阅读说明：本技术 一种含锆铝基合金及其制备方法与应用 (Zirconium-containing aluminum-based alloy and preparation method and application thereof ) 是由 贾义旺 宋东福 夏鹏 周楠 杨莉 于 2021-01-15 设计创作，主要内容包括：本发明公开了一种含锆铝基合金及其制备方法与应用,属于先进金属材料制备技术领域。该含锆铝基合金的制备方法包括以下步骤：浇铸前,将纳米TiCN颗粒分散于Al-Zr合金熔体中。通过纳米TiCN颗粒的加入,相比Al-Zr合金基体,含Zr铝合金晶粒得到明显细化。相比添加了传统晶粒细化剂Al-Ti-B的Al-Zr合金,毒化作用不再出现,晶粒细化作用十分显著。由此制得的含锆铝基合金屈服强度、抗拉强度以及断裂延伸率均得到大幅提升。该含锆铝基合金可用于生产含锆铝的器件,如航空航天器件、汽车制造器件、电子器件或体育器材等。(The invention discloses a zirconium-containing aluminum-based alloy and a preparation method and application thereof, belonging to the technical field of advanced metal material preparation. The preparation method of the zirconium-containing aluminum-based alloy comprises the following steps: before casting, the nano TiCN particles are dispersed in the Al-Zr alloy melt. By adding the nano TiCN particles, compared with an Al-Zr alloy matrix, Zr-containing aluminum alloy grains are obviously refined. Compared with Al-Zr alloy added with traditional grain refiner Al-Ti-B, the poisoning effect does not occur any more, and the grain refining effect is very obvious. The yield strength, tensile strength and fracture elongation of the prepared zirconium-containing aluminum-based alloy are greatly improved. The zirconium-aluminum-containing alloy can be used for producing zirconium-aluminum-containing devices, such as aerospace devices, automobile manufacturing devices, electronic devices or sports equipment and the like.)

1. The preparation method of the zirconium-containing aluminum-based alloy is characterized by comprising the following steps of: before casting, the nano TiCN particles are dispersed in the Al-Zr alloy melt.

2. The method according to claim 1, wherein the mass ratio of the nano TiCN particles to the Al-Zr alloy melt is 0.1-0.5: 100, respectively;

preferably, the particle size of the nano TiCN particles is 80-800 nm;

preferably, the method further comprises the step of preheating the nano TiCN particles to 200-300 ℃ before dispersing the nano TiCN particles in the Al-Zr alloy melt;

preferably, the nano TiCN particles are wrapped by aluminum foil.

3. The production method according to claim 1, wherein the raw materials of the Al — Zr alloy melt are commercially pure aluminum and a Zr-containing alloy;

preferably, the alloying element in the Zr-containing alloy contains at least one of Cu, Si, Mn, Mg, and Zn in addition to Zr;

preferably, the temperature of the Al-Zr alloy melt is 730-800 ℃.

4. The preparation method according to claim 1, wherein the nano TiCN particles are dispersed in the Al-Zr alloy melt by means of ultrasonic vibration;

preferably, the ultrasonic vibration is carried out for 3-10min under the condition that the power is 1-1.5 kW;

preferably, the frequency of the ultrasonic vibration is 10 to 20 kHz;

preferably, during the ultrasonic vibration, the ultrasonic tool head enters the Al-Zr alloy melt by 10-30 mm;

preferably, the material of the ultrasonic tool head is a Ti alloy material.

5. The preparation method according to claim 1, wherein the dispersing of the nano TiCN particles in the Al-Zr alloy melt is performed under the protection of nitrogen or inert gas atmosphere.

6. The preparation method as claimed in claim 1, wherein the nano TiCN particles are dispersed in the Al-Zr alloy melt, and then the temperature is maintained for 20-30min for the first time, then the temperature is adjusted to 720-750 ℃ for the second time, and the casting is performed after the temperature is stabilized.

7. The production method according to any one of claims 1 to 6, wherein the mold used for casting is a graphite mold;

preferably, before casting, the graphite mold is preheated for at least 30min at the temperature of 200-300 ℃;

preferably, the casting piece is subjected to air-cooling solidification after casting.

