CN110129596B - Thin strip-shaped nano Al3Preparation method of (Sc, Zr)/Al composite inoculant - Google Patents
Thin strip-shaped nano Al3Preparation method of (Sc, Zr)/Al composite inoculant Download PDFInfo
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- CN110129596B CN110129596B CN201910433317.7A CN201910433317A CN110129596B CN 110129596 B CN110129596 B CN 110129596B CN 201910433317 A CN201910433317 A CN 201910433317A CN 110129596 B CN110129596 B CN 110129596B
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
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Abstract
The invention relates to a thin strip-shaped nano Al3A preparation method of a (Sc, Zr)/Al composite inoculant relates to an aluminum-based alloy, and takes Sc 4%, Zr 4% and the balance of Al as raw materials; preparing a massive Al-4Sc-4Zr intermediate alloy by an in-situ autogenous method; forging the intermediate alloy to obtain a melt rapid quenching prefabricated part; melt rapid quenching treatment is carried out to prepare thin strip-shaped nano Al3The method prepares Sc element and Zr element into the nano composite inoculant for refining the aluminum alloy for the first time, and overcomes the defects of more process flows, complex operation, high cost and Al in the alloy in the prior art3Aggregation and precipitation of Sc particles in the melt, Al3The Sc particles have the defects of overlarge size, incapability of dispersing and distributing nucleation particles on a matrix, single nucleation type and less nucleation quantity.
Description
Technical Field
The technical scheme of the invention relates to an aluminum-based alloy, in particular to a thin strip-shaped nano Al3A preparation method of (Sc, Zr)/Al composite inoculant.
Background
Aluminum and aluminum alloys have been widely used in the fields of aviation, aerospace, automobiles, consumer electronics and other high-tech fields due to their excellent properties such as light weight, good corrosion resistance, high thermal conductivity, etc. However, as the demand for miniaturization and weight reduction of products in these industries is increasing, the disadvantage of insufficient strength of aluminum alloys is attracting more and more attention. Inoculation, which is a classical grain refinement and material strengthening method, does not require complex rolling equipment or precise heat treatment processes, as compared to other grain refinement methods, such as deformation recrystallization, and can be achieved by adding only about 1 wt.% of the material mass of the inoculant. The effective inoculation of the material mainly depends on the use of proper inoculant, so the design of the inoculant and the refining mechanism thereof are one of the key research directions of scientific and technological workers at home and abroad.
However, because aluminum alloys typically contain different alloying elements that alter the α -Al lattice constant, different aluminum alloys can vary greatly in value when the same inoculant, such as Al-5Ti-1B, is used, resulting in different grain refinement effects and even failure when inoculating certain alloys, such as the A356.2 alloy.
Sc not only has a very obvious grain refining effect, but also can improve the nucleation density in the process of material solidification, so the Sc is often used as a micro-alloying addition element for different alloys. CN105525162A discloses a preparation process for improving Al-5.2Mg-0.3Mn alloy by adding Zr and rare earth Sc elements; CN109022983A discloses a Sc-containing high-strength high-toughness magnesium alloy and a preparation method thereof; CN104674079A discloses a composite aluminum magnesium alloy containing Sc and Zr and a preparation method thereof; CN104911409A discloses a scandium-zirconium-containing boron carbide particle reinforced aluminum-based composite material and a preparation method thereof, in the four prior art, Sc element is added into different alloys in a micro-alloying and multi-step heat treatment mode to achieve the purpose of refining grains and improving performance, and the four prior art have the defects of more process flows, complex operation, higher cost and Al in the alloy3Aggregation and precipitation of Sc particles in the melt, Al3The Sc particles have the defects of overlarge size, incapability of dispersing and distributing nucleation particles on a matrix, single nucleation type and less nucleation quantity.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: providing nano Al in thin strip form3The preparation method of the (Sc, Zr)/Al composite inoculant adopts an in-situ autogenous method, intermediate alloy forging and melt rapid quenching treatment to prepare the thin-strip-shaped nano Al3The method prepares Sc element and Zr element into the nano composite inoculant for refining the aluminum alloy for the first time, and overcomes the defects of more process flows, complex operation, higher cost and Al in the alloy in the prior art3Of Sc particles in the meltAggregate precipitate, Al3The Sc particles have the defects of overlarge size, incapability of dispersing and distributing nucleation particles on a matrix, single nucleation type and less nucleation quantity.
