CN116623027A - A preparation method of titanium alloy ingot with highly uniform alloy composition - Google Patents

Abstract

The invention belongs to the field of nonferrous metal processing, and discloses a preparation method of a titanium alloy cast ingot with highly homogenized alloy components, which comprises the following steps: firstly, preparing spray powder by taking alloy components with melting point higher than 1000 ℃ in titanium alloy as raw materials, preparing spray liquid by taking alloy components with melting point lower than 1000 ℃ in titanium alloy as raw materials, then spraying spray liquid adhered with spray powder on the surfaces of titanium sponge particles, preparing titanium sponge particles with alloy component layers deposited on the surfaces, fully mixing the titanium sponge particles with alloy component layers deposited on the surfaces and the titanium sponge particles without alloy component layers deposited on the surfaces, pressing and assembling to form a consumable electrode, and finally carrying out vacuum consumable arc melting on the consumable electrode to prepare titanium alloy cast ingots. The titanium alloy cast ingot prepared by the method realizes high homogenization of alloy components, reduces the times of vacuum consumable arc melting, and avoids the problems of electrode chipping and cracking in the vacuum consumable arc melting process.

Description

A kind of preparation method of titanium alloy ingot with highly uniform alloy composition

technical field

The invention belongs to the field of nonferrous metal processing, in particular to a method for preparing titanium alloy ingots with highly uniform 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, and even small-scale fluctuations in composition can have a great adverse effect on the properties of titanium alloys. For example, the nominal composition of TA18 titanium alloy is Ti-3Al-2.5V. If the Al in the local area of the alloy When the content exceeds 7%, the brittle phase of Ti ₃ Al will be precipitated, resulting in a decline in the overall performance of the alloy, especially the plasticity of the TA18 titanium alloy is greatly reduced, and the V element is a stabilizing element for the β phase of the titanium alloy, and the β phase in the V-rich local area The content will increase significantly, and will also reduce the plasticity of TA18 titanium alloy. TA18 titanium alloy is mainly used to manufacture seamless pipes used in aircraft piping systems, and its cold rolling processing method requires it to have very good shape. 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 put forward very high requirements for the uniformity of its alloy elements , the slightly uneven distribution of Al and V elements will lead to cracking of the high-strength TA18 titanium alloy seamless pipe during cold rolling and the flaring plasticity index of the finished pipe is unqualified. Other titanium alloys such as TA16, TA21, and TC4 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 severe processing conditions and use requirements, the alloy composition must be A high degree of homogenization is achieved. In order 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 blank of titanium alloy products-the alloy composition of the titanium alloy ingot is highly uniform. Plastic processing of titanium alloy ingots for further homogenization. Obviously, ensuring a highly uniform alloy composition of titanium alloy ingots is the premise and key to realize a highly uniform alloy composition of titanium alloy products.

However, it is very difficult to achieve a highly uniform 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, mixed and pressed into consumable Electrodes, and then prepare titanium alloy ingots by vacuum consumable arc melting. Sponge titanium particles of different sizes, bean-shaped alloying element pure metal and bean-shaped alloying element master alloy are difficult to mix uniformly like metal powder, and vacuum consumable arc melting belongs to melting and solidification at the same time In the smelting method, even if the homogenization is promoted by no less than 3 times of vacuum consumable arc melting, there will still be enriched and depleted areas of the alloy composition in the titanium alloy ingot. To achieve a high degree of homogenization of 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 has invented a vacuum self-consumption melting method for homogeneous ingots of Ti-Mo alloys with high Mo content, which is used to improve the alloy composition of Ti-Mo titanium alloy ingots. The method adopts five times of vacuum consumable arc melting, and forges the Ti-Mo electrode after two times of vacuum consumable arc melting; in Chinese patent CN113832363A titanium alloy ingot and its preparation method, the The stable smelting stage and the feeding stage are carried out sequentially in the arc smelting process to promote the homogenization of the alloy composition of titanium alloy ingots; Chinese invention patent CN114091248 A has invented a simulation method for predicting the solidification process of vacuum consumable smelting ingots. The invention has a good guiding effect on 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 in the form of large particles, and the sponge titanium particles that account for the majority are poorly bonded to each other after pressing, two problems have been caused. One is the central part of the consumable electrode. The bonding force between the titanium sponge particles is not enough, and there is a problem of falling blocks during the smelting process. The second is that for large ingots, in order to avoid the problem of insufficient bonding strength between the titanium sponge particles, corresponding large electrode blocks cannot be prepared to assemble It is welded into 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 the failure of the welding points during the smelting process. Therefore, there is an urgent need for a new method for preparing titanium alloy ingots, which can not only ensure the alloy composition of titanium alloy ingots is highly uniform, but also reduce the number of times of vacuum consumable arc melting, and can effectively improve the efficiency of vacuum consumable arc melting. process security.

Contents of the invention

The purpose of the present invention is to provide a method for preparing titanium alloy ingots with highly uniform alloy components, using a spray deposition method to deposit alloy component layers on the surface of sponge particles to prepare raw materials for self-consumable electrodes, and then realize titanium alloy ingots. High homogenization of ingredients.

