CN111424195B

CN111424195B - Refiner, preparation method and application thereof, aluminum alloy and refining method thereof

Info

Publication number: CN111424195B
Application number: CN202010424965.9A
Authority: CN
Inventors: 赵庆龙; 宋业刚; 梅杰; 刘肖; 姜启川
Original assignee: Jilin University
Current assignee: Jilin University
Priority date: 2020-05-19
Filing date: 2020-05-19
Publication date: 2021-08-03
Anticipated expiration: 2040-05-19
Also published as: CN111424195A

Abstract

The invention is suitable for the technical field of alloy processing, and provides a refiner, a preparation method and application thereof, an aluminum alloy and a refining method thereof, wherein the refiner comprises titanium carbide solid solution particles; the titanium carbide solid solution particles contain solid solution metal vanadium and have a chemical formula of (Ti)_1‑x,V_x) C or (Ti)_1‑x,V_x)(C_1‑y,N_y) (ii) a In the formula, 0<x≤0.5，0<y is less than or equal to 0.6. The refiner provided by the invention has obvious refining effect, can generate obvious refining effect by adding a small amount of the refiner into the alloy structure of aluminum alloy and the like, saves the using amount of the refiner, has simple refining process, is easy to control, and has important practical application value on the control of the performance of the alloy structure of aluminum alloy and the like.

Description

Refiner, preparation method and application thereof, aluminum alloy and refining method thereof

Technical Field

The invention belongs to the technical field of alloy processing, and particularly relates to a refiner, a preparation method and application thereof, an aluminum alloy and a refining method thereof.

Background

The development of aerospace, national defense and military and transportation puts higher requirements on the light weight of materials, and the aluminum alloy is a key material for realizing light weight. The cast structure formed in the aluminum alloy solidification process can directly influence the performance indexes of the subsequent processing process, the quality of the final product, the service life and the like. Therefore, controlling the solidification structure of the aluminum alloy is an important way to control the material performance. By adding a refiner to treat the aluminum alloy melt, uniform and fine alpha-Al grains can be obtained. There are many methods for refining grains, but the addition of a refiner is simple, has remarkable effect and stable effect, and is the most common refining method. Al + over the past decadesTi-B refiner has been widely used for the refinement of aluminum alloy structure, although the refinement effect is significant, because TiB₂The refiner is easy to precipitate and aggregate and is easy to lose refining effect under the poisoning action of Zr, Cr and the like, and the attenuation resistance of the refiner cannot meet the requirements of people, so that more efficient and stable refiners and treatment technologies are continuously researched by people. The Al-Ti-C refiner overcomes the poisoning effect of Zr, Cr and the like, and the generated TiC is not easy to precipitate and aggregate, so that the Al-Ti-C refiner is better applied industrially. However, the lattice parameter of TiC is greatly different from that of aluminum, and the mismatching degree of TiC with aluminum is high, so that the nucleation efficacy is greatly influenced.

Therefore, there is a need to provide a refiner having a smaller lattice parameter difference from aluminum, a higher nucleation efficacy and a significant refining effect.

Disclosure of Invention

The embodiment of the invention aims to provide a refiner, and aims to solve the problems in the background technology.

The embodiment of the invention is realized by that the refiner comprises titanium carbide solid solution particles; the titanium carbide solid solution particles contain solid solution metal vanadium and have a chemical formula of (Ti)₁-x,V_x) C or (Ti)_1-x,V_x)(C_1-y,N_y) (ii) a In the formula, 0<x≤0.5，0<y≤0.6。

Preferably, the refiner comprises the following components in percentage by weight: 3.90 to 22.73 percent of titanium, 0.42 to 12.44 percent of vanadium, 2.00 to 5.99 percent of carbon and the balance of aluminum, wherein the sum of the weight percent of the components is 100 percent.

Preferably, the refiner comprises the following components in percentage by weight: 3.83 to 23.34 percent of titanium, 0.42 to 12.24 percent of vanadium, 0.96 to 2.89 percent of carbon, 1.12 to 3.37 percent of nitrogen and the balance of aluminum, wherein the sum of the weight percentages of the components is 100 percent.

Another object of the embodiments of the present invention is to provide a method for preparing the above-mentioned refiner, which comprises the following steps:

weighing aluminum powder, titanium powder, vanadium powder and carbon nanotubes by taking a carbon nanotube as a carbon source according to the weight percentage of the components for later use;

mixing aluminum powder, titanium powder, vanadium powder and carbon nanotubes, and then preparing a green compact;

wrapping the pressed blank by graphite paper, and then placing the pressed blank in a graphite mold;

and placing the graphite mold containing the pressed compact under the conditions that the air pressure is not higher than 10Pa and the temperature is 900-950K for hot-pressing densification, and then placing the graphite mold under the vacuum condition at the temperature of 1500-1800K for sintering treatment to obtain the refiner.

Preferably, the step of mixing aluminum powder, titanium powder, vanadium powder and carbon nanotubes and then making the mixture into a green compact specifically comprises:

mixing aluminum powder, titanium powder, vanadium powder and carbon nanotubes to obtain reactant powder;

putting reactant powder and zirconia grinding balls (the diameter is 5-22mm) into a mixing tank for ball milling, wherein the ball-material ratio is 6: 1-20: 1, the ball milling speed is 50-100 r/min, and the ball milling time is 12-24 hours, so as to obtain a mixture;

and taking out the mixture, wrapping the mixture by using aluminum foil, putting the mixture into a cylindrical die, and pressing the cylindrical die into a cylindrical green compact on a hydraulic testing machine.