The technical scheme adopted by the invention for solving the technical problem is as follows: thin strip-shaped nano Al3The preparation method of the (Sc, Zr)/Al composite inoculant adopts an in-situ autogenous method, alloy forging and melt rapid quenching technology to prepare the thin strip-shaped nano Al3The (Sc, Zr)/Al composite inoculant comprises the following specific steps:
step one, preparing raw materials:
weighing the required amount of commercially available high-purity Sc and commercially available high-purity Zr, wherein the weight percentages of the components in the target alloy are as follows: preparing raw materials including Sc 4%, Zr 4% and the balance of Al;
secondly, preparing a massive Al-4Sc-4Zr intermediate alloy by an in-situ autogenous method:
putting all the prepared raw materials weighed in the first step into a crucible of a high vacuum induction melting furnace for melting, wherein the vacuum degree is 5 × 10-4Pa, the melting temperature is 2000K, and the melting time is 10 minutes, so that the alloy is melted to prepare the massive Al-4Sc-4Zr intermediate alloy by an in-situ autogenous method;
thirdly, forging the intermediate alloy to obtain a melt rapid quenching prefabricated part:
loading the blocky Al-4Sc-4Zr intermediate alloy obtained in the second step into a crucible type resistance furnace at room temperature, uniformly preheating the loaded blocky Al-4Sc-4Zr intermediate alloy material at the temperature of 300 ℃, clamping the alloy material by using crucible tongs, forging the alloy material on a 100T hydraulic press to obtain a prefabricated part with the thickness of 7mm, the length of 50mm and the width of 50mm, wherein the operation conditions of the hydraulic press are as follows: firstly heating the intermediate alloy to 300 +/-10 ℃ according to power, then heating the intermediate alloy to a set temperature at a heating speed of 50 ℃/h, namely keeping the initial forging temperature at 380-400 ℃, and the final forging temperature at more than or equal to 350 ℃, so as to forge the massive Al-4Sc-4Z intermediate alloy to prepare a melt rapid quenching prefabricated member;
fourthly, the melt is rapidly quenched to prepare the thin-strip-shaped nano Al3(Sc, Zr)/Al composite inoculant:
forging the intermediate alloy in the third step to obtain a melt rapid quenching prefabricationCutting the workpiece into small blocks with thickness, width and length of 7mm × 7mm × 10mm by using a wire cutting machine, cleaning the small blocks with alcohol, air-drying the small blocks, putting the small blocks into a quartz glass tube, sleeving an induction heating coil outside the quartz glass tube, installing the quartz glass tube into a vacuum rapid quenching furnace, and vacuumizing the vacuum rapid quenching furnace to 5 × 10 by using a molecular pump-4And Pa, introducing argon gas for protection all the time, starting a copper roller of the vacuum rapid quenching furnace, heating the quartz glass tube to 1200 ℃ by using an induction coil when the rotating speed of the copper roller reaches 4000-8000 r/min, preserving the heat for 6 minutes, spraying the melt rapid quenching prefabricated part melted in the quartz glass tube onto the rapidly rotating copper roller, wherein the cooling rate of the molten melt rapid quenching prefabricated part reaches 105～108K/S, preparing thin strip-shaped nano Al with the width of 2-5 mm, the thickness of 0.05-0.1 mm and the length of 10-40 mm by melt rapid quenching treatment3(Sc, Zr)/Al composite inoculant in which Al is formed3The (Sc, Zr) particles are clustered, the nucleation particles are nano crystals, and the particle sizes are distributed in the range of 200-500 nm of the optimal nucleation size.
The above-mentioned thin band-like nano Al3The preparation method of the (Sc, Zr)/Al composite inoculant is characterized in that the high-vacuum induction smelting furnace is an MZG series high-vacuum induction smelting furnace.
The above-mentioned thin band-like nano Al3The preparation method of the (Sc, Zr)/Al composite inoculant is characterized in that the vacuum rapid quenching furnace is a WK-IIB type vacuum rapid quenching furnace.
The above-mentioned thin band-like nano Al3The preparation method of the (Sc, Zr)/Al composite inoculant can obtain the related raw materials and equipment by known ways, and the operation process can be mastered by a person skilled in the art.
The above-mentioned thin band-like nano Al3The (Sc, Zr)/Al composite inoculant is applied as follows:
forming thin strip-shaped nano Al3The (Sc, Zr)/Al composite inoculant is added into different aluminum alloys for inoculation treatment, and the specific operation method comprises the following steps: weighing 100g of pure aluminum, A356.2 alloy and Al-5Cu alloy as raw materials, placing the raw materials in a crucible, placing the crucible in a resistance furnace, heating to 720 ℃, adding a refining agent to carry out slag skimming treatment on the alloy melt after all the raw materials are melted into alloy, and weighing the thin-strip-shaped nano Al3Preparation method of (Sc, Zr)/Al composite inoculantThe prepared thin strip-shaped nano Al30.6-0.8 g of (Sc, Zr)/Al composite inoculant, wrapping the inoculant by using aluminum foil, adding the aluminum foil into the alloy melt subjected to slagging-off treatment, carrying out inoculation for 30-45 s, stirring by using a graphite rod, and casting the alloy melt into a steel die with the height of 120mm and the diameter of 20 mm.
The lattice constant of the alloy is smaller than that of pure aluminum due to the addition of Cu atoms with the lattice constant smaller than that of Al in the raw material Al-5Cu alloy, and the lattice constant of the alloy is larger than that of the pure aluminum due to the fact that the A356.2 alloy mainly contains Si and Mg elements. The thin strip-shaped nano Al prepared by the method of the invention3The (Sc, Zr)/Al composite inoculant is added into different aluminum alloys for inoculation treatment, and then the nano Al3The (Sc, Zr)/Al composite inoculant shows good grain refining effect on aluminum alloys with different lattice constants. Wherein the grain size of the pure aluminum is thinned to 110 μm from 820 μm of the non-pregnant treatment; the grain size of the A356.2 alloy was refined from 450 μm for non-pregnant treatments to 220 μm; the grain size of the Al-5Cu alloy is refined from 185 μm of the non-pregnant treatment to 65 μm.
