CN114438374B

CN114438374B - Al-V-Ti-B grain refiner and preparation and application method thereof

Info

Publication number: CN114438374B
Application number: CN202210117757.3A
Authority: CN
Inventors: 张云虎; 周灿云; 刘利兵; 赵江涛
Original assignee: University of Shanghai for Science and Technology
Current assignee: University of Shanghai for Science and Technology
Priority date: 2022-02-08
Filing date: 2022-02-08
Publication date: 2022-06-28
Anticipated expiration: 2042-02-08
Also published as: CN114438374A

Abstract

The invention discloses an Al-V-Ti-B grain refiner and a preparation and application method thereof, and the refiner comprises the following chemical elements in percentage by mass: v: 0.1-10 wt.%, B: 0.1-10 wt.%, Ti: 0.1-10 wt.%, 75-99.7 wt.% of Al, and the main heterogeneous nucleation point of the Al is VB modified by Ti element₂The preparation process of the particle mainly comprises two steps: the first step containing VB₂Preparing a grain refiner; the second step is to VB with Ti element₂The particles are modified. By the Ti element pair VB₂The grains are modified, free Ti is introduced, the thinning capability of the refiner on the aluminum alloy is obviously improved, and the refiner has a good application prospect.

Description

Al-V-Ti-B grain refiner and preparation and application method thereof

Technical Field

The invention belongs to the technical field of grain refinement, and particularly relates to an Al-V-Ti-B grain refiner and preparation and application methods thereof.

Background

The ideal ingot structure is that the whole section of the ingot has uniform and fine isometric crystals, because the isometric crystals have small anisotropy, uniform deformation, excellent performance and good plasticity in processing, the ingot is beneficial to casting and subsequent plastic processing, and the performance of the finally prepared product is improved. To obtain such a structure, it is usually necessary to refine the melt, and all treatments that promote nucleation and inhibit grain growth refine the grains. At present, the grain refinement technology has become an important means for improving the structure and performance of the metal material, and mainly comprises dynamic grain refinement and modification treatment.

Wherein, the dynamic grain refinement is to vibrate and stir the molten metal, on one hand, the energy input from the outside is relied on to promote the crystal nucleus to form in advance, on the other hand, the growing dendrite is broken, and the number of the crystal nucleus is increased. Currently, mechanical stirring, electromagnetic stirring, audio vibration, ultrasonic vibration, and the like have been used. Through stirring and shaking the fuse-element in the liquid cave, increased the heat exchange of fuse-element and condensation shell, the fuse-element temperature in the liquid cave reduces, and the supercooling zone increases, breaks the skeleton at crystallization front edge, has appeared a large amount of dendritic crystal fragments that can regard as the crystallization core to make the crystalline grain refine. However, this refining method usually requires the purchase of relatively complex and expensive equipment, requires high precision of operation and installation, generates relatively high energy consumption in actual use, and has limited refining effect, and the use effect is not ideal.

The modification treatment is a method for promoting nucleation in the liquid metal or changing the crystal growth process by adding a small amount of active substances into the metal liquid, and the modifier used in the production is a nucleation modifier and an adsorption modifier. The adsorption alterant has the characteristics of low melting point, capability of remarkably reducing the liquidus temperature of the alloy, large atomic radius, small solid solution amount in the alloy, enrichment on a phase interface during crystal growth, inhibition of crystal growth, formation of larger composition supercooling, formation of fine necking by crystal branches, easy fusing, promotion of crystal dissociation and crystal nucleus increase. However, it has a disadvantage that it often causes hot shortness due to the presence between dendrites and grain boundaries. The nucleation alterant has the action mechanism that substances which can generate non-spontaneous crystal nuclei are added into a melt, so that the melt achieves the purpose of refining crystal grains through heterogeneous nucleation in the solidification process. The nucleation modificator is generally added in the form of a compound or an intermediate alloy.

Nowadays, aluminum alloys have been widely used in the fields of automobiles, aerospace and the like due to the characteristics of small density, high specific strength, high strength and toughness, excellent casting performance and the like, and aluminum-silicon alloys in the aluminum alloys have very prominent use effect in some fields. Therefore, it is becoming more and more important how to improve the mechanical properties of aluminum alloys, especially aluminum-silicon alloys. In the prior art, grain refinement is one of important means for improving the mechanical properties of aluminum alloy. Wherein, the addition of nucleation alterant is one of the main means for thinning the aluminum alloy.

As for the selection of the nucleation modifier, the aluminum alloy is generally selected from compounds containing elements such as Ti, Zr, B, C, etc. as the grain refiner, i.e. the nucleation modifier. However, for the aluminum-silicon alloy with higher silicon content (more than 4 wt.%), such as the aluminum-silicon alloy with the mark of A356, the current commercial aluminum alloy refiner, such as Al-Ti-B intermediate alloy, has unsatisfactory refining effect. The research shows that in addition to the problem of sedimentation, the more important point is the TiB which plays a refining role after the Al-Ti-B intermediate alloy is added₂The particles are poisoned by the original Si atoms in the Al-Si alloy and lose the original refining effect. The Al-B, Al-Nb-B, Al-Ti-Nb-B intermediate alloy has a larger limitation although being less influenced by Si element in the Al-Si casting alloy. After the Al-B intermediate alloy is added into the aluminum alloy, B element is easily adsorbed and settled by impurity element atoms such as Ti, Zr and the like; Al-Nb-B master alloy is mainly refined into NbB particles ₂The density difference of the particles is obvious compared with Al, and the particles can be mixed in a short time<30 minutes) to settle to the bottom of the holding furnace to form slag; the Al-Ti-Nb-B master alloy has high Nb content requirement, which results in high cost. Therefore, the demand for a more economical and efficient aluminum-silicon alloy refiner is urgent in actual industrial production.

The Chinese patent application numbers are: CN201910574449.1, published as: the patent document 8/23/2019 discloses an Al-V-B refiner for casting aluminum-silicon alloy, a preparation method and application thereof, wherein the chemical element composition and the mass percentage of the Al-V-B refiner are 80.0-95.8% of aluminum, 2.1-10.0% of vanadium and 2.1-10.0% of boron; the phase composition comprises alpha-Al solid solution with aluminum as matrix and particle particles with particle size of 2-100 μm, and the particle phase contains VAl₃Phase, VB₂Phase sum AlB₂And (4) phase. In the application of casting aluminum-silicon alloy, the grain size of alpha-Al in the casting aluminum-silicon alloy is refined to be below 220 microns. The preparation method is a fluoride salt method and comprises the following steps: firstly, weighing raw materials; then Al-V-B alloy smelting is carried out.

The Chinese patent application numbers are: CN201811226151.3, published date: the patent literature of 2019, 1 month and 11 days discloses a grain refiner with a molecular formula of Al _xV_yB_zR_100-x-y-zWherein R is an element harmless to the alloy being refined; the percentage contents of each element are respectively as follows: x is 20-99.8 wt.%, y is 0.1-40 wt.%, and z is 0.1-40 wt.%. Meanwhile, the invention also discloses a preparation method and specific application of the refiner.

The two schemes are both grain refiners for aluminum-silicon alloy, but in actual use, it is found that for aluminum-silicon alloy with higher silicon content, although the refining effect of the grain refiners in the two schemes is not affected by silicon element, the overall refining effect of the aluminum-silicon alloy in industrial production is not ideal, and especially when the grain refiner is used for casting aluminum-silicon alloy in some special demand fields, the refining effect is often not stable enough or cannot reach the expected value, so that the mechanical property of the finally cast aluminum-silicon alloy cannot meet the use requirement, and further the problem occurs when the aluminum-silicon alloy is specifically applied. The main reason for the above problems is that the addition amount of the refiner in the alloy melt is required to be less than or equal to 0.5% by mass in industrial production. The amount of the refining agent added is limited, on the one hand, because of cost considerations, and on the other hand, the excessive addition of the refining agent is prevented from contaminating the molten metal. Of course, to obtain better grain refining, one would add more grain refiner to the alloy melt. For example, the amount of the refiner added in CN201910574449.1 accounts for 2% of the mass of the alloy melt. Although the fine crystal effect is better finally obtained, the method is hardly accepted in industrial production. Therefore, if the prepared refiner with the addition amount of less than 1 percent or even 0.5 percent and simultaneously having good grain refining effect becomes a problem which is urgently needed to be solved at present, the preparation method has important application value. In addition, in actual industrial production, the refiner is generally required to be capable of keeping the temperature in the metal melt for 4 hours without sedimentation degradation. This requires a fine and diffuse distribution of the effective nucleation particles in the refiner. Therefore, how to prepare the above-mentioned desired particles of the refiner is of great importance for the refining and commercial application.

