CN116623027B - A method for preparing titanium alloy ingots with highly homogenized alloy components - Google Patents

Abstract

The invention belongs to the field of non-ferrous metal processing and discloses a method for preparing titanium alloy ingots with highly homogenized alloy components. The method includes the following steps: first, using alloy components in titanium alloys with a melting point higher than 1000°C as raw materials to prepare spray powder; The alloy components in titanium alloys with a melting point lower than 1000°C are used as raw materials to prepare a spray liquid, and then the spray liquid with spray powder adhered to the surface of the sponge titanium particles is sprayed to prepare sponge titanium particles with an alloy component layer deposited on the surface, and the alloy is deposited on the surface. After the layered titanium sponge particles and the sponge titanium particles with no alloy layer deposited on the surface are fully mixed, they are pressed and assembled and welded into consumable electrodes. Finally, the consumable electrodes are vacuum consumable arc melted to make titanium alloy castings. ingot. The titanium alloy ingot prepared by the invention achieves a high degree of uniformity in alloy composition, reduces the number of vacuum consumable arc melting times, and avoids the problems of electrode blockage and cracking during the vacuum consumable arc melting process.

Description

A method for preparing titanium alloy ingots with highly homogenized alloy components

Technical field

The invention belongs to the field of non-ferrous metal processing, and in particular relates to a method for preparing titanium alloy ingots with highly homogenized alloy components.

Background technique

Titanium alloy has high specific strength, good heat resistance and good corrosion resistance. It has become one of the most important metals in industry and is widely used in aerospace, petrochemical, seawater desalination, medical equipment and other industrial fields. Common alloying elements of titanium alloys are aluminum, tin, vanadium, zirconium, manganese, etc. By using these alloying elements together, the strength of titanium alloys can be significantly improved while maintaining good plasticity and hot and cold workability. However, titanium alloys are very sensitive to composition. Even small-scale fluctuations in composition can have a great adverse impact on the performance of titanium alloys. For example, the nominal composition of TA18 titanium alloy is Ti-3Al-2.5V. If the Al content in local areas of the alloy When the content exceeds 7%, the Ti ₃ Al brittle phase will precipitate, resulting in a decrease in the overall performance of the alloy, especially a significant reduction in the plasticity of TA18 titanium alloy. The V element is a stabilizing element for the beta phase of titanium alloys, and the beta phase in V-rich local areas is The content will increase significantly and also reduce the plasticity of TA18 titanium alloy. TA18 titanium alloy is mainly used to make seamless pipes used in aircraft piping systems. Its cold rolling processing method requires it to have very good shaping. For the manufacture of low- and medium-strength TA18 titanium alloy seamless pipes, a certain degree of local enrichment of Al and V elements is allowed, but high-strength TA18 titanium alloy seamless pipes place very high requirements on the uniformity of its alloy elements. , the slight uneven distribution of Al and V elements will lead to cracking of high-strength TA18 titanium alloy seamless pipes during the cold rolling process and unqualified expansion plasticity indicators of the finished pipes. Other titanium alloys such as TA16, TA21, TC4, etc. all face the same situation, that is, under general processing and use requirements, the alloy composition is allowed to fluctuate in a small range, but under harsh processing conditions and use requirements, its alloy composition must Achieve a high degree of uniformity. To achieve a high degree of uniformity in the alloy composition of titanium alloy products, it is mainly achieved through the cooperation of the following two continuous links. One is to ensure that the alloy composition of the titanium alloy product billet - titanium alloy ingot is highly uniform; the other is to ensure that the alloy composition of titanium alloy products is highly uniform. The titanium alloy ingot is further homogenized by plastic processing. Obviously, ensuring a high degree of uniformity in the alloy composition of titanium alloy ingots is the prerequisite and key to achieving a high degree of uniformity in the alloy composition of titanium alloy products.

However, it is very difficult to achieve a high degree of uniformity in the alloy composition of titanium alloy ingots. At present, most high-quality titanium alloy ingots are prepared by vacuum consumable arc melting, that is, sponge titanium particles, bean-shaped alloy element pure metal and bean-shaped alloy element master alloy are used as raw materials, which are mixed and pressed into consumable form. electrode, and then prepare titanium alloy ingots through vacuum consumable arc melting. Sponge titanium particles of different sizes, bean-shaped alloy element pure metal, and bean-shaped alloy element master alloy are difficult to mix fully and evenly like metal powder. In addition, vacuum consumable arc melting involves simultaneous melting and solidification. According to the melting method, even if the homogenization is promoted by no less than three times of vacuum consumable arc melting, there will still be enriched and depleted areas of alloy components in the titanium alloy ingot. To achieve a high degree of uniformity in alloy composition through subsequent plastic deformation of titanium alloy ingots requires repeated forging and extrusion processes, which is very time-consuming and costly.