The thin strip-shaped nano Al prepared by the method of the invention3The (Sc, Zr)/Al composite inoculant is suitable for inoculation treatment of various aluminum alloys.
The invention has the beneficial effects that: compared with the prior art, the invention has the prominent substantive characteristics as follows:
(1) the invention utilizes an in-situ self-generation method to generate the inoculant. By in situ autogenesis is meant that the reinforcement particles are not added externally but rather by chemical reaction, one or more reinforcement phases are formed in situ within the inoculant matrix. The reinforcing phases are generated in the aluminum matrix and have good lattice matching relation with the aluminum matrix, so when the inoculant prepared by the method is added into the aluminum alloy, the nucleating agent serves as a substrate for nucleating the aluminum matrix and promotes heterogeneous nucleation, thereby achieving the effect of refining aluminum alloy grains.
(2) Theoretically, the thin strip-shaped nano-grade Al prepared by the method of the invention3(Sc, Zr)/Al inoculant, wherein the thin strip contains Al with higher volume fraction3The (Sc, Zr) dual-phase particles are clustered, the crystallographic orientation is highly consistent, and the particlesThe cluster number is large, the size is uniform, and the particle size is distributed in the range of the optimal nucleation size of 200-500 nm, so that the aluminum alloy nucleation is easier to excite and the nucleation efficiency is higher.
Compared with the prior art, the invention has the following remarkable improvements:
(1) the thin band-shaped nano Al of the invention3The (Sc, Zr)/Al inoculant is produced by in-situ autogenous reaction, and compared with the prior art, the in-situ generation technology is controllable for the size and distribution of the reinforced particles, because the reinforced Al3(Sc, Zr) is generated directly on the substrate, therefore ① Al3The (Sc, Zr) particles have clean and pollution-free surfaces and good wettability with the matrix, so that the reinforcement body and the matrix have good interface bonding performance, ② has no interface reaction, ③ reinforcement particle size can reach nanometer level, and the reinforcement effect in crystal is good.
(2) The method of the invention adopts an alloy forging method, makes up the defects of reinforced particle agglomeration and uneven size in the alloy obtained after the raw materials are inductively smelted in a vacuum induction smelting furnace, and achieves the purpose of refining and homogenizing the intermediate alloy.
(3) The method adopts a method of rapid solidification treatment in a vacuum rapid quenching furnace, after alloy forging treatment is carried out to obtain a melt rapid quenching prefabricated part, the vacuum rapid quenching furnace is used for rapid solidification treatment, the melt is sprayed onto a copper wheel rotating at a high speed, the high rotating speed of the copper wheel is used for achieving an extremely fast cooling speed, and the thin strip-shaped nano Al prepared by the method is3(Sc, Zr)/Al composite inoculant wherein Al is formed3The (Sc, Zr) particles cluster and the nucleation particles in the (Sc, Zr) particles cluster are nano-crystals, so that the thinning effect is greatly improved.
(4) The thin strip-shaped nano Al finally prepared by the method3The (Sc, Zr)/Al composite inoculant has nanoscale nucleation clusters which are dispersed in a matrix, and overcomes the defect that Al in Al-Sc alloy in the prior art3Aggregation and precipitation of Sc particles in the melt, Al3The Sc particles have the defects of overlarge size, incapability of dispersing and distributing nucleation particles on a matrix, single nucleation type and less nucleation quantity.
(5) Sodium prepared by the method of the inventionRice Al3The (Sc, Zr)/Al composite inoculant has good grain refining effect on aluminum alloys with various lattice parameters, is suitable for inoculation treatment of various aluminum alloys, and overcomes the 'singleness' of inoculant application.
(6) Compared with CN104674079A Z L aluminum magnesium alloy (Al-10Mg) compounded by Zr and rare earth Sc and a preparation method thereof, the product disclosed by CN104674079A comprises 2.5 percent of Zr, 2.5 percent of Sc, 10 percent of Mg and the balance of Al by weight percent, the preparation method is a micro-alloying method, pure aluminum is melted by using a graphite crucible resistance furnace, and then pressed into a magnesium block by using a bell jar, and then an Al-5Sc and Al-10Zr intermediate alloy is added, wherein the product cost is high due to the fact that the addition amount of Sc in the product reaches 2.5 percent, vacuum protection is not added in the preparation method, and the uniform mixing of alloy elements is difficult to ensure only by stirring by using a graphite rod by an operator, and the problem that the Al in the Al-Sc alloy is difficult to overcome is difficult to3Too large Sc particle size and a small number of defects. In the invention, Sc and Zr are used for preparing the inoculant, and the inoculant is added into different alloys, so that the performance of the alloy is improved. Compared with a microalloying method, the inoculant provided by the invention is added into the alloy in an amount of only 0.6 wt.%, namely the inoculant contains 4% of Sc, the inoculant is added into the alloy in an amount of 0.6%, namely the Sc content added into the alloy is only 0.024%, so that a good grain refining effect can be achieved, and the cost is greatly reduced.
