WO2024012036A1

WO2024012036A1 - Method for controlling alv55 alloy oxide film at back end

Info

Publication number: WO2024012036A1
Application number: PCT/CN2023/093850
Authority: WO
Inventors: 陈海军; 尹丹凤; 高雷章; 涂忠兵
Original assignee: 攀钢集团攀枝花钢铁研究院有限公司
Priority date: 2022-07-12
Filing date: 2023-05-12
Publication date: 2024-01-18
Also published as: CN115109976A; DE112023000044T5

Abstract

The present invention relates to a method for controlling an AlV55 alloy oxide film at the back end, comprising steps of: 1) placing a reactor on a smelting station and into a closed space, and pouring mixed furnace charge, wherein the furnace charge comprises V₂O₅ and metal Al; 2) igniting an igniter to trigger a reaction, to carry out aluminothermic reduction smelting; 3) after the reaction is finished, blowing inert gas into the reactor for protection; 4) measuring the surface temperature of an AlV55 alloy cake, and disassembling the furnace when the surface temperature is reduced to a preset temperature; 5) placing the AlV55 alloy cake in a water quenching tank for rapid cooling; and 6) after cooling is finished, taking out the AlV55 alloy cake, and crushing same to obtain an AlV55 alloy product. According to the method, the AlV55 alloy cake is rapidly cooled in a water quenching mode after the reaction is finished, thereby effectively reducing the product ratio of an oxide film.

Description

A back-end method to control the oxide film of AlV55 alloy

Technical field

The present invention relates to the field of metallurgy, and more specifically, to a method for back-end control of the oxide film of AlV55 alloy.

Background technique

Vanadium-aluminum alloy is used as an element additive for making titanium alloys, high-temperature alloys and some special alloys. It is widely used in advanced alloy materials in the aerospace field. It has high hardness, elasticity, seawater resistance and lightness. It is used to make water-based products. Airplanes and hydrogliders.

With the rapid development of our country's economy and the continuous improvement of people's consumption levels, our country's national defense strength and aerospace strength have been significantly enhanced, and titanium alloys used in the civil industry and aerospace fields have shown substantial growth momentum. At present, my country mainly uses AlV55 alloy to prepare Ti-6Al-4V alloy, and the market demand is huge. However, the proportion of oxide film of AlV55 alloy prepared using traditional methods is generally high, and there is no more practical control method.

Therefore, it is desirable to design a low-cost, high-efficiency, and high-quality back-end method for controlling the oxide film of AlV55 alloy.

Contents of the invention

In view of the shortcomings of the existing technology, the main purpose of the present invention is to provide a method for back-end control of the AlV55 alloy oxide film. This method effectively reduces the oxide film product ratio by rapidly cooling the AlV55 alloy cake by water quenching after the reaction is completed. .

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

According to the present invention, a back-end method for controlling the oxide film of AlV55 alloy is provided, which includes the following steps:

1) Place the reactor on the smelting platform in a closed space, pour in the mixed charge, which contains V ₂ O ₅ and metal Al;

2) Ignite the ignition agent to trigger the reaction and perform thermite reduction smelting;

3) After the reaction is completed, blow inert gas into the reactor for protection;

4) Detect the surface temperature of the AlV55 alloy cake, and remove the furnace when the surface temperature drops to the predetermined temperature;

5) Place the AlV55 alloy cake in a water quenching tank for rapid cooling; and

6) After cooling, take out the AlV55 alloy cake and crush it to obtain AlV55 alloy products.

According to an embodiment of the present invention, in step 1), the particle size of V ₂ O ₅ is ≤ 120 mesh, the particle size of metallic Al is ≤ 80 mesh, and the mixing time is 20 to 30 minutes.

According to an embodiment of the present invention, in step 2), the ignition agent is magnesium tape.

According to an embodiment of the present invention, step 3) includes passing inert gas above the molten pool of the reactor for purging.

According to an embodiment of the present invention, in step 4), the predetermined temperature is 800-1000°C.

According to an embodiment of the present invention, step 5) includes immersing the AlV55 alloy cake into the water quenching tank, so that the upper surface of the AlV55 alloy cake is 5 to 10 cm away from the liquid level of the water quenching tank.

According to an embodiment of the present invention, step 6) includes taking out the AlV55 alloy cake when the surface temperature is lower than 300°C.