Preferably, the axial pressure of the hot-pressing densification treatment is 30-40 MPa.

Preferably, the particle size of the aluminum powder is 13-50 μm; the granularity of the titanium powder is 13-48 mu m; the particle size of the vanadium powder is 40-45 mu m.

weighing aluminum powder, titanium powder, vanadium powder, carbon nanotubes and urea powder according to the weight percentage of the components by taking carbon nanotubes as a carbon source and urea powder as a carbon source and a nitrogen source for later use;

mixing aluminum powder, titanium powder, vanadium powder, carbon nanotubes and urea powder, and then preparing a green compact;

Preferably, the step of mixing the aluminum powder, the titanium powder, the carbon nanotubes and the urea powder and then making the mixture into a green compact specifically comprises:

mixing aluminum powder, titanium powder, vanadium powder, carbon nanotubes and urea powder to obtain reactant powder;

putting reactant powder and zirconia grinding balls (the diameter is 5-22 m) into a mixing tank for ball milling, wherein the ball-material ratio is 6: 1-20: 1, the ball milling speed is 50-100 r/min, and the ball milling time is 12-24 hours, so as to obtain a mixture;

Preferably, the particle size of the aluminum powder is 13-50 μm; the granularity of the titanium powder is 13-48 mu m; the particle size of the vanadium powder is 40-45 mu m; the particle size of the urea powder is 45-50 mu m.

Another purpose of the embodiment of the invention is to provide a refiner prepared by the preparation method.

Another object of an embodiment of the present invention is to provide an application of the above refiner in alloy structure refinement.

Another object of an embodiment of the present invention is to provide a method for refining an aluminum alloy, including the steps of:

carrying out melting treatment on the initial aluminum alloy, and then carrying out deslagging treatment to obtain an alloy liquid;

adding the refiner into the alloy liquid, and uniformly mixing to obtain molten metal; the mass of the refiner is 0.1-0.5% of that of the alloy liquid;

and (4) performing solidification molding treatment on the molten metal to obtain the refined aluminum alloy.

Another object of the embodiments of the present invention is to provide an aluminum alloy refined by the above refining method.

Preferably, the average grain size of the aluminum alloy is 58.73-161.63 mu m.

The refiner provided by the embodiment of the invention contains multi-element composite ceramic particles, and can generate obvious refining effect by adding a small amount of the refiner into alloy structures such as aluminum alloy and the like (after 0.5 wt% (T i 0.85.85, V0.15) of C ceramic particles are added, grains are refined by nearly 7 times, and after 0.5 wt% (Ti0.85, V0.15) (C0.7, N0.3) of ceramic particles are added, grains are refined by nearly 5.3 times), so that the consumption of the refiner is saved, the refining process is simple and easy to control, and the refiner has important practical application value for controlling the properties of the alloy structures such as aluminum alloy and the like.

Drawings

FIG. 1 shows a composite ceramic particle (Ti) containing a plurality of elements synthesized in accordance with one embodiment of the present invention_0.85,V_0.15) XRD pattern of C refiner.

FIG. 2 shows a composite ceramic particle (Ti) containing a plurality of elements synthesized in accordance with one embodiment of the present invention_0.85,V_0.15) SEM photograph of C refiner.

FIG. 3 shows a multi-component composite ceramic particle (Ti) synthesized in example two of the present invention_0.75,V_0.25) XRD pattern of C refiner.

FIG. 4 shows a multi-component composite ceramic particle (Ti) synthesized in example two of the present invention₀₇₅,V₀₂₅) SEM photograph of C refiner.

FIG. 5 shows a multi-component composite ceramic particle (Ti) synthesized in example III of the present invention_0.5,V_0.5) XRD pattern of C refiner.

FIG. 6 shows a multi-component composite ceramic particle (Ti) synthesized in example III of the present invention_0.5,V_0.5) SEM photograph of C refiner.

FIG. 7 shows a multi-component composite ceramic particle (Ti) synthesized in example four of the present invention_0.85,V_0.15)(C_0.7,N_0.3) XRD pattern of refiner.

FIG. 8 shows a multi-component composite ceramic particle (Ti) synthesized in example four of the present invention_0.85,V_0.15)(C_0.7,N_0.3) SEM photograph of the refiner.

FIG. 9 shows a multi-component composite ceramic particle (Ti) synthesized in example five of the present invention_0.7,V_0.3)(C_0.6,N_0.4) XRD pattern of refiner.

FIG. 10 shows a multi-component composite ceramic particle (Ti) synthesized in example five of the present invention_0.7,V_0.3)(C_0.6,N_0.4) SEM photograph of the refiner.

FIG. 11 shows a multi-component composite ceramic particle (Ti) synthesized in example six of the present invention_0.5,V_0.5)(C_0.4,N_0.6) XRD pattern of refiner.

FIG. 12 shows a multi-component composite ceramic particle (Ti) synthesized in example six of the present invention_0.5,V_0.5)(C_0.4,N_0.6) SEM photograph of the refiner.

FIG. 13 is an XRD pattern of the refiner synthesized in comparative example one of the present invention.

FIG. 14 is an XRD pattern of the refiner synthesized in comparative example II of the present invention.

FIG. 15 is an as-cast grain structure diagram of an unrefined aluminum alloy.

FIG. 16 shows the addition of 0.5 wt.% (Ti) in the first embodiment of the present invention_0.85,V_0.15) C as-cast grain structure diagram of aluminum alloy in ceramic particles.

