the temperature of 700-1300 DEG C to obtain an ingot, and therefore the Al-Zr intermediate alloy is obtained.
Description
Technical field
The present invention relates to aluminium intermediate alloy and preparation method, more particularly, refer to a kind of using electric furnace industrialization preparation
High-end aluminium zirconium hardener and preparation technology.
Background technology
Zirconium (Zr) is a kind of transition element, is one of highly important alloy element in current aluminium alloy.The master of zirconium
Acting on is：
1). the welding performance of alloy can be significantly improved, is all contained zirconium in middle and high strong weld aluminium alloy, solid solution can be improved
The stability of body, improves quenching degree；
2). can be used as grain refiner, have preferable Grain Refinement Effect；
3). the anti-stress corrosion performance of some aluminium alloys can be improved；
4). there is suppression recrystallization, improve recrystallization temperature, so as to improve intensity；
5). the raising to fracture toughness also has certain effect.
At present, zirconium is applied in multiple aluminium alloy systems, such as：2219 alloys in Al-Cu systems, Al-Li alloy systems
In 8090,6205 alloys in 8091, Al-Mg-Si systems, particularly in high-strength and high-toughness Al-Zn-Mg-Cu alloy system
7050 and 7055 large usage quantities, the addition of zirconium is typically between 0.06～0.25wt%.
At present, the zirconium in aluminium alloy is mainly added by the form of aluminum zirconium (Al-Zr) intermediate alloy.Such as：Shen Qing Publication
Day 2011.02.09, application publication number CN101967573A, number of patent application 201010543765.1, a kind of denomination of invention " profit
With zirconium bits and the aluminum method that alloying manufactures aluminium zirconium hardener at low temperature ".The Chinese patent application is reported using useless zirconium
Bits and aluminum alloying at low temperature, are filtered the aluminum zircaloy prepared, but the alloy melting temp are relatively low using ceramic filter plate,
Zirconium bits are difficult all to be dissolved in aluminium liquid, and zirconium bits casting yield is very low, and is filtered using ceramic filter plate, due to aluminium zirconium hardener
With aluminium liquid viscosity it is big the characteristics of, be difficult to realize industrialized production.And for example：Shen Qing Publication day 2013.03.27, application publication number
CN102994810A, number of patent application 201110266696.9, denomination of invention " preparation method of high purity aluminum-zirconium intermediate alloy ".Should
Chinese patent is reported and prepares rafifinal zircaloy using zirconium agent and rafifinal etc..Alloy prepared by the method uses zirconium agent, former
Material prepare it is relatively complicated, it is relatively costly.
As the density difference of zirconium (Zr) and aluminum (Al) is larger, (zirconium density is 6.51g/cm3, aluminum density is 2.7g/cm3),
And due to the different melting points of zirconium and aluminum larger (fusing point of zirconium is 1852 DEG C, and the fusing point of aluminum is 660 DEG C), need higher temperature
Zr element can be made fully to melt.Therefore, the preparation difficulty of Al-Zr intermediate alloys is big, usually occur in product homogeneity of ingredients compared with
Difference, zirconium content are uneven, ZrAl in microscopic structure3Particle is distributed in needle-like and size is larger, the problems such as oxide inclusion is more, this
The final using effect of Al-Zr intermediate alloys is had a strong impact on.And aluminium alloy is particularly Aero-Space, high ferro aluminium alloy pair
The prescription of Al-Zr intermediate alloys is increasingly improved, particularly the uniformity to Al-Zr intermediate alloy compositions, tissue it is uniform
Property and particle shape size there has also been more strict requirements.Traditional Al-Zr intermediate alloys have been unsatisfactory for high-end using aluminium alloy
Performance need.
Composition is uniform and stable for exploitation, degree of segregation is little, high purity and the ZrAl with fine uniform distribution3Particle it is high-end
Al-Zr intermediate alloys so as to which temperature is low with adding, effect is fast, form the advantages of organizing fine zirconia constituent content stable, meets
Following Al-alloy material and the needs of high performance unit development.
The content of the invention
An object of the present invention is to provide a kind of high-end aluminium zirconium hardener, the quality hundred of zirconium in the aluminium zirconium hardener
Divide than being 3～20%, the second phase (Al in alloy3Zr) be evenly distributed, disperse, degree of purity is higher, meets Aero-Space, high ferro
The application requirement of contour tough aluminum alloy materials.
The second object of the present invention is to propose that a kind of industrialization is prepared in the fine aluminum zirconium that the zr element of aluminium alloy adds
Between alloy method, being capable of the uniformity of zr element, degree of purity in effective control Al-Zr intermediate alloy using the method for the present invention
And Al3The distribution of Zr microscopic structures.The Al-Zr intermediate alloy usings method are simple, pollution-free, add easy to use, shorter
Time in reach the Al of tiny, disperse in optimal using effect, particularly alloy3Zr particles are conducive to the high-quality of product
Control, meets the production needs that excellent performance aluminium alloy is particularly the extraordinary aluminum alloy materials such as Aero-Space, high ferro use.
