CN110129596A - Thin ribbon shaped nanometer Al3The preparation method of (Sc, Zr)/Al composite inoculant - Google Patents
Thin ribbon shaped nanometer Al3The preparation method of (Sc, Zr)/Al composite inoculant Download PDFInfo
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- CN110129596A CN110129596A CN201910433317.7A CN201910433317A CN110129596A CN 110129596 A CN110129596 A CN 110129596A CN 201910433317 A CN201910433317 A CN 201910433317A CN 110129596 A CN110129596 A CN 110129596A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
Abstract
Thin ribbon shaped nanometer Al of the present invention3The preparation method of (Sc, Zr)/Al composite inoculant, is related to acieral, and with Sc4%, Zr4%, remaining is that Al is raw material；In-situ authigenic method prepares bulk Al-4Sc-4Zr intermediate alloy；Intermediate alloy, which forges, is made fast melt-quenching prefabricated component；Thin ribbon shaped nanometer Al is made in fast melt-quenching processing3(Sc, Zr)/Al composite inoculant, this method are that Sc element and Zr element are prepared into nano combined inovulant for the first time to be used for refining aluminum alloy, overcome that process flow existing in the prior art is more, Al in complicated for operation, at high cost, alloy3Sc particle aggregate and precipitate in the melt, Al3Sc particle size is excessive, forming core particle cannot on matrix Dispersed precipitate, the defect that forming core type is single and number of nuclei is less.
Description
Technical field
Technical solution of the present invention is related to acieral, specifically thin ribbon shaped nanometer Al3(Sc, Zr)/Al is compound pregnant
Educate the preparation method of agent.
Background technique
Aluminium and aluminium alloy are due to many excellent performances such as lightweight, good corrosion resistance and high-termal conductivity etc.,
It is widely used in Aeronautics and Astronautics, automobile, consumer electronics and other high-tech sectors.However, in these industries product it is micro-
The increasingly increase of type and lightweight growth requirement, this disadvantage of intensity of aluminum alloy deficiency cause people more and more to pay close attention to.
Inoculation is the crystal grain refinement and material reinforcement method of a kind of classics, and other crystal fining methods, such as Deformation recrystallization phase
Than inoculation does not need complicated rolling equipment or accurate heat treatment process, only by addition about quality of materials
The inovulant of 1wt.% can achieve the purpose that material refining grain size.The effective inoculation of material, which relies primarily on, to be made
With inovulant appropriate, therefore, the design and its Refining Mechanism of inovulant are always the primary study of domestic and international scientific worker
One of direction.
From crystallography angle analysis, lattice misfit (δ) shadow of the forming core efficiency of inovulant between by inovulant and forming core substrate
It rings.However, due to usually containing different alloying elements in aluminium alloy, this changes the lattice constant of α-Al, so different
Aluminium alloy is using same inovulant, such as when Al-5Ti-1B, δ value can be varied widely, so as to cause different crystal grain
Thinning effect is even resulted in the certain alloys of inoculation, such as fail when processing A356.2 alloy.Therefore, it designs and researches and develops
A kind of for all effective inovulant of inoculation of a variety of aluminium alloys containing different components is a huge challenge.
Sc not only has obviously grain refining effect, but also the Enhancing Nucleation Density in Material Coagulating Process can be improved,
Therefore, it is often used as the microalloying addition element of different-alloy.CN105525162A discloses a kind of addition Zr and rare earth Sc
The preparation process of element raising Al-5.2Mg-0.3Mn alloy；CN109022983A discloses a kind of high-strength and high ductility magnesium conjunction containing Sc
Gold and preparation method thereof；CN104674079A discloses a kind of almag and preparation method thereof compound containing Sc and Zr；
CN104911409A discloses a kind of boron carbide particles reinforced aluminum matrix composites and preparation method thereof of zirconium containing scandium, aforementioned four
It uses the mode of microalloying and multi-step heat treatment to add in variety classes alloy Sc element in the prior art to reach with this
All there is more process flow, complicated for operation, higher cost, Al in alloy in the purpose for refining crystal grain improving performance3Sc particle exists
Aggregate and precipitate, Al in melt3Sc particle size is excessive, forming core particle cannot on matrix Dispersed precipitate, forming core type it is single
The less defect with number of nuclei.
Summary of the invention
The technical problems to be solved by the present invention are: providing thin ribbon shaped nanometer Al3The system of (Sc, Zr)/Al composite inoculant
Preparation Method is handled and thin ribbon shaped nanometer Al is made using in-situ authigenic method, intermediate alloy forging and fast melt-quenching3(Sc, Zr)/Al is multiple
Inovulant is closed, this method is that Sc element and Zr element are prepared into nano combined inovulant for the first time to be used for refining aluminum alloy, is overcome
Process flow existing in the prior art is more, Al in complicated for operation, higher cost, alloy3Sc particle in the melt poly-
Collection precipitating, Al3Sc particle size is excessive, forming core particle cannot Dispersed precipitate, forming core type be single and number of nuclei on matrix
Less defect.