(7) Compared with a preparation process of CN105525162A for improving Al-5.2Mg-0.3Mn alloy by adding Zr and rare earth Sc elements, the method adopts a semi-continuous casting metallurgy method, needs the steps of homogenizing annealing, hot rolling, cold rolling, stabilizing annealing and the like, has more complex operation process and higher precision requirement on equipment temperature, and has more Sc and Zr elements which are respectively 0.25 percent and 0.12 percent. Compared with the method, the inoculation method has simple steps, is convenient to operate, and obviously reduces the addition of Sc and Zr elements.
(8) Compared with the CN109022983A high-strength high-toughness magnesium alloy containing Sc and the preparation method thereof, the method adds a plurality of alloy elements, mainly comprising 4.5-6.5 wt% of Y, 1.5-4.0 wt% of Nd, 1.5-4.0 wt% of Gd, 0.05-0.5 wt% of Sc, 0.15-1.5 wt% of Zr and the balance of Mg, and mainly comprises the following operation steps: the alloy elements are added step by step for casting, casting homogenization, preheating, extrusion, aging treatment and the like. The prior art has more complex operation steps, complicated process flow and more addition of Sc and Zr elements, which are overcome and improved in the invention.
(9) Compared with CN104911409A boron carbide particle reinforced aluminum matrix composite containing scandium and zirconium and the preparation method thereof, the method adds Al-2Sc and Al-15Zr intermediate alloy into molten aluminum at 800 ℃ for heat preservation for 40 minutes without vacuum protection, and alloy elements are difficult to be fully dissolved only depending on a long-time heat preservation mode, thereby causing Al-Sc alloy Al-Zr intermediate alloy3The invention uses an induction furnace for smelting, and the vacuum degree is 5 × 10-4Pa, the melting temperature is 2000K, and the melting time is 10 minutes, so that the alloy is melted, the massive Al-4Sc-4Zr intermediate alloy is prepared by an in-situ autogenous method, then the intermediate alloy is forged, particles in the intermediate alloy are refined, the uniform distribution of the particles is ensured, and the defects of the prior art are overcome.
(10) Compared with the previous preparation method of the superfine crystal inoculant for refining the aluminum alloy crystal grains by using CN102787260B of the inventor team, CN102787260B is to obtain a master alloy by adopting electric arc melting firstly and then carry out rapid solidification treatment to obtain a thin-strip master alloy. The method has the substantial differences that the method adopts an induction heating mode, the melting temperature is 2000K, the melting time is 10 minutes, the temperature is kept for a long time to ensure the component reaction of alloy elements in the melt, and then the step of alloy forging is added, so that the defects of uneven components and larger particle size of the intermediate alloy are overcome.
(11) Compared with the previous preparation method of the in-situ aluminum-based composite inoculant of CN102864343B by the inventor team, CN102864343B is firstly smelted by using a vacuum arc furnace and then further subjected to plasma nitriding treatment, a plasma spray gun is used for extending into a graphite crucible, sprayed plasma flame is contacted with the alloy, the plasma flame and the alloy cannot be cast into a mold after being smelted and reacted, the crucible can only be smashed after being cooled along with the crucible, and the alloy is taken out, so that the production efficiency is low and the method is not environment-friendly. The method and the equipment used in the invention have the advantages of improved production efficiency and no destructive test, and completely overcome the defects in the CN102864343B technology.
(12) Compared with the previous preparation method of the in-situ self-generated aluminum-based composite inoculant of CN105950921B of the inventor team, CN105950921B is that the master alloy is prepared by vacuum induction melting and then is rapidly solidified, and the method has the substantial difference that the method is characterized in that the step of alloy forging is added after the vacuum induction melting, so that the defects of uneven components and larger particle size of the master alloy are overcome, and the defects in the CN105950921B technology are completely overcome.
In view of the shortcomings and drawbacks of the three prior patent technologies of CN102787260B, CN102864343B and CN105950921B, the inventor of the present invention has conducted extensive research and development for over three years to complete innovative present technology, which overcomes the shortcomings and drawbacks of the prior patent technologies mentioned above, and even if the technical solution of the present invention is obtained by combining the conventional technical means in the field on the basis of the patent technologies mentioned above, it is very difficult for those skilled in the art to obtain the present invention.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 shows the thin strip-shaped nano Al prepared by the method of the invention3X-ray diffraction pattern of the (Sc, Zr)/Al composite inoculant.
FIG. 2 shows the thin strip-shaped nano Al prepared by the method of the present invention3Scanning electron microscope images of (Sc, Zr)/Al composite inoculants, wherein:
FIG. 2(a) shows a low magnification thin band-like nano Al3Scanning electron microscope images of (Sc, Zr)/Al composite inoculants;
FIG. 2(b) shows high-magnification thin band-like nano Al3Scanning electron microscope image of (Sc, Zr)/Al composite inoculantThe inset portion is an enlarged view of the area shown.