The industrialization preparation method of a kind of aluminium zirconium hardener of the present invention, it is characterised in that include the following steps：
Step A, prepares aluminum feedstock；
Aluminum material is chosen according to required obtained target Al-Zr intermediate alloy composition；Described aluminum material can be quality hundred
Divide the technical pure aluminium ingot or aluminium block than purity is 99.7%；
Step B, prepares zirconium raw material；
Zirconium material is chosen according to required obtained target Al-Zr intermediate alloy composition；Described zirconium material can be fluorine zirconic acid
Potassium (K2ZrF6), sponge zirconium, zircaloy leftover bits, zirconium bits one or more combination；
Step C, melting aluminium liquid；
Added in electric furnace by the aluminum material that step A is prepared by A charge doors；And with heating rate as 1～10 degree/min, liter
Temperature is fused into aluminium liquid in electric furnace to 700～900 degree；
Step D, refinery by de-gassing aluminium liquid；
Under the conditions of reaching 700～900 degree, pressure is passed through in electric furnace for 0.1 by the middle through-hole of hollow agitator
～0.5 MPa of argon or nitrogen；Low whipping speed is under 100～400 revs/min, after stirring 10～30 minutes, in removing
Portion's slag thing, is obtained refined aluminium liquid；
Step E, melting aluminum zircaloy liquid；
Step E-1, the zirconium material prepared step B by A charge doors are added in batches and under conditions of being spaced stirring to step D
In obtained refined aluminium liquid；
First, at 700～1300 degree, the zirconium material of a decile is added to obtained in step D and is refined in aluminium liquid, in stirring
Speed is that, under 50～300 revs/min, stirring stopped after 3～10 minutes；
Then, after being spaced 1～15 minute, the zirconium material of another decile is added, low whipping speed is 50～300 revs/min
Under, stirring stopped after 3～10 minutes；
Then, after being spaced 1～15 minute, the zirconium material of last decile is added, low whipping speed is 50～300 revs/min
Under, stirring stopped after 3～10 minutes, was cooled to 300～500 degree；
Step E-2, under the conditions of reaching 700～1300 degree, is passed through in electric furnace by the middle through-hole of hollow agitator
Pressure is 0.1～0.5 MPa of argon or nitrogen；It is, under 100～400 revs/min, to carry out 1 time or repeatedly degasification in speed
After 10～60 minutes, top slag thing is removed；
Step E-3, keeping temperature are 700～1300 degree, and refine was obtained aluminum zircaloy liquid after 10～30 minutes；
Step F, aluminium zirconium hardener of casting；
By wrought aluminum zircaloy liquid obtained in step E under 700～1300 degree, casting is obtained Al-Zr intermediate alloys；Casting
When mold temperature control less than 500 degree.The Al-Zr intermediate alloys of 1 ton of general casting cannot be greater than 120 minutes.
In the present invention, refining agent can also be added in step E, the refining agent is cryolite, calcium fluoride, chlorination
One or more combination in sodium, potassium chloride or prodan.
The present invention prepares the advantage of Al-Zr intermediate alloy methods：
1. precisely, impurity content is low for the composition of Al-Zr intermediate alloys.
2. the second phase Al in Al-Zr intermediate alloys3Zr phases are tiny, disperse, snap action after addition；Al3Zr phases have to be lost
Transmissibility, forms good tissue in the product.
3. the requirement that the satisfaction of Al-Zr intermediate alloys is lifted containing the high-end aluminum alloy organizations of Zr, stable performance.
4. the addition of Al-Zr intermediate alloys is convenient, pollution-free.
Description of the drawings
Fig. 1 is the flow chart that the present invention utilizes Electric Cooker for Al-Zr intermediate alloys.
Fig. 2 is the furnace binding schematic diagram of the improved electric furnace that the present invention prepares Al-Zr intermediate alloys.
Fig. 2A is another device structure schematic diagram that the present invention prepares Al-Zr intermediate alloys.
Fig. 3 is another kind of flow chart for utilizing Electric Cooker for Al-Zr intermediate alloys.
Fig. 4 A are the micro-organization charts that embodiment 1 is obtained Al-Zr5 intermediate alloys.
Fig. 4 B are the fracture apperances that embodiment 1 is obtained Al-Zr5 intermediate alloy ingot castings.
Fig. 4 C are the ingot casting section structure figures that embodiment 1 is obtained Al-Zr5 intermediate alloys.