8. A zirconium-containing aluminum-based alloy, characterized by being produced by the production method as recited in any one of claims 1 to 7.

9. Use of a zirconium-aluminium-based alloy according to claim 8, for the production of a zirconium-aluminium-containing device;

preferably, the device comprises an aerospace device, an automotive manufacturing device, an electronic device, or a sports equipment.

10. A zirconium-aluminum-containing device, characterized in that the device is made of a material comprising the zirconium-aluminum-containing alloy according to claim 8;

preferably, the device comprises an aerospace device, an automotive manufacturing device, an electronic device, or a sports equipment.

Technical Field

The invention relates to the technical field of advanced metal material preparation, in particular to a zirconium-containing aluminum-based alloy and a preparation method and application thereof.

Background

The high-strength and ultrahigh-strength aluminum alloy containing trace Zr element is widely applied to the field of aerospace. The Zr element is added to form Al which is dispersed finely₃The Zr phase has three advantages: firstly, the quenching sensitivity of the alloy is reduced; secondly, recrystallization in the processes of hot working and heat treatment is inhibited; thirdly, the precipitation of eta' phase is accelerated, the dislocation density is increased, and the mechanical property of the alloy is improved. The Zr-containing aluminum alloy can effectively retain the small-angle crystal boundary obtained by processing deformation, and the stress corrosion resistance of the aluminum alloy is improved. Therefore, the strength, toughness and corrosion resistance of the aluminum alloy can be comprehensively improved by adding trace Zr element.

In the current industrial production process of large aluminum alloy ingots, the casting defects of serious macrosegregation, looseness, air holes and the like are more; the second phase is coarse or the macrosegregation of alloy elements is serious, so that the problems of cracking and the like during rolling can not be eliminated in subsequent processing.

The current common approach to solve the above problems is to add Al-Ti-B or Al-Ti-C during the preparation process, but all have poisoning phenomena.

In view of this, the invention is particularly proposed.

Disclosure of Invention

One of the objectives of the present invention consists in providing a process for the preparation of zirconium-containing aluminium-based alloys by poisoning, in order to solve the above-mentioned technical problems.

The second purpose of the invention is to provide the zirconium-containing aluminum-based alloy obtained by the preparation method.

Still another object of the present invention is to provide a use of the above zirconium-aluminum-containing alloy, for example, for producing zirconium-aluminum-containing devices, such as aerospace devices, automotive manufacturing devices, electronic devices or sports equipment.

The fourth object of the present invention is to provide a zirconium-containing aluminum device whose material contains the above zirconium-containing aluminum-based alloy.

The application can be realized as follows:

in a first aspect, the present application provides a method for preparing a zirconium-containing aluminum-based alloy, comprising the steps of: before casting, the nano TiCN particles are dispersed in the Al-Zr alloy melt.

In an alternative embodiment, the mass ratio of nano TiCN particles to Al — Zr alloy melt is 0.1 to 0.5: 100.

in an alternative embodiment, the nano TiCN particles have a particle size of 80 to 800 nm.

In an alternative embodiment, the step of preheating the nano TiCN particles to 200-300 ℃ before dispersing the nano TiCN particles in the Al — Zr alloy melt is further included.

In an alternative embodiment, the nano TiCN particles are wrapped by aluminum foil.

In an alternative embodiment, the starting materials for the Al — Zr alloy melt are commercially pure aluminum and Zr-containing alloys.

In an alternative embodiment, the alloying element in the Zr-containing alloy contains at least one of Cu, Si, Mn, Mg, and Zn in addition to Zr.

In an alternative embodiment, the temperature of the Al-Zr alloy melt is 730-.

In an alternative embodiment, the nano TiCN particles are dispersed in the Al-Zr alloy melt by means of ultrasonic vibration.

In an alternative embodiment, the ultrasonic vibration is performed for 3-10min at a power of 1-1.5 kW.

In an alternative embodiment, the frequency of the ultrasonic vibrations is 10-20 kHz.

In an alternative embodiment, the ultrasonic tool tip enters the Al-Zr alloy melt by 10-30mm during the ultrasonic vibration.