Disclosure of Invention

1. Problems to be solved

Aiming at the problem that the refining effect of the existing grain refiner on the casting of aluminum-silicon alloy in the field of special requirements is not ideal, the invention provides the Al-V-Ti-B grain refiner, which effectively improves the refining effect of the refiner on aluminum alloy, especially aluminum-silicon alloy, and has stable refining effect by unique design on the components of the refiner.

The invention also provides a unique preparation method aiming at the grain refiner, so that the grain refiner with higher refining effect can be prepared, and the refining effect is stable.

The invention also provides an application method of the grain refiner, which is applied to casting aluminum-silicon alloy and proves that excellent refining effect can be obtained and the refining effect is stable.

2. Technical scheme

In order to solve the above problems, the present invention adopts the following technical solutions.

An Al-V-Ti-B grain refiner comprises the following chemical components in percentage by mass: v: 0.1-10 wt.%, B: 0.1-10 wt.%, Ti: 0.1-10 wt.%, the balance being Al, elements not affecting the refining effect and unavoidable impurity elements; in the grain refiner, the atomic ratio of (V + Ti) to B is more than or equal to 0.25 and less than or equal to 2.

As a further improvement of the technical proposal, in the grain refiner, the atomic ratio of (V + Ti) to B is more than or equal to 0.3 and less than 0.8.

As a further improvement of the technical proposal, the grain refiner contains (V/Ti) B₂Particles of (V/Ti) B₂(V/Ti) B having an average particle diameter of less than 2 μm and not less than 95%₂The particle size of the particles is less than 3 μm.

As a further improvement of the technical scheme, in the grain refiner, the mass percentage of Ti is as follows: 3.5-8 wt.%.

The preparation method of the Al-V-Ti-B grain refiner comprises the following steps:

first, make up

Configuring a V source, a B source, an Al source and a Ti source according to the set component range of the Al-V-Ti-B grain refiner;

secondly, smelting raw materials

Placing a V source, a B source, an Al source and a Ti source at a set temperature, mixing, smelting and stirring to form a melt after full reaction;

three, solidification deformation

And cooling the melt formed in the second step to form a refiner alloy material, and then carrying out plastic deformation on the refiner alloy material to prepare the wire rod with the required specification.

As a further improvement of the technical scheme, the specific process of the second step is as follows: mixing and smelting a V source, a B source and an Al source at 900-1200 ℃, preserving heat for 0.5-2 h, stirring and slagging off; and then adding a Ti source into the melt, smelting at 900-1100 ℃, preserving heat for 0.5-2 h, stirring and slagging off to form the melt after full reaction.

As a further improvement of the technical scheme, the specific process of the second step is as follows: mixing and smelting a V source, a Ti source and an Al source at 900-1200 ℃, preserving heat for 0.5-2 h, stirring and slagging off; and then adding a B source into the melt, preserving the heat for 0.5-2 hours at 900-1100 ℃, stirring and slagging off to form the melt after full reaction.

As a further improvement of the technical scheme, the specific process of the second step is as follows: and (3) mixing and smelting the V source, the Ti source, the B source and the Al source at 900-1200 ℃, preserving heat for 0.5-2 h, stirring and slagging off to form a melt after full reaction.

As a further improvement of the technical scheme, the specific process of the second step is as follows: mixing and smelting a Ti source, a B source and an Al source at 900-1200 ℃, preserving heat for 0.5-2 h, stirring and slagging off; and then adding a V source into the melt, smelting at 900-1100 ℃, preserving heat for 0.5-2 h, stirring and slagging off to form the melt after full reaction.

As a further improvement of the technical scheme, the V source is an AlV alloy or V powder or an oxide of V; the B source is KBF4 or AlB alloy; the Ti source is KTiF4 or AlTi alloy or Ti powder; the Al source is industrial pure aluminum.

The application method of the Al-V-Ti-B grain refiner comprises the following steps:

Firstly, smelting

Heating and melting the aluminum alloy to be refined;

secondly, adding a refiner

Adding the prepared Al-V-Ti-B grain refiner into the alloy solution, and preserving heat for 10-360min after the Al-V-Ti-B grain refiner is completely melted; the mass of the added Al-V-Ti-B grain refiner is 0.1 to 1 percent of the mass of the alloy solution;

third, casting

And casting the melt subjected to heat preservation into a mold, and cooling to obtain a casting.

3. Advantageous effects

Compared with the prior art, the invention has the beneficial effects that:

(1) the Al-V-Ti-B grain refiner mainly comprises Al, V, Ti and B elements, and the Ti element can enter VB in the aluminothermic reaction for preparing the refiner by uniquely researching and designing the V, Ti and B elements and the proportion₂The particles are doped and substituted to form a single phase (V/Ti) B₂The particles (see figure 1) further change the microstructure, appearance, size, agglomeration degree, element composition and distribution of the particles, and the particles have smaller atomic amplitude of a termination layer and larger surface potential well depth, so that the degree of order of an initial pre-nucleation layer can be obviously improved, and heterogeneous nucleation of Al is effectively promoted; in particular, in (V/Ti) B₂An atomic layer of a compound of Ti and V (e.g., Al) is formed on the surface of the particles ₃Ti type), the atomic arrangement of the compound atomic layer has very small mismatching degree with the alloy needing to be refined, the energy barrier of nucleation in the solidification process can be obviously reduced, heterogeneous nucleation can be effectively promoted, grain refinement is promoted finally when alloy cast ingots or castings are prepared, and (V/Ti) B is formed by doping₂Particle phase vs. TiB₂The particles have weaker capability of adsorbing Si elements, so that the adsorption of the Si elements on the surfaces of the particles is reduced, and the particles have better silicon poisoning resistance.

(2) The invention relates to a preparation method of an Al-V-Ti-B grain refiner, which designs the preparation process of the refiner uniquely and introduces Ti element doping and replaces Ti element(V/Ti) B which is fine and dispersedly distributed₂Particles, in comparison with VB in Al-V-B refiner₂The particles can provide better conditions for heterogeneous nucleation, the refining effect is obvious, and (V/Ti) B₂The particle density of the particles is smaller, and the anti-settling capacity is stronger, so that the quality of the refiner is improved.

(3) The preparation method of the aluminum alloy grain refiner has the advantages of easily obtained required raw materials, low cost, uncomplicated overall preparation process and good popularization prospect.

(4) The application method of the aluminum alloy grain refiner has the advantages that the grain refiner has excellent refining effect on aluminum alloy cast ingots or castings, particularly the refining effect on aluminum-silicon alloys, the refining effect is stable, and the refining effect is not degraded after the grain refiner is added for five hours in the actual alloy preparation process.

Drawings

Since the color of the photograph obtained in the experiment can visually reflect the grain size and state in the experiment, a color picture is used.