FIG. 17 shows the addition of 0.2 wt.% (Ti) in the second embodiment of the present invention_0.75,V_0.25) C as-cast grain structure diagram of aluminum alloy in ceramic particles.

FIG. 18 shows the addition of 0.3 wt.% (Ti) in the third embodiment of the present invention_0.5,V_0.5) C as-cast grain structure diagram of aluminum alloy in ceramic particles.

FIG. 19 shows the addition of 0.5 wt.% (Ti) in example four of the present invention_0.85,V_0.15)(C_0.7,N_0.3) An as-cast grain structure of the aluminum alloy in the form of ceramic particles.

FIG. 20 shows the addition of 0.3 wt.% (Ti) in the fifth embodiment of the present invention_0.7,V_0.3)(C_0.6,N_0.4) As-cast grain group of aluminum alloy in case of ceramic grainWeaving the picture.

FIG. 21 shows the addition of 0.1 wt.% (Ti) in example six of the present invention_0.5,V_0.5)(C_0.4,N_0.6) An as-cast grain structure of the aluminum alloy in the form of ceramic particles.

FIG. 22 is a graph of the as-cast grain structure of an aluminum alloy with the addition of 0.3 wt% TiC ceramic particles in comparative example three of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Example one

The embodiment prepares the refiner of the endogenous submicron multi-element composite ceramic particles, which can be used for refining alloy structures such as aluminum alloy and the like, but is not limited to the refining. Specifically, the refiner contains a compound represented by the formula (Ti)_0.85,V_0.15) C, the molar ratio of Ti/V is 0.85:0.15, the mass fraction of the titanium carbide solid solution particles is 25 wt.%, and the preparation method of the refiner comprises the following steps:

s11, preparing powder used for reaction compaction: using carbon nanotubes as a carbon source, weighing 75 g of aluminum powder with the particle size of 13 μm, 16.858 g of titanium powder with the particle size of 13 μm, 3.166 g of vanadium powder with the particle size of 45 μm and 4.976 g of Carbon Nanotubes (CNTs) for later use.

S12, mixing the weighed aluminum powder, titanium powder, vanadium powder and carbon nanotubes to obtain reactant powder; then, putting the prepared reactant powder and zirconia grinding balls (the diameter is 5-22mm) into a mixing tank for ball milling, wherein the ball-material ratio is set to be 6:1, the ball milling speed is 60r/min, and the ball milling time is 16 hours, so as to obtain a mixture; then, the mixture was taken out, wrapped with aluminum foil, placed in a cylindrical mold, and pressed on a hydraulic testing machine into a cylindrical green compact having a diameter of 30 mm.

S13, synthesizing the multi-element composite ceramic particle refiner by the pressed compact sintering in-situ reaction: firstly, wrapping the cylindrical pressed blank with the diameter of 30mm prepared in the step S12 by using graphite paper, and putting the pressed blank into a graphite mould used for in-situ sintering reaction; then, putting the graphite mould with the cylindrical pressed compact into a vacuum hot-pressing sintering furnace, closing a furnace door, and vacuumizing until the air pressure in the furnace is lower than 10 Pa; then, heating is started, and the heating speed is set to be 40K/min; when the measured temperature in the furnace is 950K, setting heat preservation and applying axial pressure to the cylindrical pressed compact, wherein the stress value is 40MPa, and the pressure is maintained for 20s for hot-pressing densification treatment; then continuously heating to 1800K, preserving heat for 10min, keeping the vacuum in the furnace, and cooling to room temperature along with the furnace to obtain the refiner; the characterization results of the refiner containing multi-component composite ceramic particles synthesized by in-situ reaction are shown in fig. 1 and 2. Wherein, fig. 1 is an XRD spectrum of the refiner, and fig. 2 is an SEM photograph of the refiner.

In addition, the embodiment also provides an unrefined initial aluminum alloy, and the preparation method of the initial aluminum alloy comprises the following steps of:

s21, placing the pre-weighed aluminum alloy into a crucible, placing the crucible into a resistance smelting furnace, and heating to 1023K; the aluminum alloy comprises the following components: al 95 wt.%, Cu 5 wt.%.

And S22, after the aluminum alloy is completely melted, preserving heat for 30min, adding 0.05 wt.% of slag removing agent for refining slag removal, and preserving heat for 10min after slag removal to obtain an alloy liquid.

S23, casting the alloy liquid after heat preservation into a metal mold, and obtaining blank-like aluminum alloy after solidification and cooling; the as-cast grain structure of the blank aluminum alloy (i.e., the unrefined aluminum alloy) is shown in fig. 13.

In addition, the embodiment also provides a refining method of an aluminum alloy, which is to refine the initial aluminum alloy by using the refiner of the endogenous submicron multi-element composite ceramic particles prepared in the first embodiment, and specifically includes the following steps:

s31, placing the pre-weighed aluminum alloy into a crucible, placing the crucible into a resistance smelting furnace, and heating to 1123K; the aluminum alloy comprises the following components: al 95 wt.%, Cu 5 wt.%.

And S32, after the aluminum alloy is completely melted, preserving heat for 30min, adding 0.05 wt.% of slag removing agent for refining slag removal, and preserving heat for 10min after slag removal to obtain an alloy liquid.

S33, adding the refiner of the endogenous submicron multi-element composite ceramic particles prepared in the first embodiment into the alloy liquid, and then carrying out mechanical stirring and ultrasonic treatment for 3min to obtain metal liquid; wherein the actual amount of refiner added is 0.5 wt.%.

And S34, casting the obtained molten metal into a metal mold for solidification molding treatment to obtain the aluminum alloy refined and enhanced by the multi-component composite ceramic particles.