The present invention solves technical solution used by the technical problem: thin ribbon shaped nanometer Al3(Sc, Zr)/Al is compound pregnant
Thin ribbon shaped nanometer Al is made using in-situ authigenic method, alloy forging and fast melt-quenching technology in the preparation method for educating agent3(Sc,Zr)/
Al composite inoculant, the specific steps are as follows:
The first step, the preparation of raw material:
Weigh desired amount of commercially available high-purity Sc and commercially available high-purity Zr, the quality hundred according to each component element in subject alloy
Divide ratio are as follows: Sc4%, Zr4%, remaining is Al, carries out raw material preparation；
Second step, in-situ authigenic method prepare bulk Al-4Sc-4Zr intermediate alloy:
The weighed whole preparation raw materials of the above-mentioned first step are put into the crucible of high vacuum induction melting furnace and carry out melting, very
Reciprocal of duty cycle is 5 × 10-4Pa, fusion temperature 2000K, smelting time are 10 minutes, and thus alloy melting, in-situ authigenic legal system obtain blocky
Al-4Sc-4Zr intermediate alloy；
Third step, intermediate alloy, which forges, is made fast melt-quenching prefabricated component:
Bulk Al-4Sc-4Zr intermediate alloy obtained by above-mentioned second step is encased in crucible type resistance furnace in room temperature, temperature
It is 300 DEG C, uniformly preheats the blocky Al-4Sc-4Zr intermediate alloy material being packed into, then gone out alloy feed collet with crucible tongs,
It is forged, is forged into a thickness of 7mm, a length of 50mm, the prefabricated component that width is 50mm, the operation of the hydraulic press on 100T hydraulic press
Condition is: it being first warming up to 300 ± 10 DEG C by power, then is warming up to set temperature with the heating rate of 50 DEG C/h, that is, is kept
First initial forging temperature is 380~400 DEG C, final forging temperature >=350 DEG C, and the forging of blocky Al-4Sc-4Z intermediate alloy is thus made molten
Body fast quenching prefabricated component；
Thin ribbon shaped nanometer Al is made in 4th step, fast melt-quenching processing3(Sc, Zr)/Al composite inoculant:
By above-mentioned third step intermediate alloy forge be made fast melt-quenching prefabricated component wire cutting machine cutting at thickness, width,
Length is 7mm × 7mm × 10mm small blocks, is air-dried, is put into quartz glass tube, outside quartz glass tube with after alcohol washes
Surface cover has load coil, attaches it in vacuum quick quenching furnace, vacuum in vacuum quick quenching furnace is evacuated to 5 using molecular pump ×
10-4During which Pa is passed through always argon gas protection, starts the copper roller of vacuum quick quenching furnace, reach 4000~8000r/min to its revolving speed,
Quartz glass tube is heated to 1200 DEG C by induction coil, keeps the temperature 6 minutes, and the fast melt-quenching being melted in quartz glass tube is prefabricated
Part is ejected on atwirl copper roller, and cooling rate is up to 105~108K/S, thus fast melt-quenching processing prepare width be 2~
5mm, thickness are the thin ribbon shaped nanometer Al of 0.05~0.1mm, a length of 10~40mm3(Sc, Zr)/Al composite inoculant, wherein being formed
Al3(Sc, Zr) particle clusters and forming core particle therein be it is nanocrystalline, particle size distribution best forming core size 200~
The section 500nm.
Above-mentioned thin ribbon shaped nanometer Al3The preparation method of (Sc, Zr)/Al composite inoculant, the high vacuum induction melting furnace
For MZG series high vacuum induction melting furnace.
Above-mentioned thin ribbon shaped nanometer Al3The preparation method of (Sc, Zr)/Al composite inoculant, the vacuum quick quenching furnace are WK-
IIB type vacuum quick quenching furnace.
Above-mentioned thin ribbon shaped nanometer Al3The preparation method of (Sc, Zr)/Al composite inoculant, related raw material and equipment are logical
It crosses known approach to obtain, operating procedure is that those skilled in the art will appreciate that.
Above-mentioned thin ribbon shaped nanometer Al3The application of (Sc, Zr)/Al composite inoculant is as follows:
By thin ribbon shaped nanometer Al3(Sc, Zr)/Al composite inoculant, which is added in different aluminum alloys, carries out inoculation, tool
Body operating method is: weighing raw material 100g fine aluminium, A356.2 alloy and Al-5Cu alloy, is placed in crucible, crucible is placed in electricity
720 DEG C are heated in resistance furnace, after whole melting sources become alloy, refining agent is added and just skims place to the alloy melt
Reason, weighs above-mentioned thin ribbon shaped nanometer Al3Thin ribbon shaped nanometer Al obtained by the preparation method of (Sc, Zr)/Al composite inoculant3
(Sc, Zr)/Al 0.6~0.8g of composite inoculant, and wrapped with aluminium foil, it is added to the above-mentioned alloy for just taking off Slag treatment
In melt, the incubation time is 30~45s, and alloy melt is cast to a height of 120mm after being stirred with graphite rod, and diameter is 20mm's
In punching block.
Cu atom in above-mentioned raw materials Al-5Cu alloy due to lattice constant less than Al is added, and leads to the lattice constant of alloy
Less than fine aluminium, and Si, Mg element are mainly contained in A356.2 alloy, the lattice constant of alloy is caused to be greater than fine aluminium.It will be of the invention
Thin ribbon shaped nanometer Al made from method3(Sc, Zr)/Al composite inoculant is added in different aluminum alloys after progress inoculation,
Nanometer Al3(Sc, Zr)/Al composite inoculant all shows good crystal grain refinement to the aluminium alloy of different lattice constants and imitates
Fruit.Wherein, the crystallite dimension of fine aluminium is refined by 820 μm of non-inoculation to 110 μm；The crystallite dimension of A356.2 alloy by
450 μm of non-inoculation are refined to 220 μm；The crystallite dimension of Al-5Cu alloy is refined by 185 μm of non-inoculation
To 65 μm.