Fig. 4 D are that embodiment 1 is obtained the mechanical property figure that Al-Zr5 intermediate alloys are applied in ultra-high-strength aluminum alloy.
Specific embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Referring to the structural representation that the electric furnace shown in Fig. 2, Fig. 2A is combined with the getter that dusts, it is additionally arranged in traditional electric furnace
Hollow agitator, electric furnace after referred to as transforming.One end of the pitman of the hollow agitator is provided with stirring blade；Pitman is
Hollow structure, that is, be provided with middle through-hole；Pitman is provided with valve, and valve is used for on/off gas.The middle part of hollow agitator leads to
Hole can be passed through the gas of certain pressure, and after transformation, electric furnace connected by discharge pipe between getter with being dusted.Aluminum material, zirconium material
Sent into by A charge doors, refining agent is sent into by B charge doors.Certain pressure is passed through by inlet channel in the getter that dusts
Gas.Control for convenience flows through the gas of middle through-hole, can arrange valve on the gas channels of hollow agitator.
Can ventilate during charging or obstructed gas.
In the present invention, hollow agitator is from ceramics such as the metal with resistance to aluminium liquid etch coating or graphite, carborundums
Material.The front end of hollow agitator is blade construction.Alr mode is possible with the electromagnetic agitation of electric furnace.
Traditional electric furnace can be divided into resistance furnace, induction furnace, electric arc furnace, plasma heating furnace or electron beam furnace etc., and make in the present invention
Transformation electric furnace, is in the body of heater of electric furnace to be provided with hollow agitator.Due to being industrialization, jumbo melting preparation
High-end aluminium zirconium hardener, so the smelting equipment selected is electric furnace.
Referring to shown in Fig. 2, Fig. 3, the present invention proposes the side that a kind of utilization electric furnace industrialization prepares Al-Zr intermediate alloys
Method, which includes the following steps：
Step A, prepares aluminum feedstock；
Aluminum material is chosen according to required obtained target Al-Zr intermediate alloy composition；Described aluminum material can be quality hundred
Divide the technical pure aluminium ingot or aluminium block than purity is 99.7%；
Step B, prepares zirconium raw material；
Zirconium material is chosen according to required obtained target Al-Zr intermediate alloy composition；Described zirconium material can be fluorine zirconic acid
Potassium (K2ZrF6), sponge zirconium, zircaloy leftover bits, zirconium bits one or more combination；
Step C, melting aluminium liquid；
Added in electric furnace by the aluminum material that step A is prepared by A charge doors (as shown in Figure 2)；And with heating rate as 1～10
Degree/min, be warming up to 700～900 degree, aluminium liquid is fused in electric furnace；
Step D, refinery by de-gassing aluminium liquid；
Under the conditions of reaching 700～900 degree, led to in electric furnace by the middle through-hole (as shown in Figure 2) of hollow agitator
Enter argon or nitrogen that pressure is 0.1～0.5 MPa；Low whipping speed is, under 100～400 revs/min, to stir 10～30 points
Zhong Hou, removes top slag thing, and refined aluminium liquid is obtained；
Step E, melting aluminum zircaloy liquid；
Step E-1, the zirconium material prepared step B by A charge doors (as shown in Figure 2) is in batches and under conditions of being spaced stirring
Add into refined aluminium liquid obtained in step D；
First, at 700～1300 degree, the zirconium material of a decile is added to obtained in step D and is refined in aluminium liquid, in stirring
Speed is that, under 50～300 revs/min, stirring stopped after 3～10 minutes；
Then, after being spaced 1～15 minute, the zirconium material of another decile is added, low whipping speed is 50～300 revs/min
Under, stirring stopped after 3～10 minutes；
Then, after being spaced 1～15 minute, the zirconium material of last decile is added, low whipping speed is 50～300 revs/min
Under, stirring stopped after 3～10 minutes, was cooled to 300～500 degree；
Step E-2, reach 700～1300 degree under the conditions of, by the middle through-hole (as shown in Figure 2) of hollow agitator to
Argon or nitrogen that pressure is 0.1～0.5 MPa are passed through in electric furnace；It is, under 100～400 revs/min, to carry out 1 time in speed
Or repeatedly top slag thing is removed after degasification 10～60 minutes；
Step E-3, keeping temperature are 700～1300 degree, and refine was obtained aluminum zircaloy liquid after 10～30 minutes；
In the present invention, zirconium material disposably can also be added.
Step F, casting are obtained aluminium zirconium hardener；
By wrought aluminum zircaloy liquid obtained in step E under 700～1300 degree, casting is obtained Al-Zr intermediate alloys；Casting
When mold temperature control less than 500 degree.
In the present invention, in order to reach, composition is uniform, when casting cycle needs the solidification of strict control Al-Zr intermediate alloys
Between, the Al-Zr intermediate alloys of 1 ton of general casting cannot be greater than 120 minutes.