Wherein, the material of the metal die is 45# steel, and the size of the metal die is 200mm x 150mm x 20 mm; the deslagging agent is a deslagging agent for common aluminum alloy sold in the market in the prior art.

Adding the refiner containing submicron multi-component composite ceramic particles into alloy liquid, wherein the refiner contains (Ti)_0.85V_0.15) The actual addition of the refiner of C was 0.5 wt.%, and the average grain size of the aluminum alloy was reduced from 410.27 μm before unrefined to 58.73 μm after refined by nearly 7-fold, with the experimental results shown in table 1 and fig. 16.

Example two

The embodiment prepares the refiner of the endogenous submicron multi-element composite ceramic particles, which can be used for refining alloy structures such as aluminum alloy and the like, but is not limited to the refining. Specifically, the refiner contains a compound represented by the formula (Ti)_0.75,V_0.25) C, the molar ratio of Ti/V is 0.75:0.25, the mass fraction of the titanium carbide solid solution particles is 20 wt.%, and the preparation method of the refiner comprises the following steps:

s11, preparing powder used for reaction compaction: using carbon nanotubes as carbon source, weighing 80 g of aluminum powder with the granularity of 30 μm, 11.839 g of titanium powder with the granularity of 20 μm, 4.200 g of vanadium powder with the granularity of 40 μm and 3.961 g of carbon nanotubes for later use.

S12, mixing the weighed aluminum powder, titanium powder, vanadium powder and carbon nanotubes to obtain reactant powder; then, putting the prepared reactant powder and zirconia grinding balls (the diameter is 5-22mm) into a mixing tank for ball milling, wherein the ball-material ratio is set to be 8:1, the ball milling speed is 50r/min, and the ball milling time is 15 hours, so as to obtain a mixture; then, the mixture was taken out, wrapped with aluminum foil, placed in a cylindrical mold, and pressed on a hydraulic testing machine into a cylindrical green compact having a diameter of 30 mm.

S13, synthesizing the multi-element composite ceramic particle refiner by the pressed compact sintering in-situ reaction: firstly, wrapping the cylindrical pressed blank with the diameter of 30mm prepared in the step S12 by using graphite paper, and putting the pressed blank into a graphite mould used for in-situ sintering reaction; then, putting the graphite mould with the cylindrical pressed compact into a vacuum hot-pressing sintering furnace, closing a furnace door, and vacuumizing until the air pressure in the furnace is lower than 10 Pa; then, heating is started, and the heating speed is set to be 40K/min; when the measured temperature in the furnace is 900K, setting heat preservation and applying axial pressure to the cylindrical pressed compact, wherein the stress value is 45MPa, and the pressure is kept for 15s for hot-pressing densification treatment; then continuously heating to 1500K, preserving heat for 10min, keeping the vacuum in the furnace, and cooling to room temperature along with the furnace to obtain the refiner; the characterization results of the refiner containing multi-component composite ceramic particles synthesized by in-situ reaction are shown in fig. 3 and 4. Wherein, fig. 3 is an XRD spectrum of the refiner, and fig. 4 is an SEM photograph of the refiner.

In addition, the embodiment also provides a refining method of an aluminum alloy, which is to refine the initial aluminum alloy provided by the first embodiment by using the refiner of the endogenous submicron multi-element composite ceramic particles prepared by the second embodiment, and specifically includes the following steps:

S33, adding the refiner of the endogenous submicron multi-element composite ceramic particles prepared in the second embodiment into the alloy liquid, and then mechanically stirring and ultrasonically treating for 3min to obtain metal liquid; wherein the actual amount of refiner added is 0.2 wt.%.

Adding the refiner containing submicron multi-component composite ceramic particles into alloy liquid, wherein the refiner contains (Ti)_0.75V_0.25) The actual addition of the refiner of C was 0.2 wt.%, and the average grain size of the aluminum alloy was reduced from 410.27 μm before unrefined to 143.56 μm after refined by nearly 3-fold, with the experimental results shown in table 1 and fig. 17.

EXAMPLE III

The embodiment prepares the refiner of the endogenous submicron multi-element composite ceramic particles, which can be used for refining alloy structures such as aluminum alloy and the like, but is not limited to the refining. Specifically, the refiner contains a compound represented by the formula (Ti)_0.5,V_0.5) C, the molar ratio of Ti/V is 0.5:0.5, the mass fraction of the titanium carbide solid solution particles is 10 wt.%, and the preparation method of the refiner comprises the following steps:

s11, preparing powder used for reaction compaction: using carbon nanotubes as carbon source, weighing 90 g of aluminum powder with the granularity of 30 μm, 3.897 g of titanium powder with the granularity of 45 μm, 4.147 g of vanadium powder with the granularity of 45 μm and 1.956 g of carbon nanotubes for later use.

S12, mixing the weighed aluminum powder, titanium powder, vanadium powder and carbon nanotubes to obtain reactant powder; then, putting the prepared reactant powder and zirconia grinding balls (the diameter is 5-22mm) into a mixing tank for ball milling, wherein the ball-material ratio is set to be 8:1, the ball milling speed is 65r/min, and the ball milling time is 18 hours, so as to obtain a mixture; then, the mixture was taken out, wrapped with aluminum foil, placed in a cylindrical mold, and pressed on a hydraulic testing machine into a cylindrical green compact having a diameter of 30 mm.