Thin ribbon shaped nanometer Al made from the method for the present invention3(Sc, Zr)/Al composite inoculant is suitable for the pregnant of a variety of aluminium alloys
Educate processing.
The beneficial effects of the present invention are: compared with prior art, substantive distinguishing features outstanding of the invention are as follows:
(1) present invention utilizes in-situ authigenic methods to generate inovulant.So-called in-situ authigenic refers to the non-outside of reinforcement particle
It is added, but by chemical reaction, the in-situ preparation one or more reinforced phase in the matrix of inovulant.These reinforced phases due to
Itself be created on the matrix of aluminium, and have good Lattice Matching relationship between aluminum substrate, thus will as made from the method it is pregnant
When educating in agent addition aluminium alloy, as the substrate of aluminum substrate forming core, promote heterogeneous forming core, to reach refining aluminum alloy crystal grain
Effect.
(2) in theory, the thin ribbon shaped nanoscale Al that the method for the present invention is prepared3(Sc, Zr)/Al inovulant, strip
In contain the higher Al of volume fraction3(Sc, Zr) diphase particles cluster and crystalline orientation height is consistent, particle clusters quantity compared with
More and of uniform size, particle size distribution is in the section 200~500nm of best forming core size, therefore, it is easier to excite aluminium alloy
Forming core and forming core efficiency is higher.
Compared with prior art, marked improvement of the invention is as follows:
(1) thin ribbon shaped nanoscale Al of the invention3(Sc, Zr)/Al inovulant is to react to generate by in-situ authigenic, with
The prior art is compared, in-situ preparation technology for enhance particle size and distribution be it is controllable, due to reinforcement Al3(Sc,
Zr it) is directly generated on matrix, therefore, 1. Al3The surface of (Sc, Zr) particle is clean pollution-free and with matrix wetability compared with
Good, this allows for having preferable interfacial combined function between reinforcement and matrix；2. without interfacial reaction；3. enhancing particle ruler
Very little reachable nanoscale, there is good transgranular reinforcing effect.
(2) method that alloy forging is used in the method for the present invention, compensates for raw material in vacuum induction melting furnace induction melting
Enhancing particle agglomeration in gained alloy and this non-uniform deficiency of size afterwards, reach refinement and homogenize the mesh of intermediate alloy
's.
(3) the method for the present invention is made using the method for carrying out quickly solidification processing in vacuum quick quenching furnace in alloy forging processing
After fast melt-quenching prefabricated component, carry out quick solidification processing using vacuum quick quenching furnace, on melt jet to high-speed rotating copper wheel,
Reach the cooling velocity being exceedingly fast, thus obtained thin ribbon shaped nanometer Al using the high revolving speed of copper wheel3(Sc, Zr)/Al is compound inoculated
Agent, wherein generating Al3(Sc, Zr) particle clusters and forming core particle therein be it is nanocrystalline, thinning effect is by significant increase.
(4) the final thin ribbon shaped nanometer Al obtained of the method for the present invention3(Sc, Zr)/Al composite inoculant have nanoscale and
The forming core cluster of Dispersed precipitate in the base overcomes Al in Al-Sc alloy in the prior art3The aggregation of Sc particle in the melt
Precipitating, Al3Sc particle size is excessive, forming core particle cannot on matrix Dispersed precipitate, forming core type be single and number of nuclei compared with
Few defect.
(5) nanometer Al made from the method for the present invention3Aluminium alloy of (Sc, Zr)/Al composite inoculant to a variety of lattice parameters
There is good grain refining effect, suitable for the inoculation of a variety of aluminium alloys, overcomes " unicity " of inovulant application.
(6) with CN104674079A containing Zr and rare earth Sc compound ZL almag (Al-10Mg) and preparation method thereof phase
Than, the weight percentages of components of product disclosed in CN104674079A is Zr 2.5%, Sc 2.5%, Mg 10%, remaining
For Al, preparation method is microalloying method, using graphite crucible resistance furnace, is pressed into MAG block with bell jar after fine aluminium is melted, then
Al-5Sc and Al-10Zr intermediate alloy is added, the additive amount for depositing Sc in the product causes product cost high and preparation up to 2.5%
Do not add vacuum protection in method, and is only stirred by operator using graphite rod, it is difficult to ensure that alloying element is uniformly mixed, and
It is difficult to overcome Al in Al-Sc alloy3The excessive defect with negligible amounts of Sc particle size.In the present invention using using Sc and
Zr prepares inovulant, and inovulant is added in different-alloy, reaches raising alloy property with this.With microalloying method
It compares, the additional amount of the inovulant in the present invention in the alloy only has 0.6wt.%, that is to say, that amount containing Sc is in inovulant
4%, the amount for being added to inovulant in alloy is 0.6%, that is, the Sc content being added in alloy is only 0.024%, can be played
Good grain refining effect, greatly reduces cost.
(7) the preparation work of Al-5.2Mg-0.3Mn alloy is improved with a kind of addition Zr of CN105525162A and rare earth Sc element
Skill is compared, and this method is to be needed using semi-continuous casting metallurgy method by homogenizing annealing, hot rolling, cold rolling and stabilizing annealing
Processing, operating procedure is complex, higher for the required precision of device temperature, and the additional amount of Sc and Zr element compared with
It is more, respectively 0.25% and 0.12%.Compared with this method, the method and step of inoculation is simple in the present invention, easy to operate
And the additional amount of Sc and Zr element significantly reduces.