FIG. 3 shows the addition of 0.6 wt.% of nano Al according to the present invention3The (Sc, Zr)/Al composite inoculant inoculates metallographic structure photographs of pure aluminum, wherein:
FIG. 3(a) is a photograph of the metallographic structure of as-cast pure aluminum without the addition of an inoculant;
FIG. 3(b) is the addition of 0.6 wt.% nano Al3And a metallographic structure photograph of as-cast pure aluminum in the case of the (Sc, Zr)/Al composite inoculant.
FIG. 4 is a graph of adding 0.8 wt.% of nano Al of the present invention3Metallographic photographs of (Sc, Zr)/Al composite inoculant treated A356.2 alloy, wherein:
FIG. 4(a) is a photograph of the metallographic structure of the as-cast A356.2 alloy without the addition of an inoculant;
FIG. 4(b) is the addition of 0.8 wt.% nano Al3Metallographic structure photograph of as-cast A356.2 alloy in the case of (Sc, Zr)/Al composite inoculant.
FIG. 5 is a graph of the addition of 0.7 wt.% of nano Al of the present invention3Metallographic structure photographs of Al-5Cu alloy treated by the (Sc, Zr)/Al composite inoculant, wherein:
FIG. 5(a) is a photograph of the metallographic structure of an as-cast Al-5Cu alloy without the addition of an inoculant;
FIG. 5(b) is the addition of 0.7 wt.% nano Al3Metallographic structure photograph of as-cast Al-5Cu alloy in the case of (Sc, Zr)/Al composite inoculant.
Detailed Description
Example 1
Step one, preparing raw materials:
weighing the required amount of commercially available high-purity Sc and commercially available high-purity Zr, wherein the weight percentages of the components in the target alloy are as follows: preparing raw materials including Sc 4%, Zr 4% and the balance of Al;
secondly, preparing a massive Al-4Sc-4Zr intermediate alloy by an in-situ autogenous method:
putting all the raw materials weighed in the first step into a crucible of a MZG series high vacuum induction melting furnace for melting, wherein the vacuum degree is 5 × 10-4Pa, the melting temperature of 2000K and the melting time of 10 minutes, thereby melting the alloy by an in-situ self-generation methodObtaining a massive Al-4Sc-4Zr intermediate alloy;
thirdly, forging the intermediate alloy to obtain a melt rapid quenching prefabricated part:
loading the blocky Al-4Sc-4Zr intermediate alloy obtained in the second step into a crucible type resistance furnace at room temperature, uniformly preheating the loaded blocky Al-4Sc-4Zr intermediate alloy material at the temperature of 300 ℃, clamping the alloy material by using crucible tongs, forging the alloy material on a 100T hydraulic press to obtain a prefabricated part with the thickness of 7mm, the length of 50mm and the width of 50mm, wherein the operation conditions of the hydraulic press are as follows: firstly, heating to 300 +/-10 ℃ according to power, then heating to a set temperature at a heating speed of 50 ℃/h, namely keeping the initial forging temperature to be 380 and the final forging temperature to be more than or equal to 350 ℃, and forging the massive Al-4Sc-4Z intermediate alloy to obtain a melt rapid quenching prefabricated member;
fourthly, the melt is rapidly quenched to prepare the thin-strip-shaped nano Al3(Sc, Zr)/Al composite inoculant:
cutting the melt rapid quenching prefabricated member prepared by forging the intermediate alloy in the third step into small blocks with the thickness, the width and the length of 7mm × 7mm × 10mm by using a wire cutting machine, cleaning the small blocks by using alcohol, then drying the small blocks, putting the small blocks into a quartz glass tube, sleeving an induction heating coil outside the quartz glass tube, installing the quartz glass tube into a WK-IIB type vacuum rapid quenching furnace, and vacuumizing the inside of the WK-IIB type vacuum rapid quenching furnace to 5 × 10 by using a molecular pump-4Pa, introducing argon gas for protection all the time, starting a copper roller of the vacuum rapid quenching furnace, heating the quartz glass tube to 1200 ℃ by an induction coil when the rotating speed of the copper roller reaches 4000r/min, preserving the heat for 6 minutes, spraying the melt rapid quenching prefabricated part melted in the quartz glass tube onto the rapidly rotating copper roller, wherein the cooling rate of the melt rapid quenching prefabricated part reaches 105K/S, preparing thin strip-shaped nano Al with the width of 5mm, the thickness of 0.1mm and the length of 40mm by the melt rapid quenching treatment3(Sc, Zr)/Al composite inoculant in which Al is formed3The (Sc, Zr) particles are clustered, the nucleation particles are nano crystals, and the particle sizes are distributed in the range of 200-500 nm of the optimal nucleation size.