S13, synthesizing the multi-element composite ceramic particle refiner by the pressed compact sintering in-situ reaction: firstly, wrapping the cylindrical pressed blank with the diameter of 30mm prepared in the step S12 by using graphite paper, and putting the pressed blank into a graphite mould used for in-situ sintering reaction; then, putting the graphite mould with the cylindrical pressed compact into a vacuum hot-pressing sintering furnace, closing a furnace door, and vacuumizing until the air pressure in the furnace is lower than 10 Pa; then, heating is started, and the heating speed is set to be 36K/min; when the measured temperature in the furnace is 933K, setting heat preservation and applying axial pressure to the cylindrical pressed compact, wherein the stress value is 35MPa, and the pressure is kept for 15s for hot-pressing densification; then continuously heating to 1600K, preserving the heat for 10min, keeping the vacuum in the furnace, and cooling to room temperature along with the furnace to obtain the refiner; the characterization results of the refiner containing multi-component composite ceramic particles synthesized by in-situ reaction are shown in fig. 5 and 6. Wherein, fig. 5 is an XRD spectrum of the refiner, and fig. 6 is an SEM photograph of the refiner.

In addition, the embodiment also provides a refining method of an aluminum alloy, which is to refine the initial aluminum alloy provided by the first embodiment by using the refiner of the endogenous submicron multi-element composite ceramic particles prepared by the third embodiment, and specifically includes the following steps:

S33, adding the refiner of the endogenous submicron multi-element composite ceramic particles prepared in the third embodiment into the alloy liquid, and then mechanically stirring and ultrasonically treating for 3min to obtain metal liquid; wherein the actual amount of refiner added is 0.3 wt.%.

Adding the refiner containing submicron multi-component composite ceramic particles into alloy liquid, wherein the refiner contains (Ti)_0.5V_0.5) The actual addition of the refiner of C was 0.3 wt.%, and the average grain size of the aluminum alloy was reduced from 410.27 μm before unrefined to 105.71 μm after refined by nearly 4-fold, with the experimental results shown in table 1 and fig. 18.

Example four

The embodiment prepares the refiner of the endogenous submicron multi-element composite ceramic particles, which can be used for refining alloy structures such as aluminum alloy and the like, but is not limited to the refining. Specifically, the refiner contains a compound represented by the formula (Ti)_0.85,V_0.15)(C_0.7,N_0.3) The Ti/V/C/N molar ratio of the titanium carbide solid solution particles is 0.85:0.15:0.7:0.3, the mass fraction of the titanium carbide solid solution particles is 20 wt.%, and the preparation method of the refiner comprises the following steps:

s11, preparing powder used for reaction compaction: using carbon nanotubes as carbon source, urea powder as carbon source and nitrogen source, weighing 80 g of aluminum powder with particle size of 13 μm, 13.353 g of titanium powder with particle size of 13 μm, 2.508 g of vanadium powder with particle size of 45 μm, 2.168 g of carbon nanotubes and 2.955 g of urea powder with particle size of 50 μm (CON)₂H₄) And then standby.

S12, mixing the weighed aluminum powder, titanium powder, vanadium powder, carbon nano-tubes and urea powder to obtain reactant powder; then, putting the prepared reactant powder and zirconia grinding balls (the diameter is 5-22mm) into a mixing tank for ball milling, wherein the ball-material ratio is 10:1, the ball milling speed is 70r/min, and the ball milling time is 20 hours, so as to obtain a mixture; then, the mixture was taken out, wrapped with aluminum foil, placed in a cylindrical mold, and pressed on a hydraulic testing machine into a cylindrical green compact having a diameter of 30 mm.

S13, synthesizing the multi-element composite ceramic particle refiner by the pressed compact sintering in-situ reaction: firstly, wrapping the cylindrical pressed blank with the diameter of 30mm prepared in the step S12 by using graphite paper, and putting the pressed blank into a graphite mould used for in-situ sintering reaction; then, putting the graphite mould with the cylindrical pressed compact into a vacuum hot-pressing sintering furnace, closing a furnace door, and vacuumizing until the air pressure in the furnace is lower than 10 Pa; then, heating is started, and the heating speed is set to be 37K/min; when the measured temperature in the furnace is 933K, setting heat preservation and applying axial pressure to the cylindrical pressed compact, wherein the stress value is 40MPa, and the pressure is kept for 30s for hot-pressing densification; then continuously heating to 1700K, preserving heat for 10min, keeping the vacuum in the furnace, and cooling to room temperature along with the furnace to obtain the refiner; the characterization results of the refiner containing multi-component composite ceramic particles synthesized by in-situ reaction are shown in fig. 7 and 8. Wherein, fig. 7 is an XRD spectrum of the refiner, and fig. 8 is an SEM photograph of the refiner.

In addition, the embodiment also provides a refining method of an aluminum alloy, which is to refine the initial aluminum alloy provided by the first embodiment by using the refiner of the endogenous submicron multi-element composite ceramic particles prepared by the fourth embodiment, and specifically includes the following steps:

S33, adding the refiner of the endogenous submicron multi-element composite ceramic particles prepared in the fourth embodiment into the alloy liquid, and then mechanically stirring and ultrasonically treating for 3min to obtain metal liquid; wherein the actual amount of refiner added is 0.5 wt.%.

Adding the refiner containing submicron multi-component composite ceramic particles into alloy liquid, wherein the refiner contains (Ti)_0.85,V_0.15)(C_0.7,N_0.3) The actual addition of the grain refiner of (a) was 0.5 wt.%, and the average grain size of the aluminum alloy was reduced from 410.27 μm before unrefined to 77.54 μm after refined by nearly 5.3 times, with the experimental results shown in table 1 and fig. 19.