In order to improve the uniformity of the alloy composition of titanium alloy ingots, Chinese patent CN113278812A invented a vacuum consumable melting method for high Mo content Ti-Mo alloy homogeneous ingots to improve the uniformity of the alloy composition of Ti-Mo titanium alloy ingots. Nature, this method uses five vacuum consumable arc meltings, and the Ti-Mo electrode is forged after two vacuum consumable arc meltings; in the Chinese patent CN113832363A titanium alloy ingot and its preparation method, vacuum self-generating The stable melting stage and the feeding stage performed sequentially during the consumptive arc melting process are used to promote the uniformization of the alloy composition of titanium alloy ingots; Chinese invention patent CN114091248 A invented a simulation method to predict the solidification process of vacuum consumptive melting ingots. The invention has a good guiding role in optimizing the vacuum consumable arc melting process to obtain ingots with uniform composition.

For the current preparation method of consumable electrodes, since the raw materials are all large particles, and the majority of the titanium sponge particles have poor mutual binding force after pressing, this has led to two problems. One is the central part of the consumable electrode. The bonding strength between the sponge titanium particles is not enough, and there is a problem of pieces falling off during the smelting process. The second is that for large ingots, in order to avoid the problem of insufficient bonding strength between sponge titanium particles, corresponding large electrode blocks cannot be prepared to assemble Welding to form a whole electrode, but only smaller electrode blocks can be prepared to assemble and weld into a whole electrode, which increases the number of welding points and also increases the accident rate of the smelting process being forced to stop due to solder joint failure during the smelting process. Therefore, a new method for preparing titanium alloy ingots is urgently needed, which can not only ensure that the alloy composition of titanium alloy ingots is highly uniform, but also reduce the number of vacuum consumable arc melting, and can effectively improve vacuum consumable arc melting. Process safety.

Contents of the invention

The object of the present invention is to provide a method for preparing titanium alloy ingots with highly homogenized alloy components. The spray deposition method is used to deposit alloy component layers on the surface of sponge particles to prepare raw materials for consumable electrodes, thereby realizing titanium alloy ingot alloys. High degree of homogenization of ingredients.

Therefore, the present invention provides the following technical solution: a method for preparing titanium alloy ingots with highly homogenized alloy components, which is characterized in that it includes the following steps:

Step 1: Use the alloy components in the titanium alloy with a melting point higher than 1000°C as raw materials to prepare spray powder, and use the alloy components in the titanium alloy with a melting point lower than 1000°C as raw materials to prepare spray liquid;

Step 2: Spray the spray liquid with spray powder adhered to the surface of the titanium sponge particles to prepare titanium sponge particles with an alloy component layer deposited on the surface;

Step 3: Fully mix the titanium sponge particles with the alloy component layer deposited on the surface and the sponge titanium particles without the alloy component layer deposited on the surface, and prepare a consumable electrode after mixing;

Step 4: Perform vacuum consumable arc melting on the consumable electrode to make titanium alloy ingot.

As a preferred solution of the present invention, a method for preparing a titanium alloy ingot with highly homogenized alloy components is used, wherein a co-injection method is used to spray spray liquid with spray powder adhered to the sponge titanium particles.

As a preferred solution of the present invention, a method for preparing titanium alloy ingots with highly homogenized alloy components is provided, wherein: when spraying liquid with spray powder adhered to the surface of titanium sponge particles, the titanium sponge particles are placed on a vibrating table, The titanium sponge particles maintain an upward motion on the vibrating table.

As a preferred option of the preparation method of titanium alloy ingots with highly homogenized alloy components according to the present invention, the process of spraying the spray liquid with spray powder adhered to the surface of the sponge titanium particles is carried out in a spray chamber, and the upper part of the spray chamber is provided There is an injector head, a vibration table is provided under the injector head, and the injector chamber is protected by inert gas.

As a preferred solution of the present invention, the method for preparing titanium alloy ingots with highly homogenized alloy components, wherein: the mass percentage of titanium sponge particles with an alloy component layer deposited on the surface of the consumable electrode is greater than or equal to 70 %.

As a preferred option of the preparation method of titanium alloy ingots with highly homogenized alloy components according to the present invention, the particle size of the sprayed powder is less than 10 μm, and the particle size of the sponge titanium particles is 5 to 12.5 mm.

As a preferred option of the preparation method of titanium alloy ingots with highly homogenized alloy components according to the present invention, when the spray liquid with spray powder adhered to the surface of the titanium sponge particles is sprayed, the height of the titanium sponge particles is not low. at 5cm.