In an alternative embodiment, the material of the ultrasonic tool head is a Ti alloy material.

In an alternative embodiment, the dispersion of the nano TiCN particles in the Al — Zr alloy melt is performed under a nitrogen or inert gas atmosphere.

In an optional embodiment, after the nano TiCN particles are dispersed in the Al-Zr alloy melt, the temperature is maintained for 20-30min for the first time, then the temperature is adjusted to 720-750 ℃, the temperature is maintained for 5-10min for the second time, and casting is carried out after the temperature is stable.

In an alternative embodiment, the mold used for casting is a graphite mold.

In an alternative embodiment, the graphite mold is preheated at 200-300 ℃ for at least 30min prior to casting.

In an alternative embodiment, the casting is followed by air-cooling the cast part.

In a second aspect, the present application provides a zirconium-containing aluminum-based alloy prepared by the preparation method according to any one of the preceding embodiments.

In a third aspect, the present application provides the use of a zirconium-aluminium-based alloy as in the previous embodiments, for example for the production of zirconium-aluminium-containing devices.

In alternative embodiments, the device comprises an aerospace device, an automotive manufacturing device, an electronic device, or sporting equipment.

In a fourth aspect, the present application provides a zirconium-aluminum-containing device made from a material comprising a zirconium-aluminum-containing alloy as in the previous embodiment.

In alternative embodiments, the device comprises an aerospace device, an automotive manufacturing device, an electronic device, or sporting equipment.

The beneficial effect of this application includes:

according to the method, the nanometer TiCN particles are dispersed in the Al-Zr alloy melt before casting, so that the Al-Zr alloy can be well refined. The TiCN nano-particles inhibit the growth of crystal grains through the nano-particles, and a new field of grain refinement is opened. Meanwhile, the fine and dispersed TiCN nano particles can also be used as good alpha-Al nucleation sites during solidification, and grain refinement is further promoted. Meanwhile, the hard TiCN particles can play a good role in strengthening Olympic, and are beneficial to improving the yield strength, the tensile strength and the fracture elongation of the alloy. The zirconium-aluminum-containing alloy prepared by the method has TiCN nano particles distributed in a high dispersion mode, compared with an Al-Zr alloy matrix and an Al-Zr/Al-Ti-B alloy with a Zr poisoning phenomenon, the yield strength, the tensile strength and the fracture elongation of the alloy can be obviously improved, and the zirconium-aluminum-containing alloy can be used for producing zirconium-aluminum-containing devices, such as aerospace devices, automobile manufacturing devices, electronic devices or sports equipment and the like.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

Fig. 1(a) is an XRD diffraction pattern of TiCN particles in example 1, and fig. 1(b) is a microstructure photograph of TiCN particles.

FIG. 2(a) is a macroscopic gold phase diagram of the Al-Zr/Al-Ti-B alloy in which Zr poisoning occurs in the comparative example, and FIG. 2(B) is a macroscopic gold phase diagram of the Al-Zr/TiCN alloy in example 1.

FIG. 3(a) is a photograph of the microstructure of the Al-Zr/Al-Ti-B alloy in which Zr poisoning occurred in the comparative example, and FIG. 3(B) is a photograph of the microstructure of the Al-Zr/TiCN alloy in example 1.

FIG. 4 is a scanning electron micrograph of the microstructure of the Al-Zr/TiCN alloy in example 1, wherein FIGS. 4(a) and 4(d) are respectively scanning electron micrographs of Al-Zr/TiCN grain boundaries and intergranular regions, FIGS. 4(b) and 4(c) are respectively EDS maps of two atoms of Al and Ti corresponding to the region of FIG. 4(a), and FIG. 4(e) is the EDS result of the particle of FIG. 4 (d).

FIG. 5 is a graph of mechanical property data for the Al-0.2Zr matrix of example 1, the Al-0.2Zr/TiCN alloy, and the Al-0.2Zr/Al-Ti-B alloy of the comparative example.

FIG. 6 is grain size data for the Al-0.2Zr matrix, the Al-0.2Zr/TiCN alloy of example 1, and the Al-0.2Zr/Al-Ti-B alloy of the comparative example.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The zirconium-containing aluminum-based alloy provided by the application and the preparation method and application thereof are specifically explained below.