Al-Zr intermediate alloys obtained in Jing the inventive method are carried out into analysis of components, zr element in Al-Zr intermediate alloys
Mass percentage content is that the mass percentage content of 3%～20%, impurity is less than 0.3%, balance of aluminum.
Referring to shown in Fig. 1, Fig. 2A, in the present invention, refining agent can also be added before step E-1；
Step E-1, adds refining agent, and good seal B chargings in the getter that dusts by B charge doors (as shown in Figure 2 A)
Mouthful；Then nitrogen or argon are sent into in the getter that dusts by inlet channel, gas pressure is 0.2～0.8 MPa；In air pressure
Under the conditions of, refining agent Jing tapping channels are in the aluminum zircaloy liquid that temperature is 700～1300 degree；
The refining agent is cryolite (nNaF.AlF3), calcium fluoride (CaF2), Sodium Chloride (NaCl), potassium chloride (KCl) or
Person prodan (Na2SiF6) in one or more combination.
Step E-2, the zirconium material prepared step B by A charge doors (as shown in Figure 2 A) in batches and are spaced the condition of stirring
Under add to obtained in step D and refine in aluminium liquid；
First, at 700～1300 degree, the zirconium material of a decile is added to obtained in step D and is refined in aluminium liquid, in stirring
Speed is that, under 50～300 revs/min, stirring stopped after 3～10 minutes；
Then, after being spaced 1～15 minute, the zirconium material of another decile is added, low whipping speed is 50～300 revs/min
Under, stirring stopped after 3～10 minutes；
Then, after being spaced 1～15 minute, the zirconium material of last decile is added, low whipping speed is 50～300 revs/min
Under, stirring stopped after 3～10 minutes, was cooled to 300～500 degree；
Step E-3, under the conditions of reaching 700～1300 degree, by the middle through-hole (as shown in Figure 2 A) of hollow agitator
Argon or nitrogen that pressure is 0.1～0.5 MPa are passed through in electric furnace；It is, under 100～400 revs/min, to carry out 1 in speed
After secondary or multiple degasification 10～60 minutes, top slag thing is removed；
Step E-4, keeping temperature are 700～1300 degree, and refine was obtained aluminum zircaloy liquid after 10～30 minutes.
Embodiment 1
Referring to shown in Fig. 1, Fig. 2A, the high-end Al-Zr5 intermediate alloys of industrialization system include the following steps：
Step A, prepares aluminum feedstock；
Choose commercial-purity aluminium of the mass percent purity more than or equal to 99.7%；In order to high-end Al-Zr5 will be obtained
Intermediate alloy, so the regulation during technical standard execution GB/T 1196-2008 are with reference to when aluminum material is chosen to aluminum material.
Step B, prepares zirconium raw material；
Choose potassium fluorozirconate (K of the mass percent purity for 97-98%2ZrF6)；
Step C, melting aluminium liquid；
The aluminum material that step A is prepared is added in intermediate frequency furnace by A charge doors (as shown in Figure 2 A), with heating rate
For 4 degrees/min, be warming up to 800 ± 10 degree, aluminium liquid processed is melted in improved intermediate frequency furnace；
Step D, refinery by de-gassing aluminium liquid；
Under the conditions of temperature reaches 800 ± 10 degree, by the middle through-hole (as shown in Figure 2 A) of hollow agitator to transformation
The argon (mass percent purity >=99.999%) that pressure is 0.2 MPa is passed through in intermediate frequency furnace afterwards；Low whipping speed
, under 340 revs/min, after stirring 20 minutes, to remove top slag thing, refined aluminium liquid is obtained；
Step E, melting aluminum zircaloy liquid；
Step E-1, refining agent is added by B charge doors (as shown in Figure 2 A) in the getter that dusts, and good seal B chargings
Mouthful；Then argon (mass percent purity >=99.999%), gas pressure are sent into in the getter that dusts by inlet channel
For 0.4 MPa；
The refining agent is cryolite (nNaF.AlF3), potassium chloride (KCl) and prodan (Na2SiF6) mixture,
Cryolite (the nNaF.AlF of 40g is added in the mixture of 100g3), the potassium chloride (KCl) of 40g and the prodan of 20g
(Na2SiF6)；
Step E-2, the zirconium material prepared step B by A charge doors (as shown in Figure 2 A) in batches and are spaced under stirring condition
Add into refined aluminium liquid obtained in step D, i.e.,：
First, when temperature reaches 800 ± 5 degree, the zirconium material of a decile is added in refined aluminium liquid, low whipping speed is
Under 120 revs/min, stirring stopped after 10 minutes；
Then, the zirconium material of another decile after being spaced 5 minutes, is added, low whipping speed is, under 120 revs/min, to stir 10 points
Stop after clock；
Then, the zirconium material of last decile after being spaced 5 minutes, is added, low whipping speed is, under 120 revs/min, to stir 10 points
Stop after clock, be cooled to 300 degree；
Step E-3, under the conditions of reaching 800 ± 5 degree, is passed through pressure by the middle through-hole of hollow agitator in electric furnace
Argon or nitrogen for 0.3 MPa；It is, under 220 revs/min, to carry out 3 degasification in speed, at interval of 3 minutes, 15 points of degasification
Clock, removes top slag thing；
Step E-4, keeping temperature are 800 ± 5 degree, and refine was obtained aluminum zircaloy liquid after 10 minutes；
Step F, aluminium zirconium hardener of casting；
By wrought aluminum zircaloy liquid obtained in step E under 900 ± 5 degree, casting is obtained aluminium zirconium hardener.