As a preferred embodiment of the method for preparing titanium alloy ingots with highly homogenized alloy components according to the present invention, during the co-injection process, the spray powder is directly sprayed into the atomization cone formed by the spray liquid.

As a preferred embodiment of the method for preparing titanium alloy ingots with highly homogenized alloy components according to the present invention, the number of times of vacuum consumable arc melting is no more than 2 times.

The method of the present invention can not only achieve a high degree of uniformity of the alloy composition of the titanium alloy ingot, effectively reduce the number of vacuum consumable arc melting, but also effectively improve the safety of the vacuum consumable melting process. Because after a layer of alloy elements is sprayed on the surface of the titanium sponge particles, especially when the alloy elements contain more soft elements such as Al, Sn, and Cu, the contact surface between the titanium sponge particles becomes a deposit of alloy elements. At the contact surface between the layers, during the pressing process of the electrode block, the alloy element deposition layer is soft and easily adheres and bites with each other, which greatly increases the bonding strength between the particles, thereby greatly increasing the strength of the electrode block. Therefore The electrode block can be made larger to reduce the number of subsequent welding joints and improve the safety of consumable electrodes; also because the strength of the electrode block is increased, the danger of falling blocks during the vacuum consumable arc melting process is avoided.

The invention has the following advantages:

(1) By spraying and depositing alloy component layers on the surface of sponge titanium particles, the present invention can achieve a high degree of uniformity of alloy components in titanium alloy ingots under the conditions of no more than two vacuum consumable arc meltings;

(2) The present invention sprays and deposits alloy component layers on the surface of sponge titanium particles, which increases the compactness of the consumable electrode blocks during compaction and the bonding strength between particles, and avoids the falling and falling of the consumable electrode blocks during the smelting process. rupture issues;

(3) The present invention can prepare large-sized and high-strength consumable electrode blocks by spraying and depositing alloy component layers on the surface of sponge titanium particles, thereby reducing the assembly and welding joints of the overall consumable electrode and increasing the vacuum self-consumption. Safety of arc smelting process.

Description of the drawings

Figure 1 is a flow chart for preparing a titanium alloy ingot with highly homogenized alloy components according to the present invention;

Figure 2 is a diagram of the injection device of the present invention;

Figure 3 is a schematic diagram of the 9-point sampling position of the titanium ingot head section.

Detailed ways

The present invention will be further described below in conjunction with the accompanying drawings.

With reference to Figure 1, a method for preparing titanium alloy ingots with highly homogenized alloy components according to the present invention includes the following steps:

Step 1: Use the alloy components in the titanium alloy with a melting point higher than 1000°C as raw materials to prepare spray powder, and use the alloy components in the titanium alloy with a melting point lower than 1000°C as raw materials to prepare spray liquid.

Titanium alloys with melting points higher than 1000°C include vanadium, molybdenum, zirconium, niobium, etc. According to the specific alloy components corresponding to different brands of titanium alloys, spray powder is first prepared. If a certain brand of titanium alloy contains only one alloy component with a melting point higher than 1000°C, the powder of this alloy component is used as raw material to prepare spray powder. , if it contains two or more alloy components with a melting point higher than 1000°C, thoroughly mix the two or more alloy components with a melting point higher than 1000°C as raw materials and prepare spray powder. The purity of each component of the spray powder raw materials should be higher than 99.95%, and the particle size should be less than 10 μm.

Alloy components in titanium alloys with melting points lower than 1000°C include aluminum and tin. Prepare the spray liquid according to the specific alloy ingredients corresponding to different brands of titanium alloys. If a certain brand of titanium alloy only contains one kind of alloy with a melting point lower than 1000°C. If it contains two or more alloy components with a melting point lower than 1000°C, use two or more alloy components with a melting point lower than 1000°C as raw materials to prepare the spray liquid. liquid. The purity of the alloy component raw materials used to prepare the spray liquid should be higher than 99.95%. The spray liquid is preferably prepared by vacuum induction heating melting method.

Step 2: Spray the spray liquid with spray powder adhered to the surface of the titanium sponge particles to prepare titanium sponge particles with an alloy component layer deposited on the surface;

As shown in Figure 2, the injection device includes an injection chamber 1, a vibrating table 2, a nozzle 3, a melting furnace 4, an atomizer 5, a powder feeder 6, and a powder feeding nozzle 7. The nozzle 3 is located in the upper part of the spray chamber 1, and the vibration table 2 is located in the lower part of the spray chamber 1. First, sponge titanium particles 8 with a particle size of 5 to 12.5 mm are placed on the vibration table 2 located at the lower part of the spray chamber 1. The vibration table 2 vibrates longitudinally, so that the sponge titanium particles 8 move upward under the mechanical vibration of the vibration table 2. Throwing motion, and the throwing height is not less than 5cm.