FIG. 1 shows (V/Ti) B₂Elemental distribution map of the particles;

FIG. 2 is a schematic drawing showing a structure of ((V/Ti) B) of a refiner of example 7₂Average particle size 1.1 μm);

FIG. 3 is a schematic drawing showing a structure of ((V/Ti) B) of a refiner of example 9₂Average particle size 0.98 μm);

FIG. 4 is a structural diagram (VB) of a finished refiner of comparative example 2₂Average particle size 2.01 μm);

FIG. 5 is a structure diagram (VB) of a refiner prepared in comparative example 3₂Average particle size 6.65 μm);

FIG. 6 is a structural diagram (VB) of a refiner prepared in comparative example 4₂Average particle size 2.24 μm);

FIG. 7 is a structure diagram of a refined ingot of example 23;

FIG. 8 is a structure diagram of a refined ingot of example 25;

FIG. 9 is a structure diagram of a refined ingot according to example 31;

FIG. 10 is a structure diagram of a refined ingot of example 32;

FIG. 11 is a structure diagram of a refined ingot in example 33;

FIG. 12 is a texture map of a refined ingot of example 34;

FIG. 13 is a structure diagram of a refined ingot of example 35;

Wherein the number in the refiner represents the mass percent of the element, the mass percent of Al is not represented by a number, and the mass percent of Al and the mass percent of the remaining elements are added up to nearly or equal to 100% in consideration of the possible presence of some inevitable impurity elements in an actual experiment.

Detailed Description

The invention is further described below with reference to specific embodiments and the accompanying drawings.

At present, for aluminum-silicon alloys with high silicon content (more than 4 wt.%), the refining effect of some commercial aluminum alloy refiners is not ideal, and for this reason, this embodiment provides an Al-V-Ti-B grain refiner, which uses chemical components in unique proportions, and is mainly used for casting aluminum-silicon alloys, but has better grain refining effect for magnesium-aluminum alloys or other alloys.

The alloy grain refiner comprises the following main chemical components in percentage by mass: v: 0.1-10 wt.%, B: 0.1-10 wt.%, Ti: 0.1-10 wt.%, and elements that do not affect the refining effect and unavoidable impurity elements. Wherein, the elements which do not influence the refining effect comprise Fe, Zn, Mn, Cu, Mg, Cr, Sr, Zr, Sc, Li and the like, the single content of the elements is usually not higher than 0.5 wt.%, and the total content of inevitable impurity elements is not more than 1 wt.%.

The inventor finds out in experiments that on the basis of reasonably designing the mass percentage range of the V, Ti and B elements in the grain refiner, a single-phase (V/Ti) B with V and Ti doped and replaced mutually can be formed in the grain refiner by controlling the atomic ratio of the three elements₂The particles, and further the microstructure, the appearance and the like of the particles,The size, agglomeration degree, element composition and distribution are changed, and the particles are the most main particles which play a fine crystal role in the Al-V-Ti-B refiner. The particles have smaller atomic amplitude of a termination layer and larger surface potential well depth, can obviously improve the degree of order of an initial pre-nucleation layer, effectively promote heterogeneous nucleation of Al and improve the refining effect. In particular, in (V/Ti) B₂An atomic layer of a compound of Ti and V (e.g., Al) is formed on the surface of the particles₃Ti type), the atomic arrangement of the compound atomic layer has very small mismatching degree with the alloy needing to be refined, the energy barrier of nucleation in the solidification process can be obviously reduced, heterogeneous nucleation can be effectively promoted, the grain refinement is promoted finally when the alloy ingot or casting is prepared, and the (V/Ti) B is formed by doping₂Particle phase vs. TiB₂The particles have weaker capability of adsorbing Si element, so that the adsorption of the Si element on the surface of the particles is reduced, and the particles have better silicon poisoning resistance.

Wherein, in the grain refiner, the atomic ratio of (V + Ti) to B is more than or equal to 0.25 and less than or equal to 2. However, it has been found through extensive experimental studies on the atomic ratios of the three elements that when the atomic ratio of 0.25. ltoreq. (V + Ti) to B is in the above range<0.5, when the particles in the refiner are mainly composed of (V/Ti) B₂And AlB₂Particle composition and with increasing atomic ratio, (V/Ti) B₂The proportion of the particles gradually increases. When the atomic ratio of (V + Ti) to B reaches 0.5, it is almost entirely composed of (V/Ti) B₂And (4) particle composition. When the atomic ratio of (V + Ti) to B is 0.5 < 2, the particles in the refiner are mainly composed of (V/Ti) B₂And Al₃Ti、Al₃V、Al₃(V/Ti) and the like, and (V/Ti) B with a gradually decreasing atomic ratio₂The proportion of the particles gradually increases. Therefore, the most preferable range of the atomic ratio of the three elements is 0.3. ltoreq. V + Ti with respect to the atomic ratio of B<0.8。

Meanwhile, it was found through further studies that when Ti is in the range of 3.5 to 8 wt.% in terms of the mass percent of the grain refiner, and B is in the range of 0.5 to 0.95 wt.%, (V/Ti) B₂The generation amount and the thinning effect of the particles are obvious for the aluminum alloy, particularly the aluminum-silicon alloy.

In addition, in the aboveBased on the content, the experiment shows that if the generated (V/Ti) B is controlled ₂The particles and the rest particles have smaller particle sizes, and the refining effect of the grain refiner can be obviously improved. Among them, (V/Ti) B which plays a major role in refining₂(V/Ti) B having an average particle diameter of 2 μm or less and 95% or more₂The diameter of the particles is less than 3 μm, and Al₃Ti、Al₃V、Al₃(V/Ti) and AlB₂The particle size of the particles is less than 50 μm.

To produce a catalyst having (V/Ti) B satisfying the use conditions₂The invention relates to a grain refiner of particles, which combines the component range and atomic ratio of the grain refiner, and uniquely designs the process and parameters of a preparation method, and the process and the parameters are as follows:

first, batching

The amounts of the V source, the B source, the Al source and the Ti source are configured according to the set composition range of the Al-V-Ti-B grain refiner.

Secondly, smelting raw materials

And (3) placing the V source, the B source, the Al source and the Ti source at a set temperature for mixing, smelting and stirring to form a melt after full reaction. The method is specifically divided into the following four types:

(1) mixing and smelting a V source, a B source and an Al source at 900-1200 ℃, preserving heat for 0.5-2 h, stirring and slagging off; and then adding a Ti source into the melt, smelting at 900-1100 ℃, preserving heat for 0.5-2 h, stirring and slagging off to form the melt after full reaction.

(2) Mixing and smelting a V source, a Ti source and an Al source at 900-1200 ℃, preserving heat for 0.5-2 h, stirring and slagging off; and then adding a source B into the melt, preserving the heat for 0.5-2 h, stirring and slagging off to form the melt after full reaction.

(3) And (3) mixing and smelting the V source, the Ti source, the B source and the Al source at 900-1200 ℃, preserving heat for 0.5-2 h, stirring and slagging off to form a melt after full reaction.

(4) Mixing and smelting a Ti source, a B source and an Al source at 900-1200 ℃, preserving heat for 0.5-2 h, stirring and slagging off; and then adding a V source into the melt, smelting at 900-1100 ℃, preserving heat for 0.5-2 h, stirring and slagging off to form the melt after full reaction.

Three, solidification deformation

And (4) introducing the melt formed in the step two into a mold or a crystallizer for cooling to form a refiner alloy material, and then, plastically deforming the refiner alloy material according to needs to prepare a wire rod with a required specification. The plastic deformation process can adopt a continuous casting and rolling mode, and also can adopt a mode of casting into ingots and then extruding.

In the method, a V source is AlV alloy or V powder or V oxide, a B source is KBF4 or AlB alloy, a Ti source is KTiF4 or AlTi alloy or Ti powder, and an Al source is industrial pure aluminum.

The preparation method carries out unique design on the preparation process of the refiner, and adopts Ti element doping and replacement of fine and dispersedly distributed (V/Ti) B₂Particles, in comparison with VB in Al-V-B refiner₂Particles which can provide better conditions for heterogeneous nucleation, have obvious refining effect and (V/Ti) B ₂The particle density of the particles is smaller, and the anti-settling capacity is stronger, so that the quality of the refiner is improved. In addition, the method has the advantages of easily obtained raw materials, low cost, uncomplicated integral preparation process and good popularization prospect.

The application method of the grain refiner comprises the following steps:

firstly, smelting

Heating and melting the aluminum alloy to be refined;

secondly, adding a refiner

Adding the prepared Al-V-Ti-B grain refiner into the alloy solution, and preserving the heat for 10-360min after the Al-V-Ti-B grain refiner is completely melted; the mass of the added Al-V-Ti-B grain refiner is 0.1-1% of that of the alloy solution;

third, casting

And casting the heat-preserved melt into a mold, and cooling to obtain a casting.