In embodiments of the invention 1, in order to reach, composition is uniform, needs strictly to control the molding time of Al-Zr5, one
As cast 1 ton of aluminium zirconium hardener cannot be greater than 100 minutes.
Aluminium zirconium hardener obtained in embodiment 1 is designated as into Al-Zr5, its composition is：
| Element | Al | Zr | Fe | Si | Individual element in impurity | Impurity summation |
| Mass fraction content (%) | Surplus | 5.02 | 0.15 | 0.12 | <0.05 | 0.15 |
Note：In impurity individual element be V, Ti, Mn, Cr.
Al-Zr5 intermediate alloys obtained in the preparation method of Jing embodiments 1, the early stage, mid-term, later stage sampling point in casting
Analyse, the mass percent of wherein zr element is：Casting early stage zirconium 4.97%, sampling mid-term zirconium 5.05%, samples later stage zirconium
5.11%, degree of segregation less (5.11%～4.97%).
Al-Zr5 intermediate alloys obtained in the preparation method of Jing embodiments 1, its microscopic structure as shown in Figure 4 A, divide in alloy
The tiny nascent ZrAl of the substantial amounts of disperse of cloth3Phase, is smaller in size than 30 microns, and 70 microns of full-size ＜ exists to the fracture of alloy
Observed under Stereo microscope as shown in Figure 4 B, fractograph is fine and close, without obvious slag inclusion, segregation thickness degree is less than The ingot casting thickness
5%, as shown in Figure 4 C, ingot casting fractography is fine and close, without obvious slag inclusion and pore for perusal ingot casting fractography.Zr element
The control of deviation content is between ± 0.3%.
By embodiment 1 as can be seen that the high-end Al-Zr intermediate alloys using method is simple, composition accurate, when shorter
The interior Al3Zr particles for reaching tiny, disperse in preferable using effect, particularly alloy can significantly improve the property of alloy
Can, meet composition, the production needs of the excellent performance aluminium alloy of even tissue, i.e., referred to as high-end intermediate alloy.
The application example of embodiment 1
Tried out in ultra-high-strength aluminum alloy is Al-8.8Zn-2.8Mg-2.4Cu-0.05Ti-0.1Zr, equipment is 10
The reverberatory furnace of ton, the usage amount of the Al-Zr5 intermediate alloys is 2% for always feeding intake.10 tons melting furnace temperatures reach 720 ±
Al-Zr5 intermediate alloys obtained in embodiment 1 are added when 10 degree, it is smokeless during addition, all dissolve within 10 ± 3 minutes, stokehold difference portion
Position sampling, zirconium content between 0.1～0.107% (plus zirconium is 0.0003% before zirconium), casting yield more than 99%, to processing
Sample afterwards carries out performance test, as shown in Figure 4 D, it can be seen that the tensile strength sigma of alloybWith yield strength σ0.2Contain with Zr
The increase of amount and increase, tension and yield strength are significantly improved.