Then, co-injection technology is used to spray the spray liquid with spray powder adhered to the titanium sponge particles to prepare titanium sponge particles with an alloy component layer deposited on the surface. The principle and process are as follows: under the action of the atomizer 5, the spray liquid 9 is sprayed downward from the nozzle 3 at high speed to form the spray liquid atomization cone 10, that is, a cone-shaped mist composed of countless spray liquid droplets is formed. The spray powder 11 is sprayed into the spray liquid atomization cone 10 through the powder feeding nozzle 7, and then adheres to the small droplets of the spray liquid. The small droplets of the spray liquid adhered with the spray powder are sprayed at high speed towards the titanium sponge particles 8 located on the vibrating table 2. After impacting the surface of the titanium sponge particles 8, they spread on the surface of the titanium sponge particles 8 and cool and solidify to form an alloy composition layer. Realize the co-injection process of solid-phase spray powder and liquid-phase spray liquid. During the co-injection process, since the titanium sponge particles 8 maintain an upward motion and the vibrating table 2 also moves laterally, the accessibility and uniformity of the injection are ensured.

The ratio of the flow rate of the spray liquid to the flow rate of the spray powder depends on the alloy composition of the corresponding grade of titanium alloy. The spray chamber 1 is protected by argon gas.

The present invention adopts the co-injection method to prepare the alloy component layer on the surface of sponge titanium particles 8, which has the following advantages: (1) The melting point of the injection liquid is low, which reduces the requirements for smelting equipment and nozzles; (2) It reduces the requirements for the injection process parameters. Requirements, it is easy to spray deposit on the surface of sponge titanium particles to form a firmly bonded alloy component layer; (3) It avoids the spray liquid composed of multiple alloy components from reacting with the crucible at high temperature and contaminating the spray liquid.

After the alloy component layer is deposited on the surface of the sponge titanium particles 8, it is not only beneficial to the uniformization of the alloy components of the titanium alloy ingot, but also beneficial to pressing into an electrode block with high density and high strength. Because the matrix of the alloy component layer deposited on the surface of sponge titanium particles 8 is a soft layer such as aluminum or aluminum-tin, during the pressing process, the soft layer is conducive to the coordinated movement and densification of sponge titanium particles 8, and the sponge titanium particles can easily Mutual adhesion and occlusion are generated, which greatly increases the bonding strength between particles, thereby greatly improving the strength of the electrode block. Therefore, the electrode block can be made larger, thereby reducing the number of subsequent welding joints and increasing self-consumption. The safety of the electrode; also because the strength of the electrode block is improved, the danger of falling blocks during the vacuum consumable arc melting process is avoided.

Step 3: Fully mix the titanium sponge particles with the alloy component layer deposited on the surface and the sponge titanium particles without the alloy component layer deposited on the surface, and prepare a consumable electrode after mixing;

Since vacuum consumable arc melting can further promote the uniformity of the alloy composition of titanium alloy ingots, it is not required that all titanium sponge particles be deposited with alloy composition layers, that is, the alloy composition of the titanium alloy is not required to be evenly distributed to all titanium sponge particles. On the surface, the titanium alloy alloy ingredients are only required to be evenly distributed on the surface of most of the titanium sponge particles to achieve the highly uniform alloy ingredients of titanium alloy ingots, which can reduce production costs. Weighing the production cost and the homogenization effect of the alloy composition of titanium alloy ingots, it is required that sponge titanium particles with an alloy composition layer deposited on the surface account for 70% or more of the proportion of consumable electrode raw materials.

In this step, the titanium sponge particles with the alloy component layer deposited on the surface and the sponge titanium particles without the alloy component layer deposited on the surface are fully mixed to serve as consumable electrode raw materials. A special mold is used to press the consumable electrode raw material into several smaller consumable electrode blocks under high pressure, and then the several consumable electrode blocks are assembled and welded into the final consumable electrode.

Step 4: Perform vacuum consumable arc melting on the consumable electrode to make titanium alloy ingot.

Using the consumable electrode prepared in step 3 for 1 to 2 times of vacuum consumable arc melting, a titanium alloy ingot with highly uniform alloy composition can be obtained.

Example 1

The grade of titanium alloy ingot to be prepared is TA18, and its nominal composition is Ti-3Al-2.5V.