Practical application shows that the refiner has a good refining effect on aluminum alloy, magnesium alloy and zinc alloy cast ingots or castings, particularly has an excellent refining effect on aluminum-silicon alloys, and is stable in refining effect, and the refining effect is not degraded after the refiner is added for five hours in the actual alloy preparation process.

Example 1

1000kg of an aluminum alloy grain refiner Al-10V-10Ti-10B was prepared from commercially pure aluminum, potassium fluotitanate, Al-65V alloy, potassium fluoborate (the numerical values represent the mass percentages of the elements, the mass percentage of Al is not represented by the numerical values, and the mass percentage of Al and the mass percentage of the remaining elements are added up to or equal to 100% in consideration of the possible presence of some inevitable impurity elements in practical experiments).

First, batching

Calculating and preparing industrial pure aluminum, potassium fluotitanate, Al-65V alloy and potassium fluoborate with corresponding mass according to the proportion of each component of a grain refiner Al-10V-10Ti-10B, and drying prepared raw materials, a crucible and other appliances which directly contact the raw materials (melt) in an oven at 100-200 ℃ in advance.

II, forming VB₂Granules

Putting the dried industrial pure aluminum, Al-65V intermediate alloy and potassium fluoborate powder in the step one into a crucible to be smelted at 1200 ℃, preserving heat for 2 hours after smelting, continuously stirring, and finally slagging off to form the powder containing VB₂A melt of the granules.

III, modification of Ti element

To contain VB₂Adding potassium fluotitanate into the melt of the particles, keeping the temperature for 2 hours at 1100 ℃, stirring and slagging off to form a fully reacted melt.

Fourthly, solidification

And (4) guiding the melt formed in the third step into a mold or a crystallizer for cooling to form a refiner alloy material Al-10V-10 Ti-10B.

Example 2

1kg of an aluminum alloy grain refiner Al-0.1V-0.1Ti-0.1B (numerical representation of the mass percentages of elements, considering that some inevitable impurity elements may be present in practical experiments, the mass percentage of Al and the mass percentage of the remaining elements are added up to or close to 100%) is prepared from commercially pure aluminum, Ti powder, Al-5V alloy, Al-3B alloy.

First, batching

Calculating and preparing industrial pure aluminum, Ti powder, Al-5V alloy and Al-3B alloy with corresponding mass according to the proportion of each component of a grain refiner Al-0.1V-0.1Ti-0.1B, and drying prepared raw materials, a crucible and other appliances which directly contact the raw materials (melt) in an oven at 100-200 ℃ in advance.

II, forming VB₂Granules

Putting the industrial pure aluminum, the Al-5V alloy and the Al-3B alloy which are dried in the step one into a crucible to be smelted at 900 ℃, preserving heat for 0.5h after smelting, continuously stirring, and finally slagging off to form the alloy containing VB₂A melt of the particles.

III, modification of Ti element

To contain VB₂Adding Ti powder into the melt of the particles, continuously preserving the heat for 0.5h at 900 ℃, stirring and slagging off to form a fully reacted melt.

Fourthly, solidification

And (4) guiding the melt formed in the third step into a mold or a crystallizer for cooling to form a refiner alloy material Al-0.1V-0.1 Ti-0.1B.

Example 3

100kg of an aluminum alloy grain refiner Al-5V-5Ti-5B (numerical representation of the mass percentages of elements, considering that some inevitable impurity elements may be present in practical experiments, the sum of the mass percentage of Al and the mass percentage of the remaining elements is close to or equal to 100%) was prepared from commercially pure aluminum, potassium fluotitanate, Al-65V alloy, potassium fluoborate.

First, batching

Calculating and preparing industrial pure aluminum, potassium fluotitanate, Al-65V alloy and potassium fluoborate with corresponding mass according to the proportion of each component of a grain refiner Al-5V-5Ti-5B, and drying prepared raw materials, a crucible and other appliances which directly contact the raw materials (melt) in an oven at 100-200 ℃ in advance.

II, forming VB₂Granules

Putting the dried industrial pure aluminum, Al-65V alloy and potassium fluoborate in the first step into a crucible to be smelted at 1100 ℃, preserving heat for 1.5 hours after smelting, continuously stirring, and finally slagging off to form the material containing VB₂A melt of the granules.

III, modification of Ti element

To contain VB₂Adding potassium fluotitanate into the melt of the particles, keeping the temperature for 1.5h at 1000 ℃, stirring and slagging off to form a fully reacted melt;

fourthly, solidification

And (4) guiding the melt formed in the third step into a mold or a crystallizer for cooling to form a refiner alloy material Al-5V-5 Ti-5B.

Example 4

1kg of an aluminum alloy grain refiner Al-1V-3.5Ti-1.25B (numerical values represent mass percentages of elements, and the sum of the mass percentage of Al and the mass percentage of the remaining elements is close to or equal to 100% in consideration of the possibility of the presence of some inevitable impurity elements in practical experiments) was prepared from commercially pure aluminum, potassium fluotitanate, Al-5V alloy, potassium fluoborate.

First, batching

Calculating and preparing industrial pure aluminum, potassium fluotitanate, Al-65V alloy and potassium fluoborate with corresponding mass according to the proportion of each component of a grain refiner Al-1V-3.5Ti-2B, and drying prepared raw materials, a crucible and other appliances which directly contact the raw materials (melt) in an oven at 100-200 ℃ in advance.

II, forming VB₂Granules

Putting the industrial pure aluminum, the Al-5V intermediate alloy and the potassium fluoborate powder dried in the step one into a crucible to be smelted at 980 ℃, preserving heat for 1h and continuously stirring after smelting, and finally slagging off to form the powder containing VB₂A melt of the particles.

III, modification of Ti element

To VB₂Adding potassium fluotitanate into the melt of the particles, keeping the temperature for 1 hour at 950 ℃, stirring and slagging off to form a fully reacted melt.

Fourthly, solidification

And (4) guiding the melt formed in the third step into a mold or a crystallizer for cooling to form a refiner alloy material Al-1V-3.5 Ti-2B.

Example 5

1kg of an aluminum alloy grain refiner Al-1V-8Ti-1B (numerical representation of the mass percentages of elements, considering that some inevitable impurity elements may be present in practical experiments, the sum of the mass percentages of Al and the mass percentages of the remaining elements is close to or equal to 100%) was prepared from commercially pure aluminum, potassium fluotitanate, Al-5V alloy, potassium fluoborate.

First, batching

Calculating and preparing corresponding mass of industrial pure aluminum, potassium fluotitanate, Al-5V alloy and potassium fluoborate according to the proportion of each component of a grain refiner Al-1V-8Ti-1B, and drying prepared raw materials, a crucible and other apparatuses which are in direct contact with the raw materials (melt) in an oven at 100-200 ℃ in advance.

II, forming VB₂Granules

Putting the industrial pure aluminum, the Al-5V intermediate alloy and the potassium fluoborate powder dried in the step one into a crucible to be smelted at 950 ℃, preserving heat for 1h and continuously stirring after smelting, and finally slagging off to form the powder containing VB₂A melt of the particles.

III, modification of Ti element

To VB₂Adding potassium fluotitanate into the melt of the particles, keeping the temperature for 1.5h at 950 ℃, stirring and slagging off to form fully reacted melt.

Fourthly, solidification

And (4) guiding the melt formed in the third step into a mold or a crystallizer for cooling to form a refiner alloy material Al-1V-8 Ti-1B.

Example 6

10kg of an aluminum alloy grain refiner Al-1V-5Ti-1B (numerical representation of the mass percent of elements, considering that some inevitable impurity elements may exist in practical experiments, the sum of the mass percent of Al and the mass percent of the remaining elements is close to or equal to 100%) is prepared from industrial pure aluminum, Ti powder, Al-5V alloy, Al-3B alloy.