In the current industrial production process of large aluminum alloy ingots, the casting defects of serious macrosegregation, looseness, air holes and the like are more; the second phase is coarse or the macrosegregation of alloy elements is serious, so that the problems of cracking and the like during rolling can not be eliminated in subsequent processing. The method solves the problems by thinning the large-size cast ingot structure, and can comprehensively improve the strength and the plasticity of the material. The addition of grain refiner is the most simple and economical way to achieve the refinement of large ingot structure.

Grain refinement requires that two conditions are simultaneously satisfied: high efficiency nucleation core and alloy element for inhibiting crystal grain growth. The current Zr poisoning theories are also mainly divided into two types, namely that Zr interacts with nucleation particles to reduce the nucleation efficiency of a nucleating agent, and that Zr interacts with alloy elements to reduce the inhibition effect of the alloy elements on the grain growth.

At present, the refiner which is the most mature in industry and is most widely applied is Al-Ti-B or Al-Ti-C, however, the traditional grain refiner has refining limit and obvious poisoning phenomenon occurs in the grain refining process of Zr-containing aluminum alloy.

The inventor creatively discovers through long-term research and practice that: a small amount of nano TiCN particles are added into the Zr-containing aluminum alloy, so that the poisoning phenomenon can be well avoided, and the grain size of the matrix is effectively refined.

In view of this, the present application proposes a method for preparing a zirconium-containing aluminum-based alloy, which mainly comprises the following steps: before casting, the nano TiCN particles are dispersed in the Al-Zr alloy melt.

In alternative embodiments, the mass ratio of nano TiCN particles to Al — Zr alloy melt may be 0.1 to 0.5: 100, such as 0.1: 100. 0.2: 100. 0.3: 100. 0.4: 100 or 0.5: 100, etc., and may be 0.1 to 0.5: any other value within the range of 100. It is worth to say that the mass ratio of the nano TiCN particles to the Al-Zr alloy melt is lower than 0.1: 100, too low a final particle content may lead to poor refining, higher than 0.5: 100, there is no more significant refining effect.

In alternative embodiments, the nano TiCN particles have a particle size of 80 to 800nm, such as 80nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, or the like, and may have any other value in the range of 80 to 800 nm. It is worth to say that the nano TiCN particles with the particle size less than 80nm are expensive, and the thinning effect is not good if the particle size is more than 800 nm.

Preferably, the nano TiCN particles may be preheated to 200-300 deg.C, such as 200 deg.C, 250 deg.C or 300 deg.C, before dispersing in the Al-Zr alloy melt. The preheating time is preferably not less than 20min, such as but not limited to 20min, 25min, 30min or 35 min.

The nano TiCN particles can be wrapped by aluminum foil and then added into the Al-Zr alloy melt so as to avoid excessive oxidation and burning loss caused by contact with air.

As a reference, the raw materials of the Al-Zr alloy melt in the present application are industrial pure aluminum (purity is more than or equal to 99.7%) and Zr-containing alloy (such as Al-10Zr intermediate alloy). In an alternative embodiment, the alloying elements in the Zr-containing alloy may contain at least one of Cu, Si, Mn, Mg, and Zn in addition to Zr.

In the present application, the temperature of the Al-Zr alloy melt can be 730-. The temperature can ensure the fluidity of the melt and promote the dispersion of particles, and it is worth mentioning that if the temperature of the Al-Zr alloy melt is too high, unnecessary hydrogen absorption and oxidation are easily caused.

In the preferred embodiment of the present application, the nano TiCN particles are dispersed in the Al-Zr alloy melt by means of ultrasonic vibration. The introduction of ultrasonic vibration can refine grains, effectively prevent particle clusters, improve the dispersion uniformity of TiCN particles in a matrix, promote the formation of non-dendritic structures and improve the Olympic strengthening effect, and meanwhile, fine and dispersed TiCN particles can also be used as good alpha-Al nucleation sites during solidification, so that the grain refinement is further promoted, and the strength and the hardness of the alloy are favorably improved.