Embodiment 2
Industrialization Al-Zr10 intermediate alloys include the following steps：
Step A, prepares aluminum feedstock；
The technical pure of mass percent purity 99.7% is chosen according to required obtained Al-Zr10 intermediate alloys composition
Aluminium block；
Step B, prepares zirconium raw material；
Zircaloy leftover bits are chosen according to required obtained Al-Zr10 intermediate alloys composition；
Step C, melting aluminium liquid；
Added in main frequency furnace, with heating rate as 6 by the aluminum material that step A is prepared by A charge doors (as shown in Figure 2)
Degree/min, be warming up to 900 degree, aluminium liquid is fused in electric furnace；
Step D, refinery by de-gassing aluminium liquid；
Under the conditions of temperature reaches 900 degree, by the middle through-hole (as shown in Figure 2) of hollow agitator in main frequency furnace
It is passed through the argon that pressure is 0.3 MPa；Low whipping speed is, under 120 revs/min, after stirring 10 minutes, to remove top slag thing, system
Aluminium liquid must be refined；
Step E, melting aluminum zircaloy liquid；
Step E-1, the zirconium material prepared step B by A charge doors (as shown in Figure 2) is in batches and under conditions of being spaced stirring
Add into refined aluminium liquid obtained in step D；
First, when extraction temperature reaches 1200 degree, the zirconium material of a decile is added to obtained in step D and refines aluminium liquid
In, low whipping speed is that, under 300 revs/min, stirring stopped after 3 minutes；
Then, after being spaced 5 minutes, the zirconium material of another decile is added, low whipping speed is stirring 10 under 100 revs/min
Stop after minute；
Then, after being spaced 10 minutes, the zirconium material of last decile is added, low whipping speed is stirring 10 under 80 revs/min
Stop after minute；It is cooled to 350 degree；
Step E-2, under the conditions of reaching 1200 degree, by the middle through-hole (as shown in Figure 2) of hollow agitator to electric furnace
In be passed through the argon or nitrogen that pressure is 0.4 MPa；It is, under 260 revs/min, after carrying out 1 time or 60 minutes, to remove in speed
Top slag thing；
Step E-3, keeping temperature are 1200 degree, and refine was obtained aluminum zircaloy liquid after 10 minutes；
Step F, casting are obtained aluminium zirconium hardener；
By wrought aluminum zircaloy liquid obtained in step E under 1000 degree, the aluminium zirconium hardener of 1 ton of casting needs 57 points
Clock, casting are obtained aluminium zirconium hardener.
Aluminium zirconium hardener obtained in embodiment 2 is designated as into Al-Zr10, its composition is：
| Element | Al | Zr | Fe | Si | Individual element in impurity | Impurity summation |
| Mass fraction content (%) | Surplus | 9.98 | 0.19 | 0.072 | <0.05 | 0.15 |
Note：In impurity individual element be V, Ti, Mn, Cr.
Al-Zr10 intermediate alloys are prepared Following the procedure of Example 2, the early stage, mid-term, later stage sampling point in casting
Analyse, the mass percent of wherein zr element is：Casting early stage zirconium 9.85%, sampling mid-term zirconium 10.01%, samples later stage zirconium
10.21%.Substantial amounts of block nascent ZrAl is distributed in alloy3Phase, average-size are less than 50 microns, are uniformly distributed, to alloy
Observed under fracture Stereo microscope, fractograph is fine and close, without obvious slag inclusion, segregation thickness degree is less than The ingot casting thickness
10%.
Embodiment 3
Industrialization Al-Zr15 intermediate alloys include the following steps：
Step A, prepares aluminum feedstock；
Sponge zirconium is chosen according to required obtained Al-Zr15 intermediate alloys composition；
Step B, prepares zirconium raw material；
Zircaloy leftover bits are chosen as zirconium material according to required obtained target Al-Zr intermediate alloy composition；
Step C, melting aluminium liquid；
By A charge doors (as shown in Figure 2) by transport bag transhipment come aluminium liquid pour in the crucible of main frequency furnace, adjustment aluminum
Liquid temp is 950 degree；
Step D, refinery by de-gassing aluminium liquid；
Under the conditions of reaching 950 degree, pressure is passed through by the middle through-hole (as shown in Figure 2) of hollow agitator in electric furnace
Argon or nitrogen for 0.5 MPa；Low whipping speed is, under 400 revs/min, after stirring 12 minutes, to remove top slag thing, system
Aluminium liquid must be refined；
Step E, refinery by de-gassing aluminum zircaloy liquid；
Step E-1, is 400 revs/min by the zirconium material low whipping speed that step B is prepared by A charge doors (as shown in Figure 2)
Under the conditions of add to obtained in step D and refine in aluminium liquid；
Step E-2, under the conditions of reaching 1000 degree, by the middle through-hole (as shown in Figure 2) of hollow agitator to electric furnace
In be passed through the argon or nitrogen that pressure is 0.35 MPa；It is, under 400 revs/min, after carrying out 1 time 30 minutes, to remove in speed
Top slag thing；
Step E-3, keeping temperature are 1000 degree, and refine was obtained aluminum zircaloy liquid after 10 minutes；
Step F, aluminium zirconium hardener of casting；
By wrought aluminum zircaloy liquid obtained in step F under 1000 degree, the aluminium zirconium hardener of 1 ton of casting needs 61 points
Clock, casting are obtained aluminium zirconium hardener.
Aluminium zirconium hardener obtained in embodiment 3 is designated as into Al-Zr15, its composition is：
| Element | Al | Zr | Fe | Si | Individual element in impurity | Impurity summation |
| Mass fraction content (%) | Surplus | 15.02 | 0.22 | 0.65 | <0.05 | 0.15 |
Note：In impurity individual element be V, Ti, Mn, Cr.