A method for preparing titanium alloy ingots with highly homogenized alloy components, including the following steps:

Step 1: Use vanadium metal powder as raw material to prepare spray powder, and use aluminum as raw material to prepare spray liquid;

Vanadium metal powder with a purity greater than 99.95% is used as raw material, and vanadium spray powder with a particle size of less than 10 microns is prepared through high-energy ball milling or other methods. Put high-purity aluminum with a purity greater than 99.95% into a graphite crucible, and use vacuum induction heating to smelt the high-purity aluminum to prepare aluminum spray liquid. The temperature of the spray liquid in the graphite crucible melting furnace is maintained at 730~750°C.

Step 2: Spray aluminum spray liquid with vanadium spray powder adhered to the surface of the sponge titanium particles to prepare sponge titanium particles with an aluminum-vanadium alloy layer deposited on the surface;

Sponge titanium particles with a particle size of 5-12.5mm are placed on a vibrating table, and an aluminum spray liquid with vanadium spray powder adhered to the surface of the sponge titanium particles is sprayed using a spray device. That is, through co-spraying technology, an aluminum-vanadium alloy is deposited on the surface. Composed of layered titanium sponge particles. The gas used to atomize aluminum spray liquid is argon gas, the argon gas pressure is 3.0MPa; the distance from the nozzle to the vibration table is 300mm. The ratio of the aluminum spray liquid flow rate (g/min) sprayed from the nozzle to the vanadium spray powder flow rate (g/min) sprayed from the powder nozzle is 3:2.5. The spray chamber is protected by argon gas.

During the spraying process, the vibrating table maintains mechanical vibration, and the titanium sponge particles continue to be thrown upward under the mechanical vibration of the vibrating table. The height of the titanium sponge particles being thrown upward is controlled at 5-10cm. During the injection process, the vibrating table also moves left and right at a speed of 0.6mm/s. After spraying, an aluminum-vanadium alloy layer is deposited on the surface of the titanium sponge particles.

Step 3: Fully mix the titanium sponge particles with the aluminum-vanadium alloy layer deposited on the surface and the titanium sponge particles without the aluminum-vanadium alloy layer deposited on the surface. After mixing, press and assemble and weld to form a consumable electrode.

The titanium sponge particles with an aluminum-vanadium alloy component layer deposited on the surface and the sponge titanium particles without the aluminum-vanadium alloy component layer deposited on the surface are fully mixed as raw materials for consumable electrodes, and the sponge with the aluminum-vanadium alloy component layer deposited on the surface is used as a raw material. The mass of titanium particles accounts for 70%, and the mass of titanium sponge particles with no aluminum-vanadium alloy layer deposited on the surface accounts for 30%. Then the consumable electrode raw materials are put into the mold and pressed into several electrode blocks. Finally, several electrodes are The block assembly is welded into a consumable electrode.

Step 4: Perform vacuum consumable arc melting on the consumable electrode to make titanium alloy ingot.

Through two vacuum consumable arc meltings, a TA18 titanium alloy ingot with highly uniform composition was prepared.

Take longitudinal samples from five parts of the titanium alloy ingot prepared in step 4, including the head, upper, middle, lower and bottom, and conduct component detection. The sampling method is: respectively at the position 100mm from the top surface of the titanium alloy ingot (head), the middle of the ingot (middle), the middle position between the head and the middle (upper), and the position 25mm from the bottom (bottom), and the middle position (lower part) between the bottom and the middle to measure the chemical composition of the titanium alloy ingot in the longitudinal direction.

Cut the titanium alloy ingot head along the radial direction to obtain the head section. Use the 9-point sampling method as shown in Figure 3 to sample the head section at 9 points (TP1~TP9), and measure the TP1 to TP9 points. chemical composition. R in Figure 3 represents the radius of the ingot cross section.

The chemical composition of the obtained titanium alloy ingot in the longitudinal direction is shown in Table 1, and the chemical composition of the 9-point end surface of the head of the titanium alloy ingot is shown in Table 2.

Table 1 Longitudinal chemical composition of titanium alloy ingot in Example 1

It can be seen from Table 1 that the composition uniformity of the TA18 ingot prepared using this method is good. The content deviation of the longitudinal alloy components Al and V of the ingot does not exceed 0.03% (wt.%, the same below). The impurity elements Fe, O, and C , N, H and Y element contents all meet the control range requirements of less than or equal to 0.30%, 0.12%, 0.05%, 0.025%, 0.015% and 0.005%.

Table 2 9-point chemical composition of the head end surface of the titanium alloy ingot in Example 1

It can be seen from Table 2 that the composition of the ingot has good uniformity. In the analysis results of 9 points on the head end surface, the content deviation of the alloy components Al and V does not exceed 0.03% (wt.%, the same below), and the content of the impurity element Fe meets the requirement of less than or equal to 0.3% control range required.