For reference, the ultrasonic vibration may be performed for 3 to 10min (e.g., 3min, 4min, 5min, 6min, 7min, 8min, 9min, or 10min, etc.) under the condition of 1 to 1.5kW (1kW, 1.1kW, 1.2kW, 1.3kW, 1.4kW, or 1.5kW) power, and preferably the ultrasonic vibration time is 3 to 8 min. The ultrasonic time is different according to different temperatures, the particles cannot be dispersed when the ultrasonic time is less than 3min, the ultrasonic time exceeding 10min has no obvious beneficial effect, and excessive loss is easily caused to the ultrasonic probe.

The frequency of the ultrasonic vibration may be, for example, 10 to 20kHz, such as 10kHz, 12kHz, 15kHz, 18kHz, or 20kHz, to mention a few.

In an alternative embodiment, the ultrasonic tool tip enters the Al — Zr alloy melt by 10-30mm, such as 10mm, 15mm, 20mm, 25mm, or 30mm, during the ultrasonic vibration process, so as to avoid unnecessary probe loss due to excessive probe immersion. The material of the ultrasonic tool head may be, but is not limited to, Ti alloy material.

In the application, the dispersion of the nano TiCN particles in the Al — Zr alloy melt is preferably performed under the protection of nitrogen or inert gas (such as argon), that is, under the protection of nitrogen or inert gas (such as argon), the nano TiCN particles are added into the Al-Zr alloy melt and subjected to ultrasonic vibration to disperse the nano TiCN particles in the Al-Zr alloy melt, so that the oxidation and burning loss can be further avoided.

In summary, according to the method, the Al-Zr melt and the TiCN reinforcing particles are protected by argon atmosphere in the mixing process, high-energy ultrasonic vibration is introduced, the ultrasonic vibration can generate cavitation effect and acoustic flow effect in the melt, the TiCN nano particles are dispersed and distributed in the melt, and the fine refining effect on pure aluminum and alloys such as Al-Zr or Al-Si can be realized by adding a small amount of TiCN nano particles. The TiCN nano-particles inhibit the growth of crystal grains through the nano-particles, and a new field of grain refinement is opened. Meanwhile, the fine and dispersed TiCN nano particles can also be used as good alpha-Al nucleation sites during solidification, and grain refinement is further promoted. The grain size of the Al-Zr/TiCN is only 15-25% of that of the Al-Zr/Al-Ti-B alloy in which the poisoning phenomenon occurs. Meanwhile, the hard TiCN particles can play a good role in strengthening Olympic, and are beneficial to improving the yield strength, the tensile strength and the fracture elongation of the alloy.

Further, after dispersing the nano TiCN particles in the Al-Zr alloy melt, carrying out heat preservation for 20-30min (such as 20min, 25min or 30 min) for the first time, then adjusting the temperature to 720 and 750 ℃ (such as 720 ℃, 730 ℃, 740 ℃ or 750 ℃ and the like), carrying out heat preservation for 5-10min (such as 5min, 6min, 7min, 8min, 9min or 10min and the like) for the second time, and carrying out casting after the temperature is stable.

The mold used for casting is referred to as a graphite mold.

In an alternative embodiment, the graphite mold is preheated at 200-. The method also includes removing dross from the surface of the melt before pouring the melt containing TiCN particles into the mold.

Furthermore, the casting process also comprises the step of carrying out air cooling solidification on the casting piece after casting.

The zirconium-containing aluminum-based alloy prepared by the method has high-dispersion-distribution nano TiCN particles, compared with Al-Zr matrix metal, the alloy is obviously refined, and the strength and the plasticity (particularly comprising yield strength, tensile strength and fracture elongation) are obviously improved; compared with the Al-Zr/Al-Ti-B alloy with Zr poisoning, the grain size of the alloy is remarkably reduced and is 15-25% of that of the alloy with Zr poisoning.

The aforementioned zirconium-containing aluminum-based alloy may be, but is not limited to, a 7 xxx-series high-strength aluminum alloy.

By reference, the Al-Zr/TiCN alloys provided herein may have an average grain size of 100-200 μm. While the average grain size of the Al-Zr/Al-Ti-B alloy in which Zr poisoning occurred was 600-700. mu.m.