EXAMPLE five

The embodiment prepares the refiner of the endogenous submicron multi-element composite ceramic particles, which can be used for refining alloy structures such as aluminum alloy and the like, but is not limited to the refining. Specifically, the refiner contains a compound represented by the formula (Ti)_0.7,V_0.3)(C_0.6,N_0.4) The Ti/V/C/N molar ratio of the titanium carbide solid solution particles is 0.7:0.3:0.6:0.4, the mass fraction of the titanium carbide solid solution particles is 10 wt.%, and the preparation method of the refiner comprises the following steps:

s11, preparing powder used for reaction compaction: using carbon nanotubes as carbon source, urea powder as carbon source and nitrogen source, weighing 90 g of aluminum powder with particle size of 30 μm, 5.439 g of titanium powder with particle size of 20 μm, 2.481 g of vanadium powder with particle size of 45 μm, 0.779 g of carbon nanotubes and 1.949 g of urea powder with particle size of 45 μm (CON)₂H₄) And then standby.

S12, mixing the weighed aluminum powder, titanium powder, vanadium powder, carbon nano-tubes and urea powder to obtain reactant powder; then, putting the prepared reactant powder and zirconia grinding balls (the diameter is 5-22mm) into a mixing tank for ball milling, wherein the ball-material ratio is 9:1, the ball milling speed is 70r/min, and the ball milling time is 18 hours, so as to obtain a mixture; then, the mixture was taken out, wrapped with aluminum foil, placed in a cylindrical mold, and pressed on a hydraulic testing machine into a cylindrical green compact having a diameter of 30 mm.

S13, synthesizing the multi-element composite ceramic particle refiner by the pressed compact sintering in-situ reaction: firstly, wrapping the cylindrical pressed blank with the diameter of 30mm prepared in the step S12 by using graphite paper, and putting the pressed blank into a graphite mould used for in-situ sintering reaction; then, putting the graphite mould with the cylindrical pressed compact into a vacuum hot-pressing sintering furnace, closing a furnace door, and vacuumizing until the air pressure in the furnace is lower than 10 Pa; then, heating is started, and the heating speed is set to be 30K/min; when the measured temperature in the furnace is 933K, setting heat preservation and applying axial pressure to the cylindrical pressed compact, wherein the stress value is 35MPa, and the pressure is kept for 30s for hot-pressing densification; then continuously heating to 1673K, keeping the temperature for 10min, keeping the vacuum in the furnace, and cooling to room temperature along with the furnace to obtain the refiner; the characterization results of the refiner containing multi-component composite ceramic particles synthesized by in-situ reaction are shown in fig. 9 and 10. Wherein, fig. 9 is an XRD spectrum of the refiner, and fig. 10 is an SEM photograph of the refiner.

In addition, the embodiment also provides a refining method of an aluminum alloy, which is to refine the initial aluminum alloy provided by the first embodiment by using the refiner of the endogenous submicron multi-element composite ceramic particles prepared by the fifth embodiment, and specifically includes the following steps:

S33, adding the refiner of the endogenous submicron multi-element composite ceramic particles prepared in the fifth embodiment into the alloy liquid, and then mechanically stirring and ultrasonically treating for 3min to obtain metal liquid; wherein the actual amount of refiner added is 0.3 wt.%.

Adding the refiner containing submicron multi-component composite ceramic particles into alloy liquid, wherein the refiner contains (Ti)_0.7,V_0.3)(C_0.6,N_0.4) The actual addition of the grain refiner of (a) was 0.3 wt.%, and the average grain size of the aluminum alloy was reduced from 410.27 μm before unrefined to 146.45 μm after refined by nearly 2.8 times, with the experimental results shown in table 1 and fig. 20.

EXAMPLE six

The embodiment prepares the refiner of the endogenous submicron multi-element composite ceramic particles, which can be used for refining alloy structures such as aluminum alloy and the like, but is not limited to the refining. Specifically, the refiner contains a compound represented by the formula (Ti)_0.85,V_0.15)(C_0.4,N_0.6) The Ti/V/C/N molar ratio of the titanium carbide solid solution particles is 0.5:0.5:0.4:0.6, the mass fraction of the titanium carbide solid solution particles is 30 wt.%, and the preparation method of the refiner comprises the following steps:

s11, preparing powder used for reaction compaction: using carbon nanotubes as carbon source, urea powder as carbon source and nitrogen source, weighing 70 g of aluminum powder with a particle size of 20 μm, 11.467 g of titanium powder with a particle size of 13 μm, 12.203 g of vanadium powder with a particle size of 45 μm, 0.575 g of carbon nanotubes and 8.629 g of urea powder with a particle size of 50 μm (CON)₂H₄) And then standby.

S12, mixing the weighed aluminum powder, titanium powder, vanadium powder, carbon nano-tubes and urea powder to obtain reactant powder; then, putting the prepared reactant powder and zirconia grinding balls (the diameter is 5-22mm) into a mixing tank for ball milling, wherein the ball-material ratio is set to be 8:1, the ball milling speed is 65r/min, and the ball milling time is 18 hours, so as to obtain a mixture; then, the mixture was taken out, wrapped with aluminum foil, placed in a cylindrical mold, and pressed on a hydraulic testing machine into a cylindrical green compact having a diameter of 30 mm.