Example 2

The grade of titanium alloy ingot to be prepared is TC1, and its nominal composition is Ti-2Al-1.5Mn.

A method for preparing titanium alloy ingots with highly homogenized alloy components, including the following steps:

Step 1: Use manganese metal powder as raw material to prepare spray powder, and use aluminum as raw material to prepare spray liquid;

Manganese metal powder with a purity greater than 99.95% is used as raw material, and manganese spray powder with a particle size of less than 10 microns is prepared through high-energy ball milling or other methods. Put high-purity aluminum with a purity greater than 99.95% into a graphite crucible, and use vacuum induction heating to smelt the high-purity aluminum to prepare aluminum spray liquid. The temperature of the spray liquid in the graphite crucible melting furnace is maintained at 730~750°C.

Step 2: Spray aluminum spray liquid with manganese spray powder adhered to the surface of titanium sponge particles to prepare titanium sponge particles with an aluminum-manganese alloy layer deposited on the surface;

Sponge titanium particles with a particle size of 5-12.5 mm are placed on a vibrating table, and a spray device is used to spray aluminum spray liquid with manganese spray powder adhered to the sponge titanium particles. That is, through co-spraying technology, the aluminum-manganese alloy component is deposited on the surface. layer of sponge titanium particles. The gas used to atomize aluminum spray liquid is argon gas, the argon gas pressure is 3.0MPa; the distance from the nozzle to the vibration table is 300mm. The ratio of the aluminum spray liquid flow rate (g/min) sprayed from the nozzle to the manganese spray powder flow rate (g/min) sprayed from the powder nozzle is 2:1.5. The spray chamber is protected by argon gas.

During the spraying process, the vibrating table keeps vibrating, and the titanium sponge particles continue to be thrown upward under the mechanical vibration of the vibrating table. The height of the titanium sponge particles being thrown upward is controlled at 5-10cm. During the injection process, the vibrating table also moves left and right at a speed of 0.6mm/s. After the spraying is completed, a layer of aluminum-manganese alloy composition is deposited on the surface of the titanium sponge particles.

Step 3: Fully mix the titanium sponge particles with the aluminum-manganese alloy layer deposited on the surface and the titanium sponge particles without the aluminum-manganese alloy layer deposited on the surface. After mixing, press and weld together to form a consumable electrode.

The titanium sponge particles with an aluminum-manganese alloy component layer deposited on the surface and the sponge titanium particles without the aluminum-manganese alloy component layer deposited on the surface are thoroughly mixed as raw materials for consumable electrodes, and the sponge with an aluminum-vanadium alloy component layer deposited on the surface is used as a raw material. The mass of titanium particles accounts for 75%, and the mass of titanium sponge particles with no aluminum-vanadium alloy layer deposited on the surface accounts for 25%. Then the consumable electrode raw materials are put into the mold and pressed into several electrode blocks. Finally, several electrodes are The block assembly is welded into a consumable electrode.

Step 4: Perform vacuum consumable arc melting on the consumable electrode to make titanium alloy ingot.

Through one vacuum consumable arc melting, a TC1 titanium alloy ingot with highly uniform composition was prepared.

Take longitudinal samples from five parts of the titanium alloy ingot prepared in step 4, including the head, upper, middle, lower and bottom, and conduct component detection. The sampling method is: respectively at the position 100mm from the top surface of the titanium alloy ingot (head), the middle of the ingot (middle), the middle position between the head and the middle (upper), and the position 25mm from the bottom (bottom), and the middle position (lower part) between the bottom and the middle to measure the chemical composition of the titanium alloy ingot in the longitudinal direction.

Cut the titanium alloy ingot head along the radial direction to obtain the head section. Use the 9-point sampling method as shown in Figure 2 to sample the head section at 9 points (TP1~TP9), and measure the TP1 to TP9 points. chemical composition.

The chemical composition of the obtained titanium alloy ingot in the longitudinal direction is shown in Table 3, and the chemical composition of the 9-point end surface of the head of the titanium alloy ingot is shown in Table 4.

Table 3 Longitudinal chemical composition of titanium alloy ingot in Example 2

It can be seen from Table 3 that the composition of the TC1 ingot prepared using this method has good uniformity. The deviations of the alloying elements Al and Mn in the longitudinal direction of the ingot do not exceed 0.03% (wt.%, the same below). The impurity elements Fe, O, and C , N, and H element content each meet the control range requirements of less than or equal to 0.3%, 0.15%, 0.10%, 0.05%, and 0.012%.