First, batching

Calculating and preparing industrial pure aluminum, potassium fluotitanate, Al-5V alloy and Al-3B alloy with corresponding mass according to the proportion of each component of a grain refiner Al-1V-5Ti-1B, and drying prepared raw materials, a crucible and other appliances which directly contact the raw materials (melt) in an oven at 100-200 ℃ in advance.

II, forming VB₂Granules

The dried industrial pure aluminum and Al-5V alloy in the step one,Placing Al-3B alloy into a crucible to be smelted at 950 ℃, preserving heat for 1h after smelting, continuously stirring, and finally slagging off to form a material containing VB₂A melt of the particles.

III, modification of Ti element

Fourthly, solidification

And (4) guiding the melt formed in the third step into a mold or a crystallizer for cooling to form a refiner alloy material Al-1V-5 Ti-1B.

Example 7

1kg of an aluminum alloy grain refiner Al-1.5V-1Ti-0.65B (numerical values represent mass percentages of elements, and the sum of the mass percentage of Al and the mass percentage of the remaining elements is close to or equal to 100% in consideration of the presence of some inevitable impurity elements in practical experiments) was prepared from commercially pure aluminum, potassium fluotitanate, Al-5V alloy, potassium fluoborate.

First, batching

Calculating and preparing industrial pure aluminum, potassium fluotitanate, Al-5V alloy and potassium fluoborate with corresponding mass according to the proportion of each component of a grain refiner Al-1.5V-1Ti-0.65B, and drying prepared raw materials, a crucible and other apparatuses which directly contact the raw materials (melt) in an oven at 100-200 ℃ in advance.

II, forming VB₂Granules

Putting the industrial pure aluminum, the Al-5V intermediate alloy and the potassium fluoborate powder dried in the step one into a crucible to be smelted at 950 ℃, preserving heat for 0.5h after smelting and continuously stirring, and finally slagging off to form the powder containing VB₂A melt of the particles.

III, modification of Ti element

To VB₂Adding potassium fluotitanate into the melt of the particles, keeping the temperature for 0.5h at 950 ℃, stirring and slagging off to form fully reacted melt.

Fourthly, solidification

And (4) introducing the melt formed in the step three into a casting mold for cooling to form a refiner alloy material Al-1.5V-1Ti-0.65B cast ingot.

Plastic deformation

Heating and extruding the refiner alloy cast ingot to be deformed into a wire rod with the diameter of 10 mm.

Example 8

A grain refiner Al-3V-1Ti-1B (numerical representation of the mass percentages of elements, considering the possible presence of some inevitable impurity elements in practical experiments, the sum of the mass percentages of Al and the mass percentages of the remaining elements being close to or equal to 100%) of 5kg of an aluminum alloy was prepared from commercially pure aluminum, potassium fluotitanate, Al-65V alloy, potassium fluoborate.

First, batching

Calculating and preparing corresponding mass of industrial pure aluminum, potassium fluotitanate, Al-5V alloy and potassium fluoborate according to the proportion of each component of a grain refiner Al-3V-1Ti-1B, and drying prepared raw materials, a crucible and other appliances which directly contact the raw materials (melt) in an oven at 100-200 ℃ in advance.

II, forming VB₂Granules

Putting the industrial pure aluminum, the Al-5V intermediate alloy and the potassium fluoborate powder dried in the step one into a crucible to be smelted at 1100 ℃, preserving heat for 1.5 hours after smelting and continuously stirring, and finally slagging off to form the powder containing VB₂A melt of the particles.

III, modification of Ti element

To VB₂Adding potassium fluotitanate into the melt of the particles, keeping the temperature for 0.5h at 950 ℃, stirring and slagging off to form a fully reacted melt.

Fourthly, solidification

And (4) guiding the melt formed in the third step into a mold or a crystallizer for cooling to form a refiner alloy material Al-3V-1 Ti-1B.

Example 9

1kg of an aluminum alloy grain refiner Al-1V-1Ti-0.9B (numerical values represent the mass percentages of elements, and the sum of the mass percentage of Al and the mass percentage of the remaining elements is close to or equal to 100% in consideration of inevitable impurity elements which may be present in practical experiments) was prepared from commercially pure aluminum, potassium fluotitanate, Al-5V alloy, and potassium fluoborate.

First, batching

Calculating and preparing industrial pure aluminum, potassium fluotitanate, Al-5V alloy and potassium fluoborate with corresponding mass according to the proportion of each component of a grain refiner Al-1V-1Ti-0.9B, and drying prepared raw materials, a crucible and other appliances which directly contact the raw materials (melt) in an oven at 100-200 ℃ in advance.

II, forming VB₂Granules

Putting the industrial pure aluminum, the Al-5V intermediate alloy and the potassium fluoborate powder dried in the step one into a crucible to be smelted at the temperature of 950 ℃, preserving heat for 0.5h after smelting and continuously stirring, and finally slagging off to form the powder containing VB₂A melt of the particles.

III, modification of Ti element

To contain VB₂Adding potassium fluotitanate into the melt of the particles, keeping the temperature for 0.5h at 950 ℃, stirring and slagging off to form a fully reacted melt.

Fourthly, solidification

And (4) introducing the melt formed in the step three into a wheel type crystallizer for continuous cooling, and continuously casting to form a refiner alloy material Al-1V-1 Ti-0.9B.

Fifth, plastic deformation

Continuously rolling and deforming the continuous casting refiner alloy material into a wire rod with the diameter of 9.5 mm.

Example 10

1kg of an aluminum alloy grain refiner Al-1.5V-0.5Ti-1.8B (numerical values represent the mass percentages of elements, considering that some inevitable impurity elements may be present in practical experiments, the mass percentage of Al and the mass percentage of the remaining elements are added up to or near 100%) is prepared from commercially pure aluminum, potassium fluotitanate, Al-5V alloy, potassium fluoborate.

First, batching

Calculating and preparing industrial pure aluminum, potassium fluotitanate, Al-5V alloy and potassium fluoborate with corresponding mass according to the proportion of each component of a grain refiner Al-1.5V-0.5Ti-1.8B, and drying prepared raw materials, a crucible and other apparatuses which are in direct contact with the raw materials (melt) in an oven at 100-200 ℃ in advance.

II, forming VB₂Granules

The dried industrial pure aluminum in the step one,Putting Al-5V intermediate alloy and potassium fluoborate powder into a crucible to be smelted at 950 ℃, preserving heat for 1h after smelting, continuously stirring, and finally slagging off to form a material containing VB₂A melt of the particles.

III, modification of Ti element

To contain VB₂Adding potassium fluotitanate into the melt of the particles, keeping the temperature for 0.5h at 920 ℃, stirring and slagging off to form a fully reacted melt.

Fourthly, solidification

And (4) guiding the melt formed in the third step into a mold or a crystallizer for cooling to form a refiner alloy material Al-1.5V-0.5 Ti-1.8B.

Example 11

1kg of an aluminum alloy grain refiner Al-2V-2Ti-3B (numerical representation of the mass percentages of elements, considering that some inevitable impurity elements may be present in practical experiments, the sum of the mass percentages of Al and the mass percentages of the remaining elements is close to or equal to 100%) was prepared from commercially pure aluminum, potassium fluotitanate, Al-5V alloy, potassium fluoborate.

First, batching

Calculating and preparing corresponding mass of industrial pure aluminum, potassium fluotitanate, Al-5V alloy and potassium fluoborate according to the proportion of each component of a grain refiner Al-2V-2Ti-3B, and drying prepared raw materials, a crucible and other appliances which directly contact the raw materials (melt) in an oven at 100-200 ℃ in advance.

II, forming VB₂Granules

Putting the industrial pure aluminum, the Al-5V intermediate alloy and the potassium fluoborate powder dried in the step one into a crucible to be smelted at 1000 ℃, preserving heat for 1h and continuously stirring after smelting, and finally slagging off to form the powder containing VB₂A melt of the particles.

III, modification of Ti element

To VB₂Adding potassium fluotitanate into the melt of the particles, keeping the temperature for 1h at 950 ℃, stirring and slagging off to form a fully reacted melt.