The thin strip-shaped nano Al prepared by the method3The (Sc, Zr)/Al composite inoculant is ground by using 2000# SiC abrasive paper, impurities on the surface of a sample are washed off by using alcohol through ultrasonic oscillation, and German Bruker D8 Disc is adoptedover type multifunctional X-ray instrument (XRD) CuKαRays to identify the phases contained in the inoculant, as shown in FIG. 1, the thin band-shaped nano Al of the example3The (Sc, Zr)/Al composite inoculant consists of α (Al) phase and Al3Sc phase and Al3Zr phase composition, Al3Sc phase and Al3Successful synthesis of the Zr phase means that the in-situ synthesis method in an induction smelting furnace is desirable because X-ray diffraction is a statistical rule and is generally difficult to detect when the element content is below 5%. In this example, the amount of Sc and Zr added was 4%, and it is seen from FIG. 1 that Al is3Sc and Al3The characteristic peak of the Zr phase is very obvious, which means that Al synthesized in situ3Sc and Al3The Zr phase is more abundant. The thin band-shaped Al of this example was observed with a FEI Nova Nano SEM450 field emission electron microscope3The microstructure of the (Sc, Zr)/Al composite inoculant is shown in the scanning electron microscope image of FIG. 2, wherein the dark color is aluminum matrix, and FIG. 2(a) shows that the thin strip-shaped nano Al of the present embodiment3In the (Sc, Zr)/Al composite inoculant, the gray particles are dispersed and distributed in the matrix and are more in number, and it is noted that the thin-strip inoculant prepared by the embodiment has no obvious particle agglomeration phenomenon, so that the defects of the preparation method in the prior art are greatly improved; meanwhile, the figure shows that the number of the particles is large, which is the key point that the thin strip inoculant has good grain refining effect on the aluminum alloy, and the defect that the number of nucleation particles is insufficient in the existing microalloying technology is overcome; FIG. 2(b) is an enlarged 50-fold diagram of FIG. 2(a), which shows that the particle cluster has a size of 200-500 nm and is composed of a plurality of nanocrystalline particles, and shows that the thin-strip-shaped nano Al of the present invention3α (Al) phase and Al in (Sc, Zr)/Al composite inoculant3Sc phase and Al3The Zr phase does not exist in the matrix independently, but forms Al with the size of 200-500 nm3(Sc, Zr) particle clusters composed of a plurality of nano-scale particles, which are also the thin-strip-shaped nano Al of the present invention3The reason why the (Sc, Zr)/Al composite inoculant has good grain refining effect.
Example 2
Step one, preparing raw materials:
the same as example 1;
secondly, preparing a massive Al-4Sc-4Zr intermediate alloy by an in-situ autogenous method:
the same as example 1;
thirdly, forging the intermediate alloy to obtain a melt rapid quenching prefabricated part:
the same as example 1;
fourthly, the melt is rapidly quenched to prepare the thin-strip-shaped nano Al3(Sc, Zr)/Al composite inoculant:
cutting the melt rapid quenching prefabricated member prepared by forging the intermediate alloy in the third step into small blocks with the thickness, the width and the length of 7mm × 7mm × 10mm by using a wire cutting machine, cleaning the small blocks by using alcohol, then drying the small blocks, putting the small blocks into a quartz glass tube, sleeving an induction heating coil outside the quartz glass tube, installing the quartz glass tube into a WK-IIB type vacuum rapid quenching furnace, and vacuumizing the inside of the WK-IIB type vacuum rapid quenching furnace to 5 × 10 by using a molecular pump-4Pa, introducing argon gas for protection all the time, starting a copper roller of the vacuum rapid quenching furnace, heating the quartz glass tube to 1200 ℃ by an induction coil when the rotating speed of the copper roller reaches 6000r/min, preserving the heat for 6 minutes, spraying the melt rapid quenching prefabricated part melted in the quartz glass tube onto the copper roller which rotates rapidly, wherein the cooling rate of the copper roller reaches 106K/S, preparing thin strip Al with the width of 3.5mm, the thickness of 0.06mm and the length of 20mm3(Sc, Zr)/Al composite inoculant in which Al is formed3The (Sc, Zr) particles are clustered, the nucleation particles are nano crystals, and the particle sizes are distributed in the range of 200-500 nm of the optimal nucleation size.
Example 3
Step one, preparing raw materials:
the same as example 1;
secondly, preparing a massive Al-4Sc-4Zr intermediate alloy by an in-situ autogenous method:
the same as example 1;
thirdly, forging the intermediate alloy to obtain a melt rapid quenching prefabricated part:
the same as example 1;
fourthly, the melt is rapidly quenched to prepare the thin-strip-shaped nano Al3(Sc, Zr)/Al composite inoculant:
cutting the melt rapid quenching prefabricated member prepared by forging the intermediate alloy in the third step into small blocks with the thickness, the width and the length of 7mm × 7mm × 10mm by using a wire cutting machine, cleaning the small blocks by using alcohol, then drying the small blocks, putting the small blocks into a quartz glass tube, sleeving an induction heating coil outside the quartz glass tube, installing the quartz glass tube into a WK-IIB type vacuum rapid quenching furnace, and vacuumizing the inside of the WK-IIB type vacuum rapid quenching furnace to 5 × 10 by using a molecular pump-4Pa, introducing argon gas for protection all the time, starting a copper roller of the vacuum rapid quenching furnace, heating the quartz glass tube to 1200 ℃ by an induction coil when the rotating speed of the copper roller reaches 8000r/min, preserving the heat for 6 minutes, spraying the melt rapid quenching prefabricated part melted in the quartz glass tube onto the copper roller which rotates rapidly, wherein the cooling rate of the copper roller reaches 108K/S, preparing thin strip-shaped Al with the width of 2.5mm, the thickness of 0.03mm and the length of 15mm3(Sc, Zr)/Al composite inoculant in which Al is formed3The (Sc, Zr) particles are clustered, the nucleation particles are nano crystals, and the particle sizes are distributed in the range of 200-500 nm of the optimal nucleation size.