According to an embodiment of the present invention, in step 6), when the AlV55 alloy cake is taken out, the surface temperature is higher than 130°C.

According to one embodiment of the invention, step 4) includes determining the surface temperature based on simulated data.

By adopting the above technical solution, the present invention has the following advantages compared with the prior art:

(1) According to the method of the present invention, the AlV55 alloy cake is quickly cooled by water quenching after the reaction is completed, which effectively reduces micro-cracks and avoids the formation of oxide films;

(2) In the method according to the present invention, increasing the cooling rate can also speed up the production process of AlV55 alloy products and improve production efficiency;

(3) The method according to the present invention is simple to operate. It only needs to add a water quenching step to obtain an AlV55 alloy product with a significantly reduced oxide film product ratio. The equipment modification cost is low and the effect is significant.

Description of drawings

Figure 1 shows a process flow chart of a method for back-end controlling the oxide film of AlV55 alloy according to the present invention.

Detailed ways

It should be understood that the embodiments of the invention shown in the exemplary embodiments are illustrative only. Although only a few embodiments have been described in detail herein, those skilled in the art will readily appreciate that various modifications are possible without materially departing from the teachings of the subject matter of the invention. Accordingly, all such modifications are intended to be included within the scope of the invention. Other substitutions, modifications, changes and deletions may be made to the design, operating conditions and parameters of the following exemplary embodiments without departing from the gist of the present invention.

As shown in Figure 1, the back-end method for controlling the AlV55 alloy oxide film according to the present invention generally includes the following steps:

Step S1: Place the reactor on the smelting platform in a closed space, pour in the mixed charge, which contains V ₂ O ₅ and metal Al;

Step S2: ignite the ignition agent to trigger the reaction and perform thermite reduction smelting;

Step S3: After the reaction is completed, blow inert gas into the reactor for protection;

Step S4: Detect the surface temperature of the AlV55 alloy cake, and remove the furnace when the surface temperature drops to the predetermined temperature;

Step S5: Place the AlV55 alloy cake in a water quenching tank for rapid cooling; and

Step S6: After cooling is completed, take out the AlV55 alloy cake and crush it to obtain the AlV55 alloy product.

Specifically, in step S1, the particle size of V ₂ O ₅ is ≤ 120 mesh, the particle size of metallic Al is ≤ 80 mesh, and the mixing time is 20 to 30 minutes to ensure that the raw materials are mixed evenly and the reaction is fully carried out.

In step S3, the inert gas may include at least one of argon, helium, and neon. This step may also include detecting the furnace temperature of the reactor and stopping the purge in response to the furnace temperature reaching 1100°C to 1300°C. Compared with the existing technology that fills the entire reaction system with protective gas at the beginning of the reaction until the cooling is completed, on the one hand, the method provided by the present invention starts purging immediately after the reaction ends and responds to the furnace temperature reaching a predetermined value. Stop the purge, and the predetermined value is preferably the oxide generation temperature of 1100°C to 1300°C, which ensures that the purge process continues within the oxide formation temperature range, and no oxide film will be formed after stopping the purge; on the other hand, , passing inert gas above the molten pool of the reactor for purging, which can use the smallest amount of inert gas to take away the most heat while ensuring the isolation of air. Through the solution of the present invention, the effective utilization of inert gas can be achieved to the greatest extent.

AlV55 alloy is mainly composed of a vanadium solid solution phase with a high vanadium content and a brittle phase with a low vanadium content. The closer to the equilibrium solidification process, the greater the gap in vanadium content between the two phases, and the more serious the microsegregation. Moreover, when the brittle phase and the solid solution phase coexist, microcracks are likely to appear between the two phases, resulting in defects such as poor grain boundary density and excessive oxide films in the vanadium-aluminum alloy. In step S4, the predetermined temperature can be set to be higher than the generation temperature of the brittle phase (for example, Al ₈ V ₅ ) in the AlV55 alloy, and is preferably set to 800 to 1000°C. In step S5, rapid cooling of the AlV55 alloy cake within the brittle phase generation temperature range can suppress the generation of the brittle phase, effectively reduce microcracks, and avoid the formation of oxide films. At the same time, the accelerated cooling rate can also speed up the production process of AlV55 alloy products and improve production efficiency.