Table 4 9-point chemical composition of the head end surface of the titanium alloy ingot in Example 2

It can be seen from Table 4 that the composition of the ingot has good uniformity. The deviations of the alloy elements Al and Mn in the analysis results at 9 points on the head end face do not exceed 0.04% and 0.03% respectively (wt.%, the same below). The content of the impurity element Fe Meet the control range requirement of less than or equal to 0.3%.

Example 3

The grade of titanium alloy ingot to be prepared is TC19, and its nominal composition is Ti-6Al-2Sn-4Zr-6Mo.

A method for preparing titanium alloy ingots with highly homogenized alloy components, including the following steps:

Step 1: Use zirconium metal powder and molybdenum metal powder as raw materials to prepare spray powder, and use aluminum and tin as raw materials to prepare spray liquid;

Using zirconium metal powder and molybdenum metal powder with purity greater than 99.95% as raw materials, prepare zirconium metal powder and molybdenum metal powder with particle sizes less than 10 microns through high-energy ball milling or other methods, and then press the zirconium metal powder and molybdenum metal powder into The mass ratio of 4:6 is fully mixed to prepare zirconium-molybdenum spray powder. Put aluminum and tin with a purity greater than 99.95% into a graphite crucible in a mass ratio of 6:2, and use vacuum induction heating to smelt aluminum and tin to prepare an aluminum-tin spray liquid. The aluminum-tin spray liquid is in the graphite crucible The temperature in the smelting furnace is maintained at 730~750℃.

Step 2: Spray the aluminum-tin spray liquid with zirconium-molybdenum spray powder adhered to the surface of the sponge titanium particles to prepare sponge titanium particles with a zirconium-molybdenum alloy layer deposited on the surface;

Sponge titanium particles with a particle size of 5-12.5mm are placed on a vibrating table, and an aluminum-tin spray liquid with zirconium-molybdenum spray powder adhered to the sponge titanium particles is sprayed using a spray device. That is, through co-spraying technology, aluminum is deposited on the surface. -Titanium sponge particles layered in a tin-zirconium-molybdenum alloy composition. The gas used to atomize the aluminum-tin spray liquid is argon gas, the argon gas pressure is 3.0MPa; the distance from the nozzle to the vibration table is 300mm. The ratio of the aluminum-tin spray liquid flow rate (g/min) sprayed from the nozzle to the zirconium-molybdenum spray powder flow rate (g/min) sprayed from the powder nozzle is 8:10. The spray chamber is protected by argon gas.

During the spraying process, the vibrating table keeps vibrating, and the titanium sponge particles continue to be thrown upward under the mechanical vibration of the vibrating table. The height of the titanium sponge particles being thrown upward is controlled at 5-10cm. During the injection process, the vibrating table also moves left and right at a speed of 0.6mm/s. After the spraying is completed, a layer of aluminum-tin-zirconium-molybdenum alloy composition is deposited on the surface of the sponge titanium particles.

Step 3: Fully mix the titanium sponge particles with the aluminum-tin-zirconium-molybdenum alloy layer deposited on the surface and the titanium sponge particles without the aluminum-tin-zirconium-molybdenum alloy layer deposited on the surface. After mixing, press and weld together to form a self-made composite. consumption electrode.

Fully mix titanium sponge particles with an aluminum-tin-zirconium-molybdenum alloy layer deposited on the surface and titanium sponge particles without an aluminum-tin-zirconium-molybdenum alloy layer deposited on the surface as raw materials for consumable electrodes, wherein the surface deposited with The mass of titanium sponge particles with an aluminum-tin-zirconium-molybdenum alloy composition layer accounts for 80%, and the mass of titanium sponge particles with no aluminum-tin-zirconium-molybdenum alloy composition layer deposited on the surface accounts for 20%, and then the consumable electrode raw materials are Put it into a mold and press it into several electrode blocks, and finally weld the several electrode blocks into a consumable electrode.

Step 4: Perform vacuum consumable arc melting on the consumable electrode to make titanium alloy ingot.

Through two vacuum consumable arc meltings, a TC19 titanium alloy ingot with highly uniform composition was prepared.

Take longitudinal samples from five parts of the titanium alloy ingot prepared in step 4, including the head, upper, middle, lower and bottom, and conduct component detection. The sampling method is: respectively at the position 100mm from the top surface of the titanium alloy ingot (head), the middle of the ingot (middle), the middle position between the head and the middle (upper), and the position 25mm from the bottom (bottom), and the middle position (lower part) between the bottom and the middle to measure the chemical composition of the titanium alloy ingot in the longitudinal direction.

Cut the titanium alloy ingot head along the radial direction to obtain the head section. Use the 9-point sampling method as shown in Figure 2 to sample the head section at 9 points (TP1~TP9), and measure the TP1 to TP9 points. chemical composition.