Example 4
The thin band-shaped nano Al prepared in the above example 13Adding a (Sc, Zr)/Al composite inoculant into pure aluminum for inoculation treatment:
weighing 100g of pure aluminum, placing the pure aluminum into a crucible, placing the crucible into a resistance furnace, heating to 720 ℃, adding a refining agent after melting, and carrying out slag skimming on the melt; 0.6g of thin strip-shaped nano Al is weighed3The (Sc, Zr)/Al composite inoculant is wrapped by aluminum foil and added into the molten alloy, the inoculation time is 30s, and the melt is cast into a steel die with the height of 120mm and the diameter of 20mm after being stirred by a graphite rod; the inoculated pure aluminum is cut by an electric spark cutting machine, samples with the length of 10mm, the width of 10mm and the thickness of 10mm are cut, the cut samples are respectively ground on 200#, 400#, 600#, 800#, 1200# and 2000# water mill sandpaper, then mechanical polishing treatment is carried out, impurities on the surfaces of the samples are washed away by ultrasonic oscillation by alcohol, and metallographic structure observation is carried out by using a German Zea Axio Imager M2M type microscope. The metallographic structure of pure aluminum before and after inoculation is shown in fig. 3: FIG. 3(a) is a metallographic photograph showing as-cast pure aluminum subjected to a non-pregnant treatmentThe grain size of the steel is coarse and large, which directly results in lower strength and is difficult to meet production requirements; FIG. 3(b) shows the addition of 0.6 wt.% of thin strip-like nano Al3After the (Sc, Zr)/Al composite inoculant, the crystal grains of pure aluminum are refined into uniform and fine isometric crystals, the size of the equiaxed crystals is obviously reduced to 110 mu m, and the equiaxed crystals are only 1/8 in the case of non-pregnancy treatment.
Example 5
The thin band-shaped nano Al prepared in the above example 23Adding a (Sc, Zr)/Al composite inoculant into the A356.2 alloy for inoculation:
weighing 100g of A356.2 alloy, placing the alloy in a crucible, placing the crucible in a resistance furnace, heating to 720 ℃, adding a refining agent after melting, and carrying out slag skimming on the melt; 0.8g of thin strip-shaped nano Al is weighed3The (Sc, Zr)/Al composite inoculant is wrapped by aluminum foil and added into the molten alloy, the inoculation time is 45s, and the melt is cast into a steel die with the height of 120mm and the diameter of 20mm after being stirred by a graphite rod; the inoculated pure aluminum is cut by an electric spark cutting machine, samples with the length of 10mm, the width of 10mm and the thickness of 10mm are cut, the cut samples are respectively ground on 200#, 400#, 600#, 800#, 1200# and 2000# water mill sandpaper, then mechanical polishing treatment is carried out, impurities on the surfaces of the samples are washed away by ultrasonic oscillation by alcohol, and metallographic structure observation is carried out by using a German Zea Axio Imager M2M type microscope. The metallographic structure of the a356.2 alloy before and after inoculation is shown in fig. 4: fig. 4(a) shows a metallographic photograph of the as-cast a356.2 alloy at the time of the non-pregnant treatment. The figure shows that the obvious dendrites are distributed on the matrix, the grain size is 450 mu m, and simultaneously shows that the matrix has obvious long needle-shaped silicon phases which are easy to crack the matrix, thereby being extremely unfavorable for improving the mechanical property of the alloy; FIG. 4(b) shows the addition of 0.8 wt.% of thin band-like nano Al3Metallographic structure photograph of as-cast A356.2 alloy in the case of (Sc, Zr)/Al composite inoculant. The grain size of the alloy is obviously reduced to 220 mu m, and the needle-shaped silicon phase distributed in the matrix is obviously spheroidized, so that the improvement of the alloy performance is greatly beneficial.