(8) compared with a kind of high-strength-toughness magnesium alloy containing Sc of CN109022983A and preparation method thereof, this method addition
A variety of alloying elements, mainly include Y:4.5~6.5wt%, Nd:1.5~4.0wt%, Gd:1.5~4.0wt%, Sc:0.05~
0.5wt%, Zr:0.15~1.5wt%, remaining is Mg, main operational steps are as follows: alloying element substep, which is added, to be cast, is cast
Part homogenization, preheating, extruding, ageing treatment etc..The prior art operating procedure is complex, and process flow is cumbersome, and Sc
More with the additional amount of Zr element, this is overcome and improves in the present invention.
(9) with a kind of boron carbide particles reinforced aluminum matrix composites of zirconium containing scandium of CN104911409A and preparation method thereof phase
Than, this method is to be added to Al-2Sc and Al-15Zr intermediate alloy in 800 DEG C of molten aluminums to keep the temperature 40 minutes, without vacuum protection,
The mode for relying only on long-time heat preservation is difficult to dissolve alloying element sufficiently, Al in caused Al-Sc alloy3Sc particle size mistake
Big and negligible amounts defects.Melting is carried out using induction furnace in the present invention, vacuum degree is 5 × 10-4Pa, fusion temperature 2000K,
Smelting time is 10 minutes, and thus alloy melting, in-situ authigenic legal system obtain blocky Al-4Sc-4Zr intermediate alloy, then centering again
Between alloy carry out conducting forging processing, the particle in intermediate alloy is refined and guarantees that particle is uniformly distributed, it is existing to overcome this
The defect of technology.
(10) the Ultra-fine Grained inovulant of aluminum grain refinement is used for the previous CN102787260B of the present inventor team
Preparation method compare, CN102787260B is to obtain intermediate alloy using electric arc melting first, is then quickly solidified again
It handles and strip intermediate alloy is made.The method of the present invention is that the method for the present invention is using sense with this method essential distinction outstanding
The mode that should be heated, fusion temperature 2000K, smelting time are 10 minutes, and long-time heat preservation is to guarantee alloying element in melt
It is biggish to overcome intermediate alloy ingredient unevenness, particle size for the step of ingredient reacts, and joined alloy forging again after this
Defect.
(11) with a kind of preparation of in-situ aluminium base composite material inoculant of the previous CN102864343B of the present inventor team
Method is compared, CN102864343B be using vacuum arc furnace melting then further plasma nitridation process first using
Plasma gun is put in graphite crucible, by the plasma torch and alloy contact of ejection, plasma torch and alloy melting
It after reaction, can not be cast in mold, crucible can only be smashed with after crucible cooling, alloy is taken out, therefore, production efficiency
It is lower and not environmentally.The method of the present invention is method and apparatus used in the present invention with this method essential distinction outstanding,
Production efficiency improves and without destructive testing, overcomes the defect in the presence of CN102864343B technology completely.
(12) with a kind of aluminum matrix composite inovulant of in-situ authigenic of the previous CN105950921B of the present inventor team
Preparation method compare, CN105950921B is that intermediate alloy first is made using vacuum induction melting, then is carried out at quick solidification
Reason, the method for the present invention are that the present invention joined alloy again after vacuum induction melting with this method essential distinction outstanding
The step of forging, overcomes intermediate alloy ingredient unevenness, the biggish defect of particle size, overcomes CN105950921B skill completely
Defect in the presence of art.
In view of tri- patents of CN102787260B, CN102864343B and CN105950921B that the present inventor team is previous
The research and development with great concentration more than 3 years are passed through again by deficiency present in technology and defect, the present inventor team, just complete the present invention of innovation
Technology overcomes deficiency and defect present in above-mentioned previous patented technology, even if those skilled in the art are in above-mentioned patent skill
Technical solution of the present invention is obtained on the basis of art in conjunction with ordinary skill in the art means, for a person skilled in the art
It is easy absolutely not.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is thin ribbon shaped nanometer Al made from the method for the present invention3The x-ray diffraction pattern of (Sc, Zr)/Al composite inoculant.
Fig. 2 is thin ribbon shaped nanometer Al made from the method for the present invention3The scanning electron microscopy of (Sc, Zr)/Al composite inoculant
Mirror image, in which:
Fig. 2 (a) is thin ribbon shaped nanometer Al under low power3The scanning electron microscope image of (Sc, Zr)/Al composite inoculant；
Fig. 2 (b) is thin ribbon shaped nanometer Al under high power3The scanning electron microscope image of (Sc, Zr)/Al composite inoculant,
Wherein inset portion is the enlarged drawing in shown region.
Fig. 3 is to add 0.6wt.% nanometer Al of the invention3The gold of (Sc, Zr)/Al composite inoculant inoculation fine aluminium
Phase constitution photo, in which:
Fig. 3 (a) is the metallographic structure photo of as cast condition fine aluminium when being not added with inovulant；
Fig. 3 (b) is 0.6wt.% nanometers of Al of addition3The metallographic structure of as cast condition fine aluminium is shone when (Sc, Zr)/Al composite inoculant
Piece.
Fig. 4 is to add 0.8wt.% nanometer Al of the invention3(Sc, Zr)/Al composite inoculant handles A356.2 alloy
Metallographic structure photo, in which:
Fig. 4 (a) is the metallographic structure photo of as cast condition A356.2 alloy when being not added with inovulant；
Fig. 4 (b) is 0.8wt.% nanometers of Al of addition3The metallographic of as cast condition A356.2 alloy when (Sc, Zr)/Al composite inoculant
Macrograph.