S13, synthesizing the multi-element composite ceramic particle refiner by the pressed compact sintering in-situ reaction: firstly, wrapping the cylindrical pressed blank with the diameter of 30mm prepared in the step S12 by using graphite paper, and putting the pressed blank into a graphite mould used for in-situ sintering reaction; then, putting the graphite mould with the cylindrical pressed compact into a vacuum hot-pressing sintering furnace, closing a furnace door, and vacuumizing until the air pressure in the furnace is lower than 10 Pa; then, heating is started, and the heating speed is set to be 40K/min; when the measured temperature in the furnace is 933K, setting heat preservation and applying axial pressure to the cylindrical pressed compact, wherein the stress value is 30MPa, and the pressure is kept for 20s for hot-pressing densification; then continuously heating to 1673K, keeping the temperature for 10min, keeping the vacuum in the furnace, and cooling to room temperature along with the furnace to obtain the refiner; the characterization results of the refiner containing multi-component composite ceramic particles synthesized by in-situ reaction are shown in fig. 11 and 12. Wherein, fig. 11 is an XRD spectrum of the refiner, and fig. 12 is an SEM photograph of the refiner.

In addition, the embodiment also provides a refining method of an aluminum alloy, which is to refine the initial aluminum alloy provided by the first embodiment by using the refiner of the endogenous submicron multi-element composite ceramic particles prepared by the sixth embodiment, and specifically includes the following steps:

S33, adding the refiner of the endogenous submicron multi-element composite ceramic particles prepared in the sixth embodiment into the alloy liquid, and then mechanically stirring and ultrasonically treating for 3min to obtain metal liquid; wherein the actual amount of refiner added is 0.1 wt.%.

By adding the above-mentioned submicron-containing alloy liquidAfter the grain refiner of the multi-element composite ceramic grains, the multi-element composite ceramic grains contain (Ti)_0.5,V_0.5)(C_0.4,N_0.6) The actual addition of the grain refiner of (1) was 0.1 wt.%, and the average grain size of the aluminum alloy was reduced from 410.27 μm before unrefined to 161.63 μm after refined by nearly 2.54 times, with the experimental results shown in table 1 and fig. 21.

Comparative example 1

The comparative example prepared a refiner, specifically, the preparation method of the refiner included the following steps:

s11, preparing powder used for reaction compaction: using carbon nanotubes as carbon source, weighing 80 g of aluminum powder with the particle size of 13 μm, 6.204 g of titanium powder with the particle size of 45 μm, 9.904 g of vanadium powder with the particle size of 45 μm and 3.892 g of carbon nanotubes for later use. Wherein the molar ratio of Ti/V in the Al-Ti-V-C system is 0.4:0.6, and the mass fraction of Al is 80 wt.%.

S12, mixing the weighed aluminum powder, titanium powder, vanadium powder and carbon nanotubes to obtain reactant powder; then, putting the prepared reactant powder and zirconia grinding balls (the diameter is 5-22mm) into a mixing tank for ball milling, wherein the ball-material ratio is 12:1, the ball milling speed is 65r/min, and the ball milling time is 16 hours, so as to obtain a mixture; then, the mixture was taken out, wrapped with aluminum foil, placed in a cylindrical mold, and pressed on a hydraulic testing machine into a cylindrical green compact having a diameter of 30 mm.

S13, synthesizing the multi-element composite ceramic particle refiner by the pressed compact sintering in-situ reaction: firstly, wrapping the cylindrical pressed blank with the diameter of 30mm prepared in the step S12 by using graphite paper, and putting the pressed blank into a graphite mould used for in-situ sintering reaction; then, putting the graphite mould with the cylindrical pressed compact into a vacuum hot-pressing sintering furnace, closing a furnace door, and vacuumizing until the air pressure in the furnace is lower than 10 Pa; then, heating is started, and the heating speed is set to be 38K/min; when the measured temperature in the furnace is 933K, setting heat preservation and applying axial pressure to the cylindrical pressed compact, wherein the stress value is 35MPa, and the pressure is kept for 20s for hot-pressing densification; then continuously heating to 1673K, keeping the temperature for 10min, keeping the vacuum in the furnace, and cooling to room temperature along with the furnace to obtain the refiner;the characterization results of this refiner are shown in FIG. 13. FIG. 13 shows the XRD pattern of the refining agent, from which it can be seen that (Ti) could not be produced in the refining agent_0.4V_0.6) C single phase solid solution particles.

Comparative example No. two

This comparative example prepared a refiner, the preparation method of which included the steps of:

s11, preparing powder used for reaction compaction: using carbon nanotubes as carbon source, urea powder as carbon source and nitrogen source, weighing 80 g of aluminum powder with a particle size of 20 μm, 6.076 g of titanium powder with a particle size of 20 μm, 9.699 g of vanadium powder with a particle size of 45 μm, 0.095 g of carbon nanotubes and 6.191 g of urea powder with a particle size of 50 μm (CON)₂H₄) And then standby. Wherein the molar ratio of Ti/V/C/N in the Al-Ti-V-C-N system is 0.4:0.6:0.35:0.65, and the mass fraction of Al is 80 wt.%.

S12, mixing the weighed aluminum powder, titanium powder, vanadium powder, carbon nano-tubes and urea powder to obtain reactant powder; then, putting the prepared reactant powder and zirconia grinding balls (the diameter is 5-22mm) into a mixing tank for ball milling, wherein the ball-material ratio is 10:1, the ball milling speed is 60r/min, and the ball milling time is 18 hours, so as to obtain a mixture; then, the mixture was taken out, wrapped with aluminum foil, placed in a cylindrical mold, and pressed on a hydraulic testing machine into a cylindrical green compact having a diameter of 30 mm.