Furthermore, submerging the AlV55 alloy cake into a water quenching tank can achieve a water sealing effect, effectively avoiding contact between the AlV55 alloy cake and air and reducing the use of inert gases. In embodiments of the present invention, when the AlV55 alloy cake is submerged into the water quenching tank, the upper surface of the AlV55 alloy cake can be about 5 to 10 cm away from the liquid level of the water quenching tank. In step S5, the AlV55 alloy cake can be fished out after the surface temperature is lower than 300°C. At this temperature, the oxidation reaction will no longer occur to form an oxide film. Preferably, the temperature at which the AlV55 alloy cake is taken out can be higher than 130°C, so that the AlV55 alloy cake can use its own residual temperature to evaporate the water on its surface, eliminating the need for a subsequent drying process.

The "detection" of surface temperature described in the present invention is a broad sense of detection, which can be actual temperature data directly obtained using instruments such as sensors, or simulated data indirectly obtained using computer simulation technology.

The above preparation method of the present invention will be described in detail below through detailed examples.

Example 1

Weigh 150kg of V ₂ O ₅ particles with a particle size of 120 to 160 mesh, and 132.3kg of metal Al particles with a particle size of 80 to 120 mesh, put them into the tank, mix for 20 minutes, and then pour them into the reactor. The magnesium ribbon is ignited to trigger the reaction. After completion, argon gas is blown in for protection. When the detected temperature reaches 1000°C, the furnace is dismantled. After dismantling the furnace, quickly put it into a water quenching tank for water quenching. The distance between the upper surface of the AlV55 alloy cake and the liquid level is 5cm. When the surface temperature reaches 300°C, the AlV55 alloy cake is taken out and crushed to obtain AlV55 alloy products.

After inspection, the oxide film product ratio in the obtained AlV55 alloy product was 0.3%.

Example 2

Weigh 100kg of V ₂ O ₅ particles with a particle size of ≤160 mesh and 87.7kg of metal Al particles with a particle size of ≤120 mesh, put them into the tank and mix for 25 minutes, then pour them into the reactor, ignite the magnesium ribbon to trigger the reaction, and blow in argon gas after the reaction is completed. For protection, when the detected temperature reaches 900℃, the furnace will be dismantled. After dismantling the furnace, quickly put it into a water quenching tank for water quenching. The distance between the upper surface of the AlV55 alloy cake and the liquid level is 8cm. When the surface temperature reaches 200°C, the AlV55 alloy cake is taken out and crushed to obtain the AlV55 alloy product.

After inspection, the oxide film product ratio in the obtained AlV55 alloy product was 0.15%.

Example 3

Weigh 200kg of V ₂ O ₅ particles with a particle size of 120 mesh to 160 mesh, and 176 kg of metal Al particles with a particle size of ≤80 mesh, put them into the tank, mix for 30 minutes, then pour them into the reactor, ignite the magnesium ribbon to trigger the reaction, and blow it in after the reaction is completed. Argon gas is used for protection, and when the detected temperature reaches 800°C, the furnace is dismantled. After dismantling the furnace, quickly put it into a water quenching tank for water quenching. The distance between the upper surface of the AlV55 alloy cake and the liquid level is 10cm. When the surface temperature reaches 130°C, the AlV55 alloy cake is taken out and crushed to obtain the AlV55 alloy product.

After inspection, the oxide film product ratio in the obtained AlV55 alloy product was 0.1%.

Comparative example 1

Weigh 150kg of V ₂ O ₅ particles with a particle size of 120 mesh to 160 mesh and a particle size of 80 mesh to 120 mesh. 132.3kg of metal Al particles were put into the tank and mixed for 20 minutes before being poured into the reactor. The magnesium ribbon was ignited to trigger the reaction. After the reaction was completed, argon gas was blown in for protection. After cooling to room temperature, the furnace is dismantled and crushed to obtain the AlV55 alloy product.

After inspection, the oxide film product ratio in the obtained AlV55 alloy product was 0.75%.

Comparative example 2

Weigh 100kg of V ₂ O ₅ particles with a particle size of ≤160 mesh and 87.7kg of metal Al particles with a particle size of ≤120 mesh, put them into the tank and mix for 25 minutes, then pour them into the reactor, ignite the magnesium ribbon to trigger the reaction, and blow in argon gas after the reaction is completed. To protect. After cooling to room temperature, the furnace is dismantled and crushed to obtain the AlV55 alloy product.