Fig. 5 is to add 0.7wt.% nanometer Al of the invention3(Sc, Zr)/Al composite inoculant handles Al-5Cu alloy
Metallographic structure photo, in which:
Fig. 5 (a) is the metallographic structure photo of as cast condition Al-5Cu alloy when being not added with inovulant；
Fig. 5 (b) is 0.7wt.% nanometers of Al of addition3The metallographic of as cast condition Al-5Cu alloy when (Sc, Zr)/Al composite inoculant
Macrograph.
Specific embodiment
Embodiment 1
The first step, the preparation of raw material:
Weigh desired amount of commercially available high-purity Sc and commercially available high-purity Zr, the quality hundred according to each component element in subject alloy
Divide ratio are as follows: Sc4%, Zr4%, remaining is Al, carries out raw material preparation；
Second step, in-situ authigenic method prepare bulk Al-4Sc-4Zr intermediate alloy:
The weighed whole preparation raw materials of the above-mentioned first step are put into the crucible of MZG series high vacuum induction melting furnace and are carried out
Melting, vacuum degree are 5 × 10-4Pa, fusion temperature 2000K, smelting time are 10 minutes, thus alloy melting, in-situ authigenic method
Bulk Al-4Sc-4Zr intermediate alloy is made；
Third step, intermediate alloy, which forges, is made fast melt-quenching prefabricated component:
Bulk Al-4Sc-4Zr intermediate alloy obtained by above-mentioned second step is encased in crucible type resistance furnace in room temperature, temperature
It is 300 DEG C, uniformly preheats the blocky Al-4Sc-4Zr intermediate alloy material being packed into, then gone out alloy feed collet with crucible tongs,
It is forged, is forged into a thickness of 7mm, a length of 50mm, the prefabricated component that width is 50mm, the operation of the hydraulic press on 100T hydraulic press
Condition is: it being first warming up to 300 ± 10 DEG C by power, then is warming up to set temperature with the heating rate of 50 DEG C/h, that is, is kept
First initial forging temperature is 380, final forging temperature >=350 DEG C, and it is pre- that blocky Al-4Sc-4Z intermediate alloy is thus forged obtained fast melt-quenching
Product；
Thin ribbon shaped nanometer Al is made in 4th step, fast melt-quenching processing3(Sc, Zr)/Al composite inoculant:
By above-mentioned third step intermediate alloy forge be made fast melt-quenching prefabricated component wire cutting machine cutting at thickness, width,
Length is 7mm × 7mm × 10mm small blocks, is air-dried, is put into quartz glass tube, outside quartz glass tube with after alcohol washes
Surface cover has load coil, attaches it in WK-IIB type vacuum quick quenching furnace, using molecular pump that WK-IIB type vacuum is fast
Vacuum in furnace of quenching is evacuated to 5 × 10-4During which Pa is passed through always argon gas protection, starts the copper roller of vacuum quick quenching furnace, reach to its revolving speed
Quartz glass tube is heated to 1200 DEG C by 4000r/min, induction coil, keeps the temperature 6 minutes, molten in quartz glass tube by being melted in
Body fast quenching prefabricated component is ejected on atwirl copper roller, and cooling rate is up to 105K/S, thus fast melt-quenching processing are prepared
Width is 5mm, the thin ribbon shaped nanometer Al of thickness 0.1mm, a length of 40mm3(Sc, Zr)/Al composite inoculant, wherein forming Al3(Sc,
Zr) particle clusters and forming core particle therein are nanocrystalline, and particle size distribution is in the section 200~500nm of best forming core size.
The thin ribbon shaped nanometer Al that will be thus prepared into3(Sc, Zr)/Al composite inoculant is ground with 2000#SiC sand paper
System, is washed away specimen surface impurity by ultrasonic vibration with alcohol, is penetrated using the multi-functional X- of German Bruker D8 Discover type
Line instrument (XRD) CuKαRay identifies contained phase in the inovulant, if Fig. 1 is shown, the thin ribbon shaped nanometer Al of the present embodiment3(Sc,
Zr)/Al composite inoculant is by α (Al) phase, Al3Sc phase and Al3Zr phase composition, Al3Sc phase and Al3The successful synthesis of Zr phase is anticipated
Taste in induction melting furnace synthetic method in situ be it is desirable because X-ray diffraction is statistical law, work as member under normal conditions
Cellulose content is difficult to detect when being lower than 5%.The additional amount of Sc and Zr element is 4% in the present embodiment, as can be seen from Figure 1,
Al3Sc and Al3The characteristic peak of Zr phase is clearly, it is meant that the Al of fabricated in situ3Sc and Al3Zr phase amount is more.Using the U.S.