According to embodiment 3 prepared method obtained in Al-Zr15 intermediate alloys, casting early stage, mid-term, the later stage sampling
Analyze, the mass percent of wherein zr element is：Casting early stage zirconium 14.85%, sampling mid-term zirconium 15.01%, samples later stage zirconium
15.23%.Substantial amounts of block nascent ZrAl is distributed in alloy3Phase, average-size are less than 80 microns, are uniformly distributed, to alloy
Observed under fracture Stereo microscope, fractograph is fine and close, without obvious slag inclusion, segregation thickness degree is less than The ingot casting thickness
10%.
The present invention is a kind of method of utilization Electric Cooker for high-end aluminium zirconium hardener, and to be solved is how to reduce zirconium
Segregation and the second phase (Al3Zr) size and be uniformly distributed, and intermediate alloy degree of purity technical problem, the method is by high temperature
Zirconium material is added in aluminium liquid, by alloying process control, refinery by de-gassing, the technological means cast, it is achieved thereby that zirconium is relatively low
Segregation, and the second phase (Al3Zr) the technique effect of uniform, Dispersed precipitate and low impurity content.
Claims (7)
1. a kind of industrialization preparation method of high-end aluminium zirconium hardener, it is characterised in that include the following steps：
Step A, prepares aluminum feedstock；
Mass percentage content according to zr element in required obtained target Al-Zr intermediate alloy is 3%～20%, impurity
Mass percentage content is less than 0.3%, and the composition of balance of aluminum is choosing aluminum material；Described aluminum material can be that mass percent is pure
Spend technical pure aluminium ingot or the aluminium block for 99.7%；
Step B, prepares zirconium raw material；
Zirconium material is chosen according to required obtained target Al-Zr intermediate alloy composition；Described zirconium material can be potassium fluorozirconate, sea
Continuous zirconium, zircaloy leftover bits, the one or more combination of zirconium bits；
Step C, melting aluminium liquid；
Added in electric furnace by the aluminum material that step A is prepared by A charge doors；And with heating rate as 1～10 degree/min, be warming up to
700～900 degree, aluminium liquid is fused in electric furnace；
Step D, refinery by de-gassing aluminium liquid；
Under the conditions of reaching 700～900 degree, pressure is passed through in electric furnace for 0.1～0.5 by the middle through-hole of hollow agitator
MPa argon or nitrogen；Low whipping speed is, under 100～400 revs/min, after stirring 10～30 minutes, to remove top slag
Thing, is obtained refined aluminium liquid；
Step E, melting aluminum zircaloy liquid；
Step E-1, the zirconium material prepared step B by A charge doors are added to step D in batches and under conditions of being spaced stirring and are obtained
Refined aluminium liquid in；
First, at 700～1300 degree, the zirconium material of a decile is added to obtained in step D and is refined in aluminium liquid, low whipping speed
For, under 50～300 revs/min, stirring stopped after 3～10 minutes；
Then, after being spaced 1～15 minute, the zirconium material of another decile is added, low whipping speed is, under 50～300 revs/min, to stir
Stop after mixing 3～10 minutes；
Then, after being spaced 1～15 minute, the zirconium material of last decile is added, low whipping speed is, under 50～300 revs/min, to stir
Stop after mixing 3～10 minutes, be cooled to 300～500 degree；
Step E-2, under the conditions of reaching 700～1300 degree, is passed through pressure by the middle through-hole of hollow agitator in electric furnace
Argon or nitrogen for 0.1～0.5 MPa；In speed be under 100～400 revs/min carry out 1 time or repeatedly degasification 10～
After 60 minutes, top slag thing is removed；
Step E-3, keeps extraction temperature to be 700～1300 degree, and refine was obtained aluminum zircaloy liquid after 10～30 minutes；
Step F, aluminium zirconium hardener of casting；
By wrought aluminum zircaloy liquid obtained in step E under 700～1300 degree, casting is obtained Al-Zr intermediate alloys；During casting
Mold temperature control is less than 500 degree.