In some embodiments, the mass fraction of TiCN particles in the zirconium-aluminum-based alloy is less than 2%.

In addition, the application also provides the application of the zirconium-aluminum-containing alloy, for example, the zirconium-aluminum-containing alloy can be used for producing devices containing zirconium and aluminum, such as aerospace devices, automobile manufacturing devices, electronic devices or sports equipment and the like.

Correspondingly, the application also provides a zirconium-aluminum-containing device, and the preparation material of the zirconium-aluminum-containing device contains the zirconium-aluminum-containing alloy. Similarly, the device may also include aerospace devices, automotive devices, electronic devices, sporting equipment, or the like.

The features and properties of the present invention are described in further detail below with reference to examples.

Example 1

The embodiment provides a preparation method of an Al-0.2Zr/TiCN alloy, which comprises the following steps:

step 1: melting industrial pure aluminum to 750 ℃ in a resistance furnace, then adding an Al-Zr intermediate alloy, preserving heat for 30 minutes, and fully mixing to ensure that the melt component is Al-0.2 wt.% Zr alloy.

Step 2: TiCN nano-particles with 0.5 percent of Al-0.2 wt.% Zr alloy mass are wrapped by high-purity aluminum foil and preheated for 2 hours at 250 ℃. Under the protection of argon atmosphere, adding TiCN nano-particles into the Al melt in the step 1. Wherein the TiCN nanoparticles have an average particle size of 80 nm.

And step 3: and (3) immersing a Ti alloy ultrasonic probe into the melt, wherein the immersion depth is 20mm, ultrasonic treatment is carried out for 5min, the ultrasonic power is 1.0kW, and the frequency is 15 kHz. Obtain a mixed melt, and keep the temperature for 25 min. And then, cooling the melt to 730 ℃, preserving the heat for 8min until the temperature is stable, casting the melt into a graphite mold preheated for 35min at 250 ℃, and carrying out air cooling solidification to obtain the Al-0.2Zr/TiCN alloy, wherein the TiCN accounts for 0.1 mass percent.

The XRD diffraction pattern of the TiCN particles in this example is shown in fig. 1(a), and the microstructure photograph of the TiCN particles is shown in fig. 1 (b). The macroscopic gold phase diagram of the Al-0.2Zr/TiCN alloy obtained in this example is shown in FIG. 2(b), and the microscopic structure photograph of the Al-0.2Zr/TiCN alloy is shown in FIG. 3 (b). The microstructure of the Al-0.2Zr/TiCN alloy is shown in FIG. 4, in which FIG. 4(a) and FIG. 4(d) are respectively the scanning electron micrographs of Al-Zr/TiCN grain boundary and intragranular region, and FIG. 4(b) and FIG. 4(c) are respectively the EDS surface scans of the Al and Ti atoms corresponding to the region of FIG. 4 (a). Fig. 4(e) is the EDS results for the particles in fig. 4 (d).

In addition, in the present example, the yield strength, tensile strength, and elongation at break data of the Al-0.2Zr matrix and the Al-0.2Zr/TiCN alloy finally obtained are shown in FIG. 5, and the grain size data of the Al-0.2Zr matrix and the Al-0.2Zr/TiCN alloy finally obtained are shown in FIG. 6.

Example 2

The embodiment provides a preparation method of an Al-0.2Zr/TiCN alloy, which comprises the following steps:

step 1: melting industrial pure aluminum to 750 ℃ in a resistance furnace, then adding an Al-Zr intermediate alloy, preserving heat for 30 minutes, and fully mixing to ensure that the melt component is Al-0.2 wt.% Zr alloy.

Step 2: TiCN nano-particles with 0.2 percent of Al-0.2 wt.% Zr alloy mass are wrapped by high-purity aluminum foil and preheated for 2 hours at 250 ℃. Under the protection of argon atmosphere, adding TiCN nano-particles into the Al melt in the step 1. Wherein the TiCN nanoparticles have an average particle size of 80 nm.