FEI Nova Nano SEM450 field emission microscope observes the thin ribbon shaped Al of the present embodiment3(Sc, Zr)/Al is compound inoculated
The microscopic appearance of agent, as shown in the scanning electron microscope image of Fig. 2, wherein furvous is aluminum substrate, Fig. 2 (a) display, at this
The thin ribbon shaped nanometer Al of embodiment3In (Sc, Zr)/Al composite inoculant, grizzled particle in the base Dispersed precipitate and quantity compared with
It is more, it is notable that have no apparent particle agglomeration phenomenon in strip inovulant prepared by the present embodiment and occur, this is greatly
The deficiency for improving prior art preparation method；Meanwhile showing that the quantity of particle is more in the figure, this is also strip inovulant
There is the key of good dies thinning effect to aluminium alloy, it is insufficient also to compensate for forming core amounts of particles in existing micro-alloying technology
Defect；50 times of the amplification figures that Fig. 2 (b) is Fig. 2 (a), wherein showing, the size of particle clusters is for the section 200~500nm and by more
A nano-crystalline granule composition, shows thin ribbon shaped nanometer Al of the invention3α (Al) phase in (Sc, Zr)/Al composite inoculant,
Al3Sc phase and Al3Zr phase not separately exists in matrix, but forms the Al having a size of the section 200~500nm3(Sc,
Zr) particle clusters, cluster are made of multiple nanoscale particles, these nano particle clusters are also thin ribbon shaped nanometer of the invention
Al3(Sc, Zr)/Al composite inoculant has the reason of good dies thinning effect.
Embodiment 2
The first step, the preparation of raw material:
With embodiment 1；
Second step, in-situ authigenic method prepare bulk Al-4Sc-4Zr intermediate alloy:
With embodiment 1；
Third step, intermediate alloy, which forges, is made fast melt-quenching prefabricated component:
With embodiment 1；
Thin ribbon shaped nanometer Al is made in 4th step, fast melt-quenching processing3(Sc, Zr)/Al composite inoculant:
By above-mentioned third step intermediate alloy forge be made fast melt-quenching prefabricated component wire cutting machine cutting at thickness, width,
Length is 7mm × 7mm × 10mm small blocks, is air-dried, is put into quartz glass tube, outside quartz glass tube with after alcohol washes
Surface cover has load coil, attaches it in WK-IIB type vacuum quick quenching furnace, using molecular pump that WK-IIB type vacuum is fast
Vacuum in furnace of quenching is evacuated to 5 × 10-4During which Pa is passed through always argon gas protection, starts the copper roller of vacuum quick quenching furnace, reach to its revolving speed
Quartz glass tube is heated to 1200 DEG C by 6000r/min, induction coil, keeps the temperature 6 minutes, molten in quartz glass tube by being melted in
Body fast quenching prefabricated component is ejected on atwirl copper roller, and cooling rate is up to 106K/S, preparing width is 3.5mm, and thickness is
The thin ribbon shaped Al of 0.06mm, a length of 20mm3(Sc, Zr)/Al composite inoculant, wherein forming Al3(Sc, Zr) particle clusters and its
In forming core particle be it is nanocrystalline, particle size distribution is in the section 200~500nm of best forming core size.
Embodiment 3
The first step, the preparation of raw material:
With embodiment 1；
Second step, in-situ authigenic method prepare bulk Al-4Sc-4Zr intermediate alloy:
With embodiment 1；
Third step, intermediate alloy, which forges, is made fast melt-quenching prefabricated component:
With embodiment 1；
Thin ribbon shaped nanometer Al is made in 4th step, fast melt-quenching processing3(Sc, Zr)/Al composite inoculant:
By above-mentioned third step intermediate alloy forge be made fast melt-quenching prefabricated component wire cutting machine cutting at thickness, width,
Length is 7mm × 7mm × 10mm small blocks, is air-dried, is put into quartz glass tube, outside quartz glass tube with after alcohol washes
Surface cover has load coil, attaches it in WK-IIB type vacuum quick quenching furnace, using molecular pump that WK-IIB type vacuum is fast
Vacuum in furnace of quenching is evacuated to 5 × 10-4During which Pa is passed through always argon gas protection, starts the copper roller of vacuum quick quenching furnace, reach to its revolving speed
Quartz glass tube is heated to 1200 DEG C by 8000r/min, induction coil, keeps the temperature 6 minutes, molten in quartz glass tube by being melted in
Body fast quenching prefabricated component is ejected on atwirl copper roller, and cooling rate is up to 108K/S, preparing width is 2.5mm, and thickness is
The thin ribbon shaped Al of 0.03mm, a length of 15mm3(Sc, Zr)/Al composite inoculant, wherein forming Al3(Sc, Zr) particle clusters and its
In forming core particle be it is nanocrystalline, particle size distribution is in the section 200~500nm of best forming core size.
Embodiment 4
By thin ribbon shaped nanometer Al obtained by above-described embodiment 13(Sc, Zr)/Al composite inoculant be added in fine aluminium into
Row inoculation:
It weighs 100g fine aluminium to be placed in crucible, crucible is placed in resistance furnace and is heated to 720 DEG C, refining is added after to be melted
Agent just takes off Slag treatment to melt；Weigh 0.6g thin ribbon shaped nanometer Al3(Sc, Zr)/Al composite inoculant is simultaneously wrapped with aluminium foil
It wraps, is added in the alloy of fusing, melt is cast to a height of 120mm after being stirred with graphite rod, directly by incubation time 30s
Diameter is in the punching block of 20mm；Fine aluminium after inoculation is cut with electro-spark cutting machine, cuts out a length of 10mm, width is
10mm, the sample of thickness 10mm, by the sample after cutting respectively in 200#, 400#, 600#, 800#, 1200# and 2000# water mill
It is ground on sand paper, then carries out mechanical polishing processing, specimen surface impurity is washed away by ultrasonic vibration with alcohol, uses moral
State's Zeiss Axio Imager M2M type microscope carries out metallographic structure observation.Metallographic structure such as Fig. 3 of fine aluminium before and after inoculation
Shown in: Fig. 3 (a) is shown as the metallograph of the as cast condition fine aluminium of non-inoculation, and the coarse crystallite dimension of the fine aluminium is 820 μ
M, this will result directly in its lower intensity, it is difficult to meet production needs；Fig. 3 (b) is shown as the thin ribbon shaped of addition 0.6wt.%
Nanometer Al3After (Sc, Zr)/Al composite inoculant, the crystal grain of fine aluminium is refined into uniformly tiny equiax crystal, and size is obviously reduced
Be 110 μm, only non-inoculation when 1/8.