Fourthly, solidification

And (4) guiding the melt formed in the third step into a mold or a crystallizer for cooling to form columnar or strip refiner alloy material Al-2V-2 Ti-3B.

Example 12

First, batching

Calculating and preparing industrial pure aluminum, potassium fluotitanate, Al-5V alloy and potassium fluoborate with corresponding mass according to the proportion of each component of a grain refiner Al-1V-1Ti-0.9B, and drying prepared raw materials, a crucible and other appliances which are directly contacted with the raw materials (melt) in an oven at 100-200 ℃ in advance.

Secondly, forming particles

And (3) putting the dried industrial pure aluminum, Al-5V intermediate alloy and potassium fluotitanate powder in the step one into a crucible for smelting at 980 ℃, preserving heat for 1h after melting, continuously stirring, and finally slagging off.

Adding potassium fluoborate into the melt, keeping the temperature for 1h at 950 ℃, stirring and slagging off to form a fully reacted melt.

Thirdly, solidification

And (4) guiding the melt formed in the step two into a mold or a crystallizer for cooling to form a refiner alloy material Al-1V-1 Ti-0.9B.

Example 13

First, make up

Secondly, forming particles

And (3) putting the dried industrial pure aluminum, Al-5V intermediate alloy, potassium fluotitanate and potassium fluoborate powder in the step one into a crucible to be smelted at 980 ℃, preserving heat for 2 hours after smelting and continuously stirring, and finally slagging off to form a melt containing particles.

Thirdly, solidification

And (4) guiding the melt formed in the second step into a mold or a crystallizer for cooling to form a refiner alloy material Al-1V-1 Ti-0.9B.

Example 14

First, batching

Secondly, forming particles

And (3) putting the dried industrial pure aluminum, potassium fluotitanate and potassium fluoborate powder in the step one into a crucible to be smelted at 1050 ℃, keeping the temperature for 1.5 hours after the powder is smelted, continuously stirring, and finally slagging off. Adding Al-5V alloy into the melt, keeping the temperature for 1.5h at 1000 ℃, stirring and slagging off to form a fully reacted melt.

Thirdly, solidification

Example 15

1kg of an aluminum alloy grain refiner Al-1V-1Ti-0.95B (numerical values represent the mass percentages of elements, and the sum of the mass percentage of Al and the mass percentage of the remaining elements is close to or equal to 100% in consideration of inevitable impurity elements which may be present in practical experiments) was prepared from commercially pure aluminum, potassium fluotitanate, Al-5V alloy, and potassium fluoborate.

First, make up

Calculating and preparing industrial pure aluminum, potassium fluotitanate, Al-5V alloy and potassium fluoborate with corresponding mass according to the proportion of each component of a grain refiner Al-1V-1Ti-0.95B, and drying prepared raw materials, a crucible and other appliances which are directly contacted with the raw materials (melt) in an oven at 100-200 ℃ in advance.

Secondly, forming particles

Thirdly, solidification

And (4) guiding the melt formed in the step two into a mold or a crystallizer for cooling to form a refiner alloy material Al-1V-1 Ti-0.95B.

Example 16

1kg of an aluminum alloy grain refiner Al-1V-1Ti-0.5B (numerical values represent the mass percentages of elements, and the sum of the mass percentage of Al and the mass percentage of the remaining elements is close to or equal to 100% in consideration of inevitable impurity elements which may be present in practical experiments) was prepared from commercially pure aluminum, potassium fluotitanate, Al-5V alloy, and potassium fluoborate.

First, batching

Calculating and preparing industrial pure aluminum, potassium fluotitanate, Al-5V alloy and potassium fluoborate with corresponding mass according to the proportion of each component of a grain refiner Al-1V-1Ti-0.5B, and drying prepared raw materials, a crucible and other appliances which are directly contacted with the raw materials (melt) in an oven at 100-200 ℃ in advance.

Secondly, forming particles

Thirdly, solidification

And (4) guiding the melt formed in the step two into a mold or a crystallizer for cooling to form a refiner alloy material Al-1V-1 Ti-0.5B.

Comparative example 1

1kg of an aluminum alloy grain refiner Al-1.5V-1Ti-0.65B (numerical values represent mass percentages of elements, and the sum of the mass percentage of Al and the mass percentage of the remaining elements is close to or equal to 100% in consideration of the possible presence of some inevitable impurity elements in practical experiments) was prepared from commercially pure aluminum, V powder, potassium fluotitanate, and potassium fluoborate.

First, batching

Calculating and preparing industrial pure aluminum, V powder, potassium fluotitanate and potassium fluoborate with corresponding mass according to the proportion of each component of a grain refiner Al-1.5V-1Ti-0.65B, and drying prepared raw materials, a crucible and other apparatuses which are in direct contact with the raw materials (melt) in an oven at 100-200 ℃ in advance.

Secondly, smelting raw materials

And (3) putting the industrial pure aluminum, the V powder, the potassium fluotitanate and the potassium fluoborate dried in the step one into a crucible to be smelted at 830 ℃, preserving heat for 3 hours after smelting, stirring and slagging off to form a melt after full reaction.

Thirdly, solidification

And (4) guiding the melt formed in the second step into a mold or a crystallizer for cooling to form a refiner alloy material Al-1.5V-1 Ti-0.65B.

Comparative example 2

1kg of grain refiner Al-7Si-1.5V-0.65B (numbers represent the mass percentages of elements, considering that some inevitable impurity elements may be present in practical experiments, the sum of the mass percentages of Al and the mass percentages of the remaining elements is close to or equal to 100%) is prepared from commercially pure aluminum, pure silicon, Al5V alloy, potassium fluoborate.

First, batching

Calculating and preparing corresponding mass of industrial pure aluminum, pure silicon, Al5V alloy and potassium fluoborate according to the proportion of each component of grain refiner Al-7Si-1.5V-0.65B, and drying prepared raw materials, crucibles and other appliances which are in direct contact with the raw materials (melt) in an oven at 100-200 ℃ in advance.

Secondly, smelting raw materials

Mixing and smelting pure aluminum, Al5V alloy and pure silicon at 950 ℃, keeping the temperature for 1h, stirring and skimming, then adding potassium fluoborate into the melt, keeping the temperature for 0.5h at 950 ℃, stirring and skimming to form a fully reacted melt.

Fourthly, solidification

And (4) guiding the melt formed in the third step into a mold or a crystallizer for cooling to form a refiner alloy material Al-7 Si-1.5V-0.65B.

Comparative example 3

1kg of an aluminum alloy grain refiner Al-1.5V-0.65B (numerical values represent the mass percentages of the elements, considering that some inevitable impurity elements may be present in practical experiments, the sum of the mass percentages of Al and the mass percentages of the remaining elements is close to or equal to 100%) is prepared from commercially pure aluminum, Al5V alloy, potassium fluoborate.

First, make up

Calculating and preparing pure aluminum, Al5V alloy and potassium fluoborate with corresponding mass according to the proportion of each component of a grain refiner Al-1.5V-0.65B, and drying prepared raw materials, crucibles and other appliances which directly contact the raw materials (melt) in an oven at 100-200 ℃ in advance.

II, forming VB₂Granules

Putting the industrial pure aluminum, Al5V alloy and potassium fluoborate dried in the step one into a graphite clay crucible for smelting at 850 ℃, preserving heat for 1h after smelting, stirring and slagging off, and finally forming the product containing VB ₂A melt of the particles.

Thirdly, solidification

And (4) introducing the melt formed in the second step into a mold or a crystallizer for cooling to form a refiner alloy material Al-1.5 V0.65B.

Comparative example 4

First, batching

Calculating and preparing industrial pure aluminum, AlV alloy and potassium fluoborate with corresponding mass according to the proportion of each component of a grain refiner Al-1.5V-0.65B, and drying prepared raw materials, a crucible and other appliances which directly contact the raw materials (melt) in an oven at 100-200 ℃ in advance.