And step 3: and (3) immersing a Ti alloy ultrasonic probe into the melt, wherein the immersion depth is 20mm, carrying out ultrasonic treatment for 5min, the ultrasonic power is 1.0kW, the frequency is 15kHz, obtaining a mixed melt, and carrying out heat preservation for 25 min. And cooling the melt to 730 ℃, preserving the heat for 35min until the temperature is stable, casting the melt into a graphite mold preheated for 35min at 250 ℃, and performing air cooling solidification to obtain the Al-0.2Zr/TiCN alloy, wherein the TiCN accounts for 0.2 mass percent.

Example 3

The embodiment provides a preparation method of an Al-0.2Zr/TiCN alloy, which comprises the following steps:

step 1: melting industrial pure aluminum to 750 ℃ in a resistance furnace, then adding an Al-Zr intermediate alloy, preserving heat for 30 minutes, and fully mixing to ensure that the melt component is Al-0.2 wt.% Zr alloy.

Step 2: TiCN nano-particles with 0.3 percent of Al-0.2 wt.% Zr alloy mass are wrapped by high-purity aluminum foil and preheated for 2 hours at 250 ℃. Under the protection of argon atmosphere, adding TiCN nano-particles into the Al melt in the step 1. Wherein the TiCN nanoparticles have an average particle size of 80 nm.

And step 3: and (3) immersing a Ti alloy ultrasonic probe into the melt, wherein the immersion depth is 20mm, carrying out ultrasonic treatment for 5min, the ultrasonic power is 1.0kW, the frequency is 15kHz, obtaining a mixed melt, and carrying out heat preservation for 25 min. And cooling the melt to 730 ℃, preserving the heat for 8min until the temperature is stable, casting the melt into a graphite mold preheated for 35min at 250 ℃, and performing air cooling solidification to obtain the Al-0.2Zr/TiCN alloy, wherein the mass percent of TiCN is 0.3%.

Example 4

The embodiment provides a preparation method of an Al-0.2Zr/TiCN alloy, which comprises the following steps:

step 1: melting industrial pure aluminum to 750 ℃ in a resistance furnace, then adding an Al-Zr intermediate alloy, preserving heat for 30 minutes, and fully mixing to ensure that the melt component is Al-0.2 wt.% Zr alloy.

Step 2: TiCN nano-particles with 0.4 percent of Al-0.2 wt.% Zr alloy mass are wrapped by high-purity aluminum foil and preheated for 2 hours at 250 ℃. Under the protection of argon atmosphere, adding TiCN nano-particles into the Al melt in the step 1. Wherein the TiCN nanoparticles have an average particle size of 80 nm.

And step 3: and (3) immersing a Ti alloy ultrasonic probe into the melt, wherein the immersion depth is 20mm, carrying out ultrasonic treatment for 5min, the ultrasonic power is 1.0kW, the frequency is 15kHz, obtaining a mixed melt, and carrying out heat preservation for 25 min. And then, cooling the melt to 730 ℃, preserving the heat for 8min until the temperature is stable, casting the melt into a graphite mold preheated for 35min at 250 ℃, and carrying out air cooling solidification to obtain the Al-0.2Zr/TiCN alloy, wherein the TiCN accounts for 0.4 mass percent.

Example 5

The embodiment provides a preparation method of an Al-0.2Zr/TiCN alloy, which comprises the following steps:

step 1: melting industrial pure aluminum in a resistance furnace to 730 ℃, then adding an Al-Zr intermediate alloy, preserving heat for 20 minutes, and fully mixing to ensure that the melt component is Al-0.2 wt.% Zr alloy.

Step 2: TiCN nano-particles with 0.1 percent of Al-0.2 wt.% Zr alloy mass are wrapped by high-purity aluminum foil and preheated for 3 hours at 200 ℃. Under the protection of nitrogen atmosphere, adding TiCN nano-particles into the Al melt in the step 1. Wherein the TiCN nano-particles have an average particle size of 800 nm.