Embodiment 5
By thin ribbon shaped nanometer Al obtained by above-described embodiment 23(Sc, Zr)/Al composite inoculant is added to A356.2 conjunction
Inoculation is carried out in gold:
It weighs 100gA356.2 alloy to be placed in crucible, crucible is placed in resistance furnace and is heated to 720 DEG C, is added after to be melted
Enter refining agent and Slag treatment is just taken off to melt；Weigh 0.8g thin ribbon shaped nanometer Al3(Sc, Zr)/Al composite inoculant simultaneously uses aluminium foil
It is wrapped, is added in the alloy of fusing, melt is cast to a height of by incubation time 45s after being stirred with graphite rod
120mm, diameter are in the punching block of 20mm；Fine aluminium after inoculation is cut with electro-spark cutting machine, is cut out a length of
10mm, width 10mm, the sample of thickness 10mm, by the sample after cutting respectively in 200#, 400#, 600#, 800#, 1200# and
It is ground on 2000# silicon carbide paper, then carries out mechanical polishing processing, it is miscellaneous by ultrasonic vibration to wash away specimen surface with alcohol
Matter carries out metallographic structure observation using Zeiss, Germany Axio Imager M2M type microscope.A356.2 alloy before and after inoculation
Metallographic structure it is as shown in Figure 4: Fig. 4 (a) is shown as the metallograph of as cast condition A356.2 alloy when non-inoculation.It is seen in figure
Apparent dendrite is distributed on matrix out, crystallite dimension is 450 μm, is found out simultaneously, there are obviously grow needle-shaped silicon in matrix
Phase, needle-shaped silicon are mutually easy to isolate matrix, this is totally unfavorable to the promotion of alloy mechanical property；Fig. 4 (b) is shown as adding
The thin ribbon shaped nanometer Al of 0.8wt.%3The metallographic structure photo of as cast condition A356.2 alloy when (Sc, Zr)/Al composite inoculant.It should
The needle-shaped silicon mutually obvious nodularization that the crystallite dimension of alloy is obviously reduced to be distributed in 220 μm and matrix, mentions alloy property
It rises greatly beneficial.
Embodiment 6
By thin ribbon shaped nanometer Al obtained by above-described embodiment 33(Sc, Zr)/Al composite inoculant is added to Al-5Cu conjunction
Inoculation is carried out in gold:
It weighs 100gAl-5Cu alloy to be placed in crucible, crucible is placed in resistance furnace and is heated to 720 DEG C, is added after to be melted
Enter refining agent and Slag treatment is just taken off to melt；Weigh 0.7g thin ribbon shaped nanometer Al3(Sc, Zr)/Al composite inoculant simultaneously uses aluminium foil
It is wrapped, is added in the alloy of fusing, melt is cast to a height of by incubation time 40s after being stirred with graphite rod
120mm, diameter are in the punching block of 20mm；Fine aluminium after inoculation is cut with electro-spark cutting machine, is cut out a length of
10mm, width 10mm, the sample of thickness 10mm, by the sample after cutting respectively in 200#, 400#, 600#, 800#, 1200# and
It is ground on 2000# silicon carbide paper, then carries out mechanical polishing processing, it is miscellaneous by ultrasonic vibration to wash away specimen surface with alcohol
Matter carries out metallographic structure observation using Zeiss, Germany Axio Imager M2M type microscope.Al-5Cu alloy before and after inoculation
Metallographic structure it is as shown in Figure 5: the metallographic structure photo of as cast condition Al-5Cu alloy when Fig. 5 (a) is shown as being not added with inovulant is seen
The crystal grain of the alloy is the mixing of equiax crystal and column crystal out, having a size of 185 μm；Fig. 5 (b) is shown as 0.7wt.% nanometers of addition
Al3The metallographic structure photo of as cast condition Al-5Cu alloy when (Sc, Zr)/Al composite inoculant, the crystal grain in the alloy all become
For equiax crystal, uniform small grains, having a size of 65 μm.
Raw material and equipment involved in above-described embodiment are obtained by known approach, and operating procedure is the art
What technical staff will appreciate that.