Secondly, smelting raw materials

Mixing and smelting industrial pure aluminum, Al5V alloy and potassium fluoborate at 950 ℃, keeping the temperature for 1h, stirring and skimming, keeping the temperature at 950 ℃ for 0.5h, stirring and skimming to form a melt after full reaction.

Fourthly, solidification

And (4) guiding the melt formed in the third step into a mold or a crystallizer for cooling to form a refiner alloy material Al-1.5V-0.65B.

Example 17

First, batching

The raw materials are Al-10V-10Ti-10B grain refiner prepared in example 1 and industrial aluminum-silicon alloy (A356.2), and the raw materials are weighed according to a certain proportion, wherein the adding amount of the Al-10V-10Ti-10B grain refiner is 0.1 percent of the mass of the A356.2 alloy and is added into A356.2 alloy melt.

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace is increased to 740 ℃, then adding the Al-10V-10Ti-10B refiner into the crucible, stirring and preserving heat for 1 hour.

Thirdly, casting and solidifying

And pouring the alloy liquid in the crucible into a cast iron casting mold preheated to 350 ℃, and cooling to room temperature to obtain an ingot after refining the industrial aluminum-silicon alloy.

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The metallographic pictures were measured by the line-cut method (national standard GBT6394-2017) to have an average grain size of about 225. + -. 29 μm.

Example 18

First, make up

The raw materials are Al-0.1V-0.1Ti-0.1B grain refiner prepared in example 2 and industrial aluminum silicon alloy (A356.2), and the raw materials are weighed according to a certain proportion, wherein the adding amount of the Al-0.1V-0.1Ti-0.1B grain refiner is added into the A356.2 alloy melt according to 1% of the mass of the A356.2 alloy.

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace rises to 740 ℃, then adding Al-0.1V-0.1Ti-0.1B refiner into the crucible, stirring and preserving heat for 1 hour.

Thirdly, casting and solidifying

And pouring the alloy liquid in the crucible into a cast iron casting mold preheated to 350 ℃, and cooling to room temperature to obtain the cast ingot refined from the industrial aluminum-silicon alloy.

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The metallographic pictures were measured by the line-cut method (national standard GBT6394-2017) to have an average grain size of about 245. + -. 39 μm.

Example 19

First, batching

The raw materials are the Al-5V-5Ti-5B grain refiner prepared in the example 3 and the industrial aluminum-silicon alloy (A356.2), and the raw materials are weighed according to a certain proportion, wherein the adding amount of the Al-5V-5Ti-5B grain refiner is 0.5 percent of the mass of the A356.2 alloy and is added into the A356.2 alloy melt.

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace rises to 740 ℃, then adding an Al-5V-5Ti-5B refiner into the crucible, stirring and preserving heat for 1 hour.

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The metallographic pictures were measured by the line-cut method (national standard GBT6394-2017) to have an average grain size of about 216. + -. 19. mu.m.

Example 20

First, make up

The raw materials are Al-1V-3.5Ti-1.25B grain refiner prepared in example 4 and industrial aluminum silicon alloy (A356.2), and the raw materials are weighed according to a certain proportion, wherein the adding amount of the Al-1V-3.5Ti-1.25B grain refiner is 0.4 percent of the mass of the A356.2 alloy and is added into the A356.2 alloy melt.

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace rises to 740 ℃, then adding Al-1V-3.5Ti-1.25B refiner into the crucible, stirring and preserving heat for 1 hour.

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The average grain size of the metallographic pictures was measured by means of a line cut method (national standard GBT6394-2017) to be about 209. + -.12. mu.m.

Example 21

First, batching

The raw materials are the Al-1V-8Ti-1B grain refiner prepared in the example 5 and the industrial aluminum-silicon alloy (A356.2), and the raw materials are weighed according to a certain proportion, wherein the adding amount of the Al-1V-8Ti-1B grain refiner is 0.2 percent of the mass of the A356.2 alloy and is added into the A356.2 alloy melt.

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace rises to 740 ℃, then adding the Al-1V-8Ti-1B refiner into the crucible, stirring and preserving heat for 1 hour.

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

Example 22

First, batching

The raw materials are the Al-1V-5Ti-1B grain refiner prepared in the example 6 and the industrial aluminum-silicon alloy (A356.2), and the raw materials are weighed according to a certain proportion, wherein the adding amount of the Al-1V-5Ti-1B grain refiner is 0.3 percent of the mass of the A356.2 alloy and is added into the A356.2 alloy melt.

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace rises to 740 ℃, then adding the Al-1V-5Ti-1B refiner into the crucible, stirring and preserving heat for 1 hour.

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The average grain size of the metallographic pictures was measured by the line-cut method (national standard GBT6394-2017) to be about 198. + -. 16. mu.m.

Example 23

First, make up

The raw materials are Al-1.5V-1Ti-0.65B grain refiner prepared in example 7 and industrial aluminum silicon alloy (A356.2), and the raw materials are weighed according to a certain proportion, wherein the adding amount of the Al-1.5V-1Ti-0.65B grain refiner is 0.3 percent of the mass of the A356.2 alloy and is added into the A356.2 alloy melt.

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace is increased to 740 ℃, then adding Al-1.5V-1Ti-0.65B refiner into the crucible, stirring and preserving heat for 1 hour.

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The average grain size of the metallographic pictures was measured by means of a line cut method (national standard GBT6394-2017) and was approximately 206. + -.19. mu.m.

Example 24

First, batching

The raw materials are the Al-3V-1Ti-1B grain refiner prepared in the example 8 and the industrial aluminum-silicon alloy (A356.2), and the raw materials are weighed according to a certain proportion, wherein the adding amount of the Al-3V-1Ti-1B grain refiner is 0.8 percent of the mass of the A356.2 alloy and is added into the A356.2 alloy melt.

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace rises to 740 ℃, then adding the Al-3V-1Ti-1B refiner into the crucible, stirring and preserving heat for 1 hour.

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The metallographic pictures were measured by the line-cut method (national standard GBT6394-2017) to have an average grain size of about 201. + -. 16. mu.m.

Example 25

First, make up

The raw materials are Al-1V-1Ti-0.9B grain refiner prepared in example 9 and industrial aluminum silicon alloy (A356.2), and the raw materials are weighed according to a certain proportion, wherein the adding amount of the Al-1V-1Ti-0.9B grain refiner is 0.2 percent of the mass of the A356.2 alloy and is added into the A356.2 alloy melt.

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace rises to 740 ℃, then adding the Al-1V-1Ti-0.9B refiner into the crucible, stirring and preserving heat for 1 hour.

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The average grain size of the metallographic pictures was determined to be about 185. + -.13 μm by means of a line cut (national standard GBT 6394-2017).

Example 26

First, batching

The raw materials were Al-1.5V-0.5Ti-1.8B grain refiner prepared in example 10 and industrial Al-Si system alloy (A356.2) and were weighed in a certain proportion, wherein the Al-1.5V-0.5Ti-1.8B grain refiner was added to the A356.2 alloy melt in an amount of 0.3% by mass of the A356.2 alloy.

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace rises to 740 ℃, then adding Al-1.5V-0.5Ti-1.8B refiner into the crucible, stirring and preserving heat for 1 hour.

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The average grain size of the metallographic pictures was measured by means of a line-cut method (national standard GBT6394-2017) to be about 220. + -.26. mu.m.

Example 27

First, batching

The raw materials were the Al-2V-2Ti-3B grain refiner prepared in example 11 and an industrial Al-Si alloy (A356.2) and were weighed in a certain proportion, wherein the Al-2V-2Ti-3B grain refiner was added to the A356.2 alloy melt in an amount of 0.3% by mass of the A356.2 alloy.

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace is increased to 740 ℃, then adding the Al-2V-2Ti-3B refiner into the crucible, stirring and preserving heat for 1 hour.

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The metallographic pictures were measured by the line-cut method (national standard GBT6394-2017) to have an average grain size of about 210. + -. 19. mu.m.