S13, synthesizing the multi-element composite ceramic particle refiner by the pressed compact sintering in-situ reaction: firstly, wrapping the cylindrical pressed blank with the diameter of 30mm prepared in the step S12 by using graphite paper, and putting the pressed blank into a graphite mould used for in-situ sintering reaction; then, putting the graphite mould with the cylindrical pressed compact into a vacuum hot-pressing sintering furnace, closing a furnace door, and vacuumizing until the air pressure in the furnace is lower than 10 Pa; then, heating is started, and the heating speed is set to be 40K/min; when the measured temperature in the furnace is 933K, setting heat preservation and applying axial pressure to the cylindrical pressed compact, wherein the stress value is 30MPa, and the pressure is kept for 20s for hot-pressing densification; then continuously heating to 1673K, keeping the temperature for 10min, keeping the vacuum in the furnace, and cooling to room temperature along with the furnace to obtain the refiner; the refinementThe results of the characterization of the agents are shown in figure 14. Wherein, figure 14 is the XRD pattern of the refiner. As can be seen from the figure, no (Ti) could be produced in the refiner_0.4V_0.6)(C_0.35N_0.65) Single phase solid solution particles.

Comparative example No. three

The comparative example provides a method for refining an aluminum alloy, which is to refine the initial aluminum alloy provided by the first embodiment by using the existing TiC ceramic particle refiner, and specifically comprises the following steps:

S33, adding the existing TiC ceramic particle refiner into the alloy liquid, and then carrying out mechanical stirring and ultrasonic treatment for 3min to obtain metal liquid; wherein the actual addition of the TiC ceramic particle refiner is 0.3 wt.%.

After adding the existing TiC ceramic particle refiner to the alloy liquid, wherein the actual addition amount of the TiC ceramic particle refiner is 0.3 wt.%, the average grain size of the aluminum alloy is reduced from 410.27 μm before non-refining to 203.43 μm after refining, and the experimental results are shown in table 1 and fig. 22.

As can be seen from the examples I to VI and the comparative examples I and II, the refiner provided by the embodiment of the invention generates the multi-element composite ceramic particles (Ti)_1-x,V_x) C and (Ti)_1-x,V_x)(C_1-y,N_y) Needs to satisfy 0<x≤0.5，0<y≤0.6。

In addition, as can be seen from the first to sixth examples and the third comparative example, the refining effect of the refiner containing the single-phase solid solution particles of the endogenous submicron multi-component composite ceramic provided by the embodiment of the invention is better than that of the existing TiC ceramic particle refiner.

In summary, the embodiments of the present invention utilize endogenous submicron multi-component composite ceramic particles (Ti)_1-x,V_x) C and (Ti)_1-x,V_x)(C_y,N_1-y) After the refiner refines the aluminum alloy, the grain size of the aluminum alloy is obviously refined; wherein the additive contains submicron (Ti)_0.85,V_0.15) C, when the addition amount of the refiner is 0.5 wt%, the grain size is reduced from 410.27 mu m to 58.73 mu m, which is reduced by nearly 7 times; with additions containing submicron (Ti)_0.85,V_0.15)(C_0.7,N_0.3) When the addition amount of the refiner of the ceramic particles is 0.5 wt.%, the grain size is reduced from 410.27 μm to 77.54 μm, which is nearly 5.3 times.

Table 1 below is a statistical result of average grain sizes of the unrefined initial aluminum alloys and the refined same aluminum alloys in examples one to six and comparative example three.

TABLE 1

Sample (I)	Average grain size
		Unrefined starting aluminium alloy	410.27μm
Example one refined aluminum alloy	58.73μm
		Example two refined aluminum alloy	143.56μm
Example three refined aluminum alloy	105.71μm
		Example four refined aluminum alloy	77.54μm
Example five refined aluminum alloys	146.45μm
		Example six refined aluminum alloy	161.63μm
Aluminum alloy after refining of comparative example III	203.43μm

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. A refiner, characterized in that the refiner comprises titanium carbide solid solution particles; the titanium carbide solid solution particles contain solid solution metal vanadium and have a chemical formula of (Ti)_1-x,V_x) C or (Ti)_1-x,V_x)(C_1-y,N_y) (ii) a In the formula, 0.15X is not less than 0.5 and y is not less than 0.3 and not more than 0.6; the refiner comprises the following components in percentage by weight: 3.90-22.73% of titanium, 0.42-12.44% of vanadium, 2.00-5.99% of carbon and the balance of aluminum, wherein the sum of the weight percentages of the components is 100%, or the refiner comprises the following components in percentage by weight: 3.83-23.34% of titanium, 0.42-12.24% of vanadium, 0.96-2.89% of carbon, 1.12-3.37% of nitrogen and the balance of aluminum, wherein the sum of the weight percentages of the components is 100%;

the preparation method of the refiner comprises the following steps:

placing a graphite mold containing a pressed blank under the conditions that the air pressure is not higher than 10Pa and the temperature is 900-950K for hot-pressing densification treatment, and then placing the graphite mold under the vacuum condition at the temperature of 1500-1800K for sintering treatment to obtain the refiner;

or comprises the following steps:

2. Use of the refiner of claim 1 for refining the texture of an alloy.

3. A method for thinning an aluminum alloy is characterized by comprising the following steps:

adding the refiner of claim 1 to the alloy liquid, and uniformly mixing to obtain molten metal; the mass of the refiner is 0.1-0.5% of that of the alloy liquid;

4. An aluminum alloy refined by the refining method as claimed in claim 3.

5. An aluminium alloy according to claim 4, wherein the aluminium alloy has an average grain size of 58.73-161.63 μm.