And step 3: and (3) immersing a Ti alloy ultrasonic probe into the melt, wherein the immersion depth is 10mm, carrying out ultrasonic treatment for 3min, the ultrasonic power is 1.2kW, the frequency is 20kHz, obtaining a mixed melt, and carrying out heat preservation for 20 min. And then, cooling the melt to 720 ℃, preserving the heat for 5min until the temperature is stable, casting the melt into a graphite mold preheated for 40min at the temperature of 200 ℃, and carrying out air cooling solidification to obtain the Al-0.2Zr/TiCN alloy, wherein the TiCN accounts for 0.1 mass percent.

Example 6

The embodiment provides a preparation method of an Al-0.2Zr/TiCN alloy, which comprises the following steps:

step 1: melting industrial pure aluminum to 800 ℃ in a resistance furnace, then adding an Al-Zr intermediate alloy, preserving heat for 25 minutes, and fully mixing to ensure that the melt component is Al-0.2 wt.% Zr alloy.

Step 2: TiCN nano-particles with the mass of 0.5% of Al-0.2 wt.% Zr alloy are wrapped by high-purity aluminum foil and preheated for 20min at 300 ℃. Under the protection of argon atmosphere, adding TiCN nano-particles into the Al melt in the step 1. Wherein the TiCN nanoparticles have an average particle size of 500 nm.

And step 3: and (3) immersing a Ti alloy ultrasonic probe into the melt, wherein the immersion depth is 30mm, carrying out ultrasonic treatment for 10min, the ultrasonic power is 1.5kW, and the frequency is 10kHz, so as to obtain a mixed melt, and carrying out heat preservation for 30 min. And then, cooling the melt to 750 ℃, preserving the heat for 10min until the temperature is stable, casting the melt into a graphite mold preheated for 30min at 300 ℃, and carrying out air cooling solidification to obtain the Al-0.2Zr/TiCN alloy, wherein the TiCN accounts for 0.5 mass percent.

Comparative example

The comparative example provides a method of making an Al-0.2Zr/Al-Ti-B alloy:

step 1: melting industrial pure aluminum to 750 ℃ in a resistance furnace, then adding an Al-Zr intermediate alloy, preserving heat for 30 minutes, and fully mixing to ensure that the melt component is Al-0.2 wt.% Zr alloy.

Step 2: an Al-Ti-B master alloy with Al-0.2 wt.% Zr mass of 0.5% was preheated at 250 ℃ for 2 hours. And (3) adding the Al-Ti-B intermediate alloy into the Al melt in the step (1) under the protection of argon atmosphere, and preserving the heat for 30 minutes.

And step 3: and (3) immersing a Ti alloy ultrasonic probe into the melt, wherein the immersion depth is 20mm, carrying out ultrasonic treatment for 5min, the ultrasonic power is 1.0kW, the frequency is 15kHz, obtaining a mixed melt, and carrying out heat preservation for 25 min. And then, cooling the melt to 730 ℃, preserving the heat for 8min until the temperature is stable, casting the melt into a graphite mold preheated for 35min at 250 ℃, and carrying out air cooling solidification to obtain the Al-0.2Zr/Al-Ti-B alloy, wherein the mass percent of Al-Ti-B is 0.5%.

The macroscopically metallographic picture of the Al-0.2Zr/Al-Ti-B alloy obtained in the comparative example is shown in FIG. 2(a), the microstructure picture is shown in FIG. 3(a), the yield strength, the tensile strength and the elongation at break are shown in FIG. 5, and the crystal grain size is shown in FIG. 6.

Comparing fig. 2(a) with fig. 2(b) and fig. 3(a) with fig. 3(b) can result in: the addition of TiCN avoids the Zr poisoning phenomenon of the traditional grain refiner (Al-Ti-B) in the grain refining process, and compared with Al-0.2Zr/Al-Ti-B alloy, Al-0.2Zr/TiCN grains are obviously refined, and the result can be also proved by figure 6.

Further, referring to fig. 5, it can be seen that the strength and plasticity of the material are improved due to the addition of the nano TiCN particles.

In summary, the preparation method provided by the application is simple and reasonable, and in the casting process of the Al-Zr/TiCN, the matrix crystal grains are obviously refined and the mechanical property is obviously improved through the dispersion effects of argon protection, addition temperature and ultrasonic vibration. The method has lower economic cost and better industrial popularization, and has stronger competitiveness in technology and economy.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.