Claims (1)
1. thin ribbon shaped nanometer Al3The preparation method of (Sc, Zr)/Al composite inoculant, it is characterised in that: using in-situ authigenic method, close
Bodkin, which is made, is made thin ribbon shaped nanometer Al with fast melt-quenching technology3(Sc, Zr)/Al composite inoculant, the specific steps are as follows:
The first step, the preparation of raw material:
Weigh desired amount of commercially available high-purity Sc and commercially available high-purity Zr, the mass percent according to each component element in subject alloy
Are as follows: Sc4%, Zr4%, remaining is Al, carries out raw material preparation；
Second step, in-situ authigenic method prepare bulk Al-4Sc-4Zr intermediate alloy:
The weighed whole preparation raw materials of the above-mentioned first step are put into the crucible of high vacuum induction melting furnace and carry out melting, vacuum degree
It is 5 × 10-4Pa, fusion temperature 2000K, smelting time are 10 minutes, and thus alloy melting, in-situ authigenic legal system obtain blocky Al-
4Sc-4Zr intermediate alloy；
Third step, intermediate alloy, which forges, is made fast melt-quenching prefabricated component:
Bulk Al-4Sc-4Zr intermediate alloy obtained by above-mentioned second step is encased in crucible type resistance furnace in room temperature, temperature is
300 DEG C, the blocky Al-4Sc-4Zr intermediate alloy material being packed into uniformly is preheated, is then gone out alloy feed collet with crucible tongs,
It is forged, is forged into a thickness of 7mm, a length of 50mm, the prefabricated component that width is 50mm, the operation of the hydraulic press on 100T hydraulic press
Condition is: it being first warming up to 300 ± 10 DEG C by power, then is warming up to set temperature with the heating rate of 50 DEG C/h, that is, is kept
First initial forging temperature is 380~400 DEG C, final forging temperature >=350 DEG C, and the forging of blocky Al-4Sc-4Z intermediate alloy is thus made molten
Body fast quenching prefabricated component；
Thin ribbon shaped nanometer Al is made in 4th step, fast melt-quenching processing3(Sc, Zr)/Al composite inoculant:
Above-mentioned third step intermediate alloy is forged, fast melt-quenching prefabricated component wire cutting machine cutting is made into thickness, width, length
For 7mm × 7mm × 10mm small blocks, is air-dried, be put into quartz glass tube with after alcohol washes, quartz glass tube outside set
There is load coil, attach it in vacuum quick quenching furnace, vacuum in vacuum quick quenching furnace is evacuated to 5 × 10 using molecular pump- 4During which Pa is passed through always argon gas protection, starts the copper roller of vacuum quick quenching furnace, reach 4000~8000r/min to its revolving speed, feels
It answers coil that quartz glass tube is heated to 1200 DEG C, keeps the temperature 6 minutes, the fast melt-quenching prefabricated component that will be melted in quartz glass tube
It is ejected on atwirl copper roller, cooling rate is up to 105~108K/S, thus fast melt-quenching processing prepare width be 2~
5mm, thickness are the thin ribbon shaped nanometer Al of 0.05~0.1mm, a length of 10~40mm3(Sc, Zr)/Al composite inoculant, wherein being formed
Al3(Sc, Zr) particle clusters and forming core particle therein be it is nanocrystalline, particle size distribution best forming core size 200~
The section 500nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004949A (en) * | 2019-11-29 | 2020-04-14 | 广东凤铝铝业有限公司 | Aluminum alloy casting method |
| CN112129325A (en) * | 2020-08-13 | 2020-12-25 | 苏州中科寰宇智能科技有限公司 | High-strength and high-thermal-stability glass code disc for rotary encoder |
| CN114350995A (en) * | 2022-01-13 | 2022-04-15 | 河北工业大学 | Preparation method of thin strip refining alterant for A356.2 alloy |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2455503A1 (en) * | 2011-03-15 | 2012-05-23 | Sun Xing Chemical & Metallurgical Materials (Shenzhen) Co. Ltd. | Grain refiner for magnesium and magnesium alloy and preparation method thereof |
| CN103060588A (en) * | 2013-02-04 | 2013-04-24 | 吉林大学 | Non-crystalline Zr-based alloy inoculant for casting aluminum alloy and preparation method of non-crystalline Zr-based alloy inoculant |
| WO2015138748A1 (en) * | 2014-03-12 | 2015-09-17 | NanoAL LLC | Aluminum superalloys for use in high temperature applications |
| CN105821260A (en) * | 2016-05-20 | 2016-08-03 | 湖南东方钪业股份有限公司 | Aluminum, scandium and zirconium intermediate alloy for aluminum alloy and production method thereof |
-
2019
- 2019-05-23 CN CN201910433317.7A patent/CN110129596B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2455503A1 (en) * | 2011-03-15 | 2012-05-23 | Sun Xing Chemical & Metallurgical Materials (Shenzhen) Co. Ltd. | Grain refiner for magnesium and magnesium alloy and preparation method thereof |
| CN103060588A (en) * | 2013-02-04 | 2013-04-24 | 吉林大学 | Non-crystalline Zr-based alloy inoculant for casting aluminum alloy and preparation method of non-crystalline Zr-based alloy inoculant |
| WO2015138748A1 (en) * | 2014-03-12 | 2015-09-17 | NanoAL LLC | Aluminum superalloys for use in high temperature applications |
| CN105821260A (en) * | 2016-05-20 | 2016-08-03 | 湖南东方钪业股份有限公司 | Aluminum, scandium and zirconium intermediate alloy for aluminum alloy and production method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 周瑞发: "《纳米材料技术》", 31 July 2003, 北京：国防工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004949A (en) * | 2019-11-29 | 2020-04-14 | 广东凤铝铝业有限公司 | Aluminum alloy casting method |
| CN111004949B (en) * | 2019-11-29 | 2021-02-02 | 佛山市三水凤铝铝业有限公司 | Aluminum alloy casting method |
| CN112129325A (en) * | 2020-08-13 | 2020-12-25 | 苏州中科寰宇智能科技有限公司 | High-strength and high-thermal-stability glass code disc for rotary encoder |
| CN114350995A (en) * | 2022-01-13 | 2022-04-15 | 河北工业大学 | Preparation method of thin strip refining alterant for A356.2 alloy |
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