After inspection, the oxide film product ratio in the obtained AlV55 alloy product was 0.9%.

Comparative example 3

Weigh 200kg of V ₂ O ₅ particles with a particle size of 120 mesh to 160 mesh, and 176 kg of metal Al particles with a particle size of ≤80 mesh, put them into the tank, mix for 30 minutes, then pour them into the reactor, ignite the magnesium ribbon to trigger the reaction, and blow it in after the reaction is completed. Argon gas for protection. After cooling to room temperature, the furnace is dismantled and crushed to obtain the AlV55 alloy product.

After inspection, the oxide film product ratio in the obtained AlV55 alloy product was 1.0%.

In summary, the method of the present invention can be used to control the oxide film product ratio of AlV55 within 0.3%, which is significantly lower than the oxide film product ratio of AlV55 alloy products produced by existing methods, and has broad market application prospects.

The above are exemplary embodiments disclosed by the present invention. The order disclosed in the above embodiments of the present invention is only for description and does not represent the advantages and disadvantages of the embodiments. However, it should be noted that the above discussion of any embodiments is only illustrative, and is not intended to imply that the scope of the disclosure of the embodiments of the present invention (including the claims) is limited to these examples. Without departing from the scope defined by the claims, it can be Make various changes and modifications. The functions, steps and/or actions of the method claims in accordance with the disclosed embodiments described herein need not be performed in any particular order. In addition, although the elements disclosed in the embodiments of the present invention may be described or claimed in individual form, they may also be understood as plural unless expressly limited to the singular.

Those of ordinary skill in the art should understand that the above discussion of any embodiments is only an example. It is not intended to imply that the disclosed scope of the embodiments of the present invention (including the claims) is limited to these examples; under the idea of the embodiments of the present invention, the technical features in the above embodiments or different embodiments can also be combined. , and there are many other variations of different aspects of the embodiments of the invention described above, which are not provided in detail for the sake of brevity. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the embodiments of the present invention shall be included in the protection scope of the embodiments of the present invention.

Claims

A back-end method for controlling the oxide film of AlV55 alloy, which is characterized by including the following steps:

1) Place the reactor on the smelting platform in a closed space, and pour in the mixed charge, which contains V 2 O 5 and metal Al;

2) Ignite the ignition agent to trigger the reaction and perform thermite reduction smelting;

3) After the reaction is completed, blow inert gas into the reactor for protection;

4) Detect the surface temperature of the AlV55 alloy cake, and remove the furnace when the surface temperature drops to a predetermined temperature;

5) Place the AlV55 alloy cake in a water quenching tank for rapid cooling; and

6) After cooling is completed, the AlV55 alloy cake is fished out and crushed to obtain an AlV55 alloy product.
The method for back-end control of AlV55 alloy oxide film according to claim 1, characterized in that in step 1), the particle size of V 2 O 5 is ≤ 120 mesh, the particle size of metallic Al is ≤ 80 mesh, and the mixing time is 20 to 30 minutes.
The method for back-end control of AlV55 alloy oxide film according to claim 1, characterized in that in step 2), the ignition agent is magnesium tape.
The method for back-end control of AlV55 alloy oxide film according to claim 1, characterized in that step 3) includes passing an inert gas above the molten pool of the reactor for purging.
The method for back-end control of AlV55 alloy oxide film according to claim 1, characterized in that in step 4), the predetermined temperature is 800-1000°C.
The method for back-end control of AlV55 alloy oxide film according to claim 1, characterized in that step 5) includes immersing the AlV55 alloy cake into the water quenching tank so that the upper surface of the AlV55 alloy cake is at a certain distance from the AlV55 alloy cake. The liquid level in the water quenching tank is 5 to 10 cm.
The method for back-end control of AlV55 alloy oxide film according to claim 1, characterized in that step 6) includes removing the AlV55 alloy cake when the surface temperature is lower than 300°C. fish out.
The method for back-end control of AlV55 alloy oxide film according to claim 7, characterized in that in step 6), when the AlV55 alloy cake is fished out, the surface temperature is higher than 130°C.
The method for back-end control of AlV55 alloy oxide film according to claim 1, wherein step 4) includes determining the surface temperature based on simulation data.