Example 28

First, make up

The raw materials are Al-1V-1Ti-0.9B grain refiner prepared in example 12 and industrial aluminum silicon alloy (A356.2), and the raw materials are weighed according to a certain proportion, wherein the adding amount of the Al-1V-1Ti-0.9B grain refiner is 0.2 percent of the mass of the A356.2 alloy and is added into the A356.2 alloy melt.

Secondly, smelting

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The metallographic pictures were measured by the line-cut method (national standard GBT6394-2017) to have an average grain size of about 211. + -. 21 μm.

Example 29

First, batching

The raw materials were Al-1V-1Ti-0.9B grain refiner prepared in example 13 and industrial Al-Si system alloy (A356.2), and the raw materials were weighed according to a certain ratio, wherein the amount of Al-1V-1Ti-0.9B grain refiner added was 0.2% of the mass of A356.2 alloy and added to the A356.2 alloy melt.

Secondly, smelting

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The average grain size of the metallographic pictures was measured by means of a line-cut method (national standard GBT6394-2017) and was approximately 218. + -.27. mu.m.

Example 30

First, batching

The raw materials were Al-1V-1Ti-0.9B grain refiner prepared in example 14 and industrial Al-Si system alloy (A356.2), and the raw materials were weighed according to a certain ratio, wherein the amount of Al-1V-1Ti-0.9B grain refiner added was 0.2% of the mass of A356.2 alloy and added to the A356.2 alloy melt.

Secondly, smelting

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The average grain size of the metallographic pictures was measured by the line-cutting method (national standard GBT6394-2017) to be about 228. + -.31. mu.m.

Example 31

First, batching

The raw materials are Al-1.5V-1Ti-0.65B grain refiner prepared in comparative example 1 and industrial aluminum silicon alloy (A356.2), and the raw materials are weighed according to a certain proportion, wherein the adding amount of the Al-1.5V-1Ti-0.65B grain refiner is 0.3 percent of the mass of the A356.2 alloy and is added into the A356.2 alloy melt.

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace rises to 740 ℃, then adding Al-1.5V-1Ti-0.65B refiner into the crucible, stirring and preserving heat for 1 hour.

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The metallographic pictures were measured by the line-cut method (national standard GBT6394-2017) to have an average grain size of about 362. + -. 68 μm.

Example 32

First, batching

The raw materials are Al-7Si-1.5V-0.65B grain refiner and industrial aluminum-silicon alloy (A356.2) prepared in comparative example 2, and the raw materials are weighed according to a certain proportion, wherein the addition amount of the Al-7Si-1.5V-0.65B grain refiner is 0.3 percent of the mass of the A356.2 alloy and is added into the A356.2 alloy melt.

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace rises to 740 ℃, then adding Al-7Si-1.5V-0.65B refiner into the crucible, stirring and preserving heat for 1 hour.

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The metallographic pictures were measured by the line-cut method (national standard GBT6394-2017) to have an average grain size of about 278. + -. 25 μm.

Example 33

First, make up

The raw materials are Al-1.5V-0.65B grain refiner prepared in comparative example 3 and industrial aluminum silicon alloy (A356.2), and the raw materials are weighed according to a certain proportion, wherein the adding amount of the Al-1.5V-0.65B grain refiner is 0.3 percent of the mass of the A356.2 alloy and is added into the A356.2 alloy melt.

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace is increased to 740 ℃, then adding Al-1.5V-0.65B refiner into the crucible, stirring and preserving heat for 1 hour.

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The average grain size of the metallographic pictures was measured by means of a line-cut method (national standard GBT6394-2017) to be about 283. + -.28. mu.m.

Example 34

First, make up

The raw materials are Al-1.5V-0.65B grain refiner prepared in comparative example 4 and industrial aluminum silicon alloy (A356.2), and the raw materials are weighed according to a certain proportion, wherein the adding amount of the Al-1.5V-0.65B grain refiner is 0.3 percent of the mass of the A356.2 alloy and is added into the A356.2 alloy melt.

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace rises to 740 ℃, then adding Al-1.5V-0.65B refiner into the crucible, stirring and preserving heat for 1 hour.

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The average grain size of the metallographic pictures was determined to be about 297. + -.43 μm by the line-cut method (national standard GBT 6394-2017).

Example 35

First, make up

Secondly, smelting

Putting the industrial aluminum-silicon alloy into a crucible, then putting the crucible into a muffle furnace for heating, preserving heat for 1 hour for melting after the temperature in the furnace rises to 740 ℃, then adding Al-1.5V-1Ti-0.65B refiner into the crucible, stirring and preserving heat for 4 hours.

Thirdly, casting and solidifying

Fourth, metallographic analysis and grain size measurement

And grinding and polishing the refined cast ingot, then carrying out electrochemical corrosion anode coating, and taking a picture in a metallographic microscope polarization mode. The average grain size of the metallographic pictures was measured by the line-cut method (national standard GBT6394-2017) to be about 200. + -.12. mu.m.

The examples described herein are merely illustrative of the preferred embodiments of the present invention and do not limit the spirit and scope of the present invention, and various modifications and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the design concept of the present invention shall fall within the protection scope of the present invention.

Claims

1. An Al-V-Ti-B grain refiner, characterized in that: the grain refiner comprises the following chemical components in percentage by mass: v: 0.1-10 wt.%, B: 0.1-10 wt.%, Ti: 0.1-10 wt.%, the balance being Al, elements not affecting the refining effect and unavoidable impurity elements; in the grain refiner, the atomic ratio of (V + Ti) to B is more than or equal to 0.25 and less than or equal to 2;

the grain refiner contains (V/Ti) B₂Particles of (V/Ti) B₂(V/Ti) B having an average particle diameter of less than 2 μm and not less than 95%₂The particle size of the particles is less than 3 μm.

2. An Al-V-Ti-B grain refiner as claimed in claim 1, wherein: in the grain refiner, the atomic ratio of (V + Ti) to B is more than or equal to 0.3 and less than 0.8.

3. A method for preparing an Al-V-Ti-B grain refiner as claimed in claim 1 or 2, comprising the steps of:

first, batching

secondly, smelting raw materials

three, solidification deformation

4. A method for preparing an Al-V-Ti-B grain refiner according to claim 3, wherein: the specific process of the second step is as follows: mixing and smelting a V source, a B source and an Al source at 900-1200 ℃, preserving heat for 0.5-2 h, stirring and slagging off; and then adding a Ti source into the melt, smelting at 900-1100 ℃, preserving heat for 0.5-2 h, stirring and slagging off to form the melt after full reaction.

5. A method of producing an Al-V-Ti-B grain refiner according to claim 3, characterized in that: the specific process of the second step is as follows: mixing and smelting a V source, a Ti source and an Al source at 900-1200 ℃, preserving heat for 0.5-2 h, stirring and slagging off; and then adding a source B into the melt, preserving the heat for 0.5-2 h at 900-1100 ℃, stirring and slagging off to form the melt after full reaction.

6. A method of producing an Al-V-Ti-B grain refiner according to claim 3, characterized in that: the specific process of the second step is as follows: and mixing and smelting the V source, the Ti source, the B source and the Al source at 900-1200 ℃, preserving heat for 0.5-2 h, stirring and slagging off to form a melt after full reaction.

7. A method of producing an Al-V-Ti-B grain refiner according to claim 3, characterized in that: the specific process of the second step is as follows: mixing and smelting a Ti source, a B source and an Al source at 900-1200 ℃, preserving heat for 0.5-2 h, stirring and slagging off; and then adding a V source into the melt, smelting at 900-1100 ℃, preserving heat for 0.5-2 h, stirring and slagging off to form the melt after full reaction.

8. A method for preparing an Al-V-Ti-B grain refiner according to any one of claims 3 to 6, characterized in that: the V source is AlV alloy or V powder or V oxide; the B source is KBF4 or AlB alloy; the Ti source is KTiF4 or AlTi alloy or Ti powder or Ti scrap; the Al source is industrial pure aluminum.

9. A method of using the Al-V-Ti-B grain refiner of claim 1 or 2, comprising the steps of:

first, smelting

Heating and melting the aluminum alloy to be refined;

Secondly, adding a refiner

third, casting