Example 6
The thin band-shaped nanometer A prepared in the above example 3l3Adding a (Sc, Zr)/Al composite inoculant into the Al-5Cu alloy for inoculation:
weighing 100g of Al-5Cu alloy, placing the alloy in a crucible, placing the crucible in a resistance furnace, heating to 720 ℃, adding a refining agent after melting, and carrying out slag skimming on the melt; 0.7g of thin strip-shaped nano Al is weighed3The (Sc, Zr)/Al composite inoculant is wrapped by aluminum foil and added into the molten alloy, the inoculation time is 40s, and the melt is cast into a steel die with the height of 120mm and the diameter of 20mm after being stirred by a graphite rod; the inoculated pure aluminum is cut by an electric spark cutting machine, samples with the length of 10mm, the width of 10mm and the thickness of 10mm are cut, the cut samples are respectively ground on 200#, 400#, 600#, 800#, 1200# and 2000# water mill sandpaper, then mechanical polishing treatment is carried out, impurities on the surfaces of the samples are washed away by ultrasonic oscillation by alcohol, and metallographic structure observation is carried out by using a German Zea Axio Imager M2M type microscope. The metallographic structure of the Al-5Cu alloy before and after inoculation is shown in FIG. 5: FIG. 5(a) is a photograph of the metallographic structure of the as-cast Al-5Cu alloy without the addition of an inoculant agent, and shows that the grains of the alloy are a mixture of equiaxed and columnar grains and have a size of 185 μm; FIG. 5(b) shows the addition of 0.7 wt.% nano Al3The metallographic structure photograph of the as-cast Al-5Cu alloy when the (Sc, Zr)/Al composite inoculant is adopted, all crystal grains in the alloy are changed into isometric grains, and the crystal grains are fine and uniform and have the size of 65 mu m.
The raw materials and equipment involved in the above examples are available in a known manner, and the operation process can be grasped by those skilled in the art.
Claims (1)
1. Thin strip-shaped nano Al3The preparation method of the (Sc, Zr)/Al composite inoculant is characterized by comprising the following steps: preparing thin strip-shaped nano Al by adopting an in-situ autogenous method, alloy forging and melt rapid quenching technology3The (Sc, Zr)/Al composite inoculant comprises the following specific steps:
step one, preparing raw materials:
weighing the required amount of commercially available high-purity Sc and commercially available high-purity Zr, wherein the weight percentages of the components in the target alloy are as follows: preparing raw materials including Sc 4%, Zr 4% and the balance of Al;
secondly, preparing a massive Al-4Sc-4Zr intermediate alloy by an in-situ autogenous method:
putting all the prepared raw materials weighed in the first step into a crucible of a high vacuum induction melting furnace for melting, wherein the vacuum degree is 5 × 10-4Pa, the melting temperature is 2000K, and the melting time is 10 minutes, so that the alloy is melted to prepare the massive Al-4Sc-4Zr intermediate alloy by an in-situ autogenous method;
thirdly, forging the intermediate alloy to obtain a melt rapid quenching prefabricated part:
loading the blocky Al-4Sc-4Zr intermediate alloy obtained in the second step into a crucible type resistance furnace at room temperature, uniformly preheating the loaded blocky Al-4Sc-4Zr intermediate alloy material at the temperature of 300 ℃, clamping the alloy material by using crucible tongs, forging the alloy material on a 100T hydraulic press to obtain a prefabricated part with the thickness of 7mm, the length of 50mm and the width of 50mm, wherein the operation conditions of the hydraulic press are as follows: firstly heating the intermediate alloy to 300 +/-10 ℃ according to power, then heating the intermediate alloy to a set temperature at a heating speed of 50 ℃/h, namely keeping the initial forging temperature at 380-400 ℃, and the final forging temperature at more than or equal to 350 ℃, so as to forge the massive Al-4Sc-4Zr intermediate alloy to prepare a melt rapid quenching prefabricated member;
fourthly, the melt is rapidly quenched to prepare the thin-strip-shaped nano Al3(Sc, Zr)/Al composite inoculant:
cutting the melt rapid quenching prefabricated member prepared by forging the intermediate alloy in the third step into small blocks with the thickness, the width and the length of 7mm × 7mm × 10mm by using a wire cutting machine, cleaning the small blocks by using alcohol, then drying the small blocks, putting the small blocks into a quartz glass tube, sleeving an induction heating coil outside the quartz glass tube, installing the quartz glass tube into a vacuum rapid quenching furnace, and vacuumizing the vacuum rapid quenching furnace to 5 × 10 by using a molecular pump- 4And Pa, introducing argon gas for protection all the time, starting a copper roller of the vacuum rapid quenching furnace, heating the quartz glass tube to 1200 ℃ by using an induction coil when the rotating speed of the copper roller reaches 4000-8000 r/min, preserving the heat for 6 minutes, spraying the melt rapid quenching prefabricated part melted in the quartz glass tube onto the rapidly rotating copper roller, wherein the cooling rate of the molten melt rapid quenching prefabricated part reaches 105～108K/S, preparing thin strip-shaped nano Al with the width of 2-5 mm, the thickness of 0.05-0.1 mm and the length of 10-40 mm by melt rapid quenching treatment3(Sc, Zr)/Al composite inoculant in which Al is formed3(Sc, Zr) particle clusters in which the nucleation particles are nanocrystals, the Al3The particle size distribution of the (Sc, Zr) particle clusters is in the range of 200-500 nm of the optimal nucleation size.
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