2. a kind of industrialization preparation method of high-end aluminium zirconium hardener, it is characterised in that include the following steps：
Step A, prepares aluminum feedstock；
Mass percentage content according to zr element in required obtained target Al-Zr intermediate alloy is 3%～20%, impurity
Mass percentage content is less than 0.3%, and the composition of balance of aluminum is choosing aluminum material；Described aluminum material can be that mass percent is pure
Spend technical pure aluminium ingot or the aluminium block for 99.7%；
Step B, prepares zirconium raw material；
Zirconium material is chosen according to required obtained target Al-Zr intermediate alloy composition；Described zirconium material can be potassium fluorozirconate, sea
Continuous zirconium, zircaloy leftover bits, the one or more combination of zirconium bits；
Step C, melting aluminium liquid；
Added in electric furnace by the aluminum material that step A is prepared by A charge doors；And with heating rate as 1～10 degree/min, be warming up to
700～900 degree, aluminium liquid is fused in electric furnace；
Step D, refinery by de-gassing aluminium liquid；
Under the conditions of reaching 700～900 degree, pressure is passed through in electric furnace for 0.1～0.5 by the middle through-hole of hollow agitator
MPa argon or nitrogen；Low whipping speed is, under 100～400 revs/min, after stirring 10～30 minutes, to remove top slag
Thing, is obtained refined aluminium liquid；
Step E, melting aluminum zircaloy liquid；
Step E-1, adds refining agent, and good seal B charge doors in the getter that dusts by B charge doors；Then pass through air inlet
Passage sends into nitrogen or argon in the getter that dusts, and gas pressure is 0.2～0.8 MPa；Under air pressure conditions, refining agent Jing
Tapping channel is in the aluminum zircaloy liquid that temperature is 700～1300 degree；
The refining agent is the one or more combination in cryolite, calcium fluoride, Sodium Chloride, potassium chloride or prodan；
Step E-2, the zirconium material prepared step B by A charge doors are added to step D in batches and under conditions of being spaced stirring and are obtained
Refined aluminium liquid in；
First, at 700～1300 degree, the zirconium material of a decile is added to obtained in step D and is refined in aluminium liquid, low whipping speed
For, under 50～300 revs/min, stirring stopped after 3～10 minutes；
Then, after being spaced 1～15 minute, the zirconium material of another decile is added, low whipping speed is, under 50～300 revs/min, to stir
Stop after mixing 3～10 minutes；
Then, after being spaced 1～15 minute, the zirconium material of last decile is added, low whipping speed is, under 50～300 revs/min, to stir
Stop after mixing 3～10 minutes, be cooled to 300～500 degree；
Step E-3, under the conditions of reaching 700～1300 degree, is passed through pressure by the middle through-hole of hollow agitator in electric furnace
Argon or nitrogen for 0.1～0.5 MPa；In speed be under 100～400 revs/min carry out 1 time or repeatedly degasification 10～
After 60 minutes, top slag thing is removed；
Step E-4, keeps extraction temperature to be 700～1300 degree, and refine was obtained aluminum zircaloy liquid after 10～30 minutes；
Step F, casting are obtained aluminium zirconium hardener；
By wrought aluminum zircaloy liquid obtained in step E under 700～1300 degree, casting is obtained Al-Zr intermediate alloys；During casting
Mold temperature control is less than 500 degree.
3. the industrialization preparation method of a kind of high-end aluminium zirconium hardener according to claim 1 and 2, it is characterised in that：
The Al-Zr intermediate alloys of 1 ton of casting cannot be greater than 120 minutes.
4. the industrialization preparation method of a kind of high-end aluminium zirconium hardener according to claim 1 and 2, it is characterised in that：
In obtained aluminium zirconium hardener, the mass percent of Zr is the quality hundred that the mass percent of 3～20, Fe is 0.1～0.3, Si
Divide than being less than 0.15 and the Al of surplus for 0.05～0.3, mass percent of impurity.
5. the industrialization preparation method of a kind of high-end aluminium zirconium hardener according to claim 1 and 2, it is characterised in that：
The nascent ZrAl of bulk in aluminium zirconium hardener3Phase, at 20～80 microns, be evenly distributed average-size disperse.
6. the industrialization preparation method of a kind of high-end aluminium zirconium hardener according to claim 1 and 2, it is characterised in that：
In step E melting aluminum zircaloy liquid, the stirring of agitator can also be the electromagnetic agitation of electric furnace.
7. the industrialization preparation method of a kind of high-end aluminium zirconium hardener according to claim 1 and 2, it is characterised in that：
The aluminium zirconium hardener of step F casting, in ingot casting of different shapes or blank.
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| CN109536723B (en) * | 2018-12-27 | 2020-11-06 | 西南铝业（集团）有限责任公司 | Method for recovering aluminum lithium alloy processing scraps |
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| CN114438357A (en) * | 2022-02-11 | 2022-05-06 | 中原工学院 | Method for eliminating segregation of elements titanium and zirconium by casting aluminum alloy welding wire ingot |
| CN115109957A (en) * | 2022-06-22 | 2022-09-27 | 江苏鼎胜新能源材料股份有限公司 | Refining method for reducing impurity content of aluminum water |
| CN116024463A (en) * | 2023-03-02 | 2023-04-28 | 海安宏宇合金材料有限公司 | High-hardness low-friction-coefficient aluminum alloy material and preparation method thereof |
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