The chemical composition of the obtained titanium alloy ingot in the longitudinal direction is shown in Table 5, and the chemical composition of the 9-point end surface of the head of the titanium alloy ingot is shown in Table 6.

Table 5 Longitudinal chemical composition of titanium alloy ingot in Example 3

It can be seen from Table 5 that the composition uniformity of the TC19 ingot prepared using this method is good, and the deviation of each alloying element Al, Sn, Zr and Mo in the longitudinal direction of the ingot does not exceed 0.03% (wt.%, the same below), 0.03%, 0.02% and 0.05%. And the content of the impurity elements Fe, Si, O, C, N, and H each meets the control range requirements of less than or equal to 0.15%, 0.15%, 0.15%, 0.10%, 0.05%, and 0.015%.

Table 6 9-point chemical composition of the head end surface of the titanium alloy ingot in Example 3

It can be seen from Table 6 that the composition of the ingot has good uniformity. The deviations of each alloying element Al, Sn, Zr and Mo in the analysis results of 9 points on the head end face do not exceed 0.03% (wt.%, the same below), 0.03%, 0.05% and 0.04%. And the impurity element Fe and Si element content respectively meet the control range requirements of less than or equal to 0.15% and 0.15%.

The basic principles, main features and advantages of the present invention have been shown and described above. Those skilled in the art should understand that the above embodiments do not limit the present invention in any way, and any technical solutions obtained by equivalent substitution or equivalent transformation fall within the protection scope of the present invention.

The above are only preferred embodiments of the present invention, and the present invention is not limited to the contents of the embodiments. For those skilled in the art, various changes and modifications may be made within the scope of the technical solution of the present invention, and any changes and modifications made are within the protection scope of the present invention.

Claims (9)

1. A method for preparing titanium alloy ingots with highly homogenized alloy components, which is characterized in that it includes the following steps: Step 1: Use the alloy components in the titanium alloy with a melting point higher than 1000°C as raw materials to prepare spray powder, and use the alloy components in the titanium alloy with a melting point lower than 1000°C as raw materials to prepare spray liquid; Step 2: Spray the spray liquid with spray powder adhered to the surface of the titanium sponge particles to prepare titanium sponge particles with an alloy component layer deposited on the surface; Step 3: Fully mix the titanium sponge particles with the alloy component layer deposited on the surface and the sponge titanium particles without the alloy component layer deposited on the surface, and prepare a consumable electrode after mixing; Step 4: Perform vacuum consumable arc melting on the consumable electrode to make titanium alloy ingot. 2. A method for preparing titanium alloy ingots with highly homogenized alloy components according to claim 1, characterized in that a co-injection method is used to spray spray liquid with spray powder adhered to the sponge titanium particles. 3. A method for preparing titanium alloy ingots with highly homogenized alloy components according to claim 2, characterized in that when the spray liquid with spray powder adhered to the surface of the sponge titanium particles is sprayed, the sponge titanium particles are placed on a vibrating surface. On the table, the titanium sponge particles maintain an upward motion on the vibrating table. 4. A method for preparing a titanium alloy ingot with a highly uniform alloy composition according to any one of claims 1 to 3, characterized in that the process of spraying the spray liquid with spray powder adhered to the surface of the sponge titanium particles is in the spray chamber. To carry out, the upper part of the spray chamber is equipped with a spray head, and the lower part of the spray head is equipped with a vibration table. The spray chamber is protected by inert gas. 5. A method for preparing a titanium alloy ingot with a highly homogenized alloy composition according to claim 1, characterized in that the mass percentage of titanium sponge particles with an alloy composition layer deposited on the surface of the consumable electrode Greater than or equal to 70%. 6. A method for preparing a titanium alloy ingot with highly homogenized alloy components according to any one of claims 1 to 3 and 5, characterized in that the particle size of the sprayed powder is less than 10 μm, and the particle size of the titanium sponge particles is The diameter is 5~12.5mm. 7. A method for preparing titanium alloy ingots with highly homogenized alloy components according to claim 4, characterized in that when the spray liquid with spray powder adhered to the surface of the titanium sponge particles is sprayed, the titanium sponge particles are thrown upward. The height is not less than 5cm. 8. A method for preparing titanium alloy ingots with highly homogenized alloy components according to claim 2 or 3, characterized in that during the co-injection process, the spray powder is directly sprayed into the atomization cone formed by the spray liquid. middle. 9. A method for preparing titanium alloy ingots with highly homogenized alloy components according to any one of claims 1, 2, 5 and 7, characterized in that the number of vacuum consumable arc melting times does not exceed 2 times. .