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

Step 1: using an alloy component in a titanium alloy with a melting point higher than 1000°C as a raw material to prepare spray powder, and using an alloy component in a titanium alloy with a melting point lower than 1000°C as a raw material to prepare a spray liquid;

Step 2: Spray the spray liquid with the spray powder adhered to the surface of the sponge titanium particle, and prepare the sponge titanium particle with the alloy composition layer deposited on the surface;

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

Step 4: Vacuum consumable arc melting is carried out on the consumable electrodes to produce titanium alloy ingots.

As a preferred solution of the method for preparing a titanium alloy ingot with a highly uniform alloy composition according to the present invention, a co-spraying method is used to spray the spray liquid adhered to the spray powder to the sponge titanium particles.

As a preferred solution of the method for preparing titanium alloy ingots with highly uniform alloy components in the present invention, wherein: when spraying the spray liquid with spray powder adhered to the surface of the sponge titanium particles, the sponge titanium particles are placed on a vibrating table, Sponge titanium particles keep throwing upwards on the vibrating table.

As a preferred solution of the method for preparing titanium alloy ingots with highly uniform alloy components according to the present invention, wherein: the process of spraying the spray liquid with spray powder adhered to the surface of the titanium sponge particles is carried out in the spray chamber, and the upper part of the spray chamber is set There is a spray head, a vibrating table is set under the spray head, and the spray chamber is protected by inert gas.

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

As a preferred solution of the method for preparing titanium alloy ingots with highly uniform alloy components in the present invention, wherein: the particle size of the sprayed powder is less than 10 μm, and the particle size of the titanium sponge particles is 5-12.5 mm.

As a preferred solution of the method for preparing titanium alloy ingots with highly uniform alloy components in the present invention, wherein: when spraying the spray liquid with spray powder adhered to the surface of the sponge titanium particles, the throwing height of the sponge titanium particles is not low at 5cm.

As a preferred solution of the method for preparing a titanium alloy ingot with highly uniform alloy composition in the present invention, wherein: during the co-spraying process, the spray powder is directly sprayed into the atomization cone formed by the spray liquid.

As a preferred solution of the method for preparing a titanium alloy ingot with a highly uniform alloy composition in the present invention, wherein: the number of vacuum consumable arc melting is no more than 2 times.

By adopting the method of the present invention, in addition to realizing high uniformity of the alloy composition of the titanium alloy ingot, effectively reducing the number of times of vacuum consumable arc smelting, and effectively improving the safety of the vacuum consumable smelting process. Because after spraying a layer of alloying elements on the surface of the titanium sponge particles, especially when the alloying elements contain more soft elements such as Al, Sn, Cu, etc., the contact surface between the titanium sponge particles becomes a deposition of alloying elements. In the contact surface between the layers, during the pressing process of the electrode block, the alloy element deposition layer is relatively soft, and it is easy to produce mutual bonding and occlusion, which greatly increases the bonding strength between the particles, thereby greatly improving the strength of the electrode block, so The electrode block can be made larger to reduce the number of welding spots for subsequent welding and improve the safety of the consumable electrode; also because the strength of the electrode block is improved, the danger of block falling during the vacuum consumable arc melting process is avoided.

The present invention has the following advantages:

(1) In the present invention, by spray-depositing the alloy composition layer on the surface of the sponge titanium particles, the high degree of uniformity of the alloy composition of the titanium alloy ingot can be realized under the condition of no more than two vacuum consumable arc melting;

(2) The present invention increases the compactness of the consumable electrode block during compaction and the bonding strength between the particles by spraying and depositing the alloy composition layer on the surface of the sponge titanium particles, and avoids the loss of the consumable electrode block during the smelting process. rupture problem;

(3) The present invention can prepare a large-sized and high-strength consumable electrode block by spraying and depositing an alloy composition layer on the surface of the sponge titanium particle, thereby reducing the welding joints of the overall consumable electrode and increasing the vacuum self-consumable electrode block. The safety of arc melting process.

Description of drawings

Fig. 1 is a kind of highly homogenized titanium alloy ingot preparation flowchart of the present invention;

Fig. 2 is a figure of the injection device of the present invention;

Fig. 3 is a schematic diagram of sampling positions at 9 points in the head section of a titanium ingot.

Detailed ways

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

In conjunction with Fig. 1, a method for preparing a titanium alloy ingot with a highly uniform alloy composition of the present invention comprises the following steps:

Step 1: Using titanium alloy components with a melting point higher than 1000°C as raw materials to prepare spray powder, and using titanium alloy components with melting points lower than 1000°C as raw materials to prepare spray liquid.

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

The alloy components of titanium alloys with a melting point below 1000°C include aluminum and tin, etc., and the spray liquid is prepared according to the specific alloy components corresponding to different grades of titanium alloys. If a certain grade of titanium alloy contains only one alloy composition, the alloy composition is used as a raw material to prepare the spray liquid, and if it contains two or more alloy components with a melting point lower than 1000 °C, two or more alloy components with a melting point lower than 1000 °C are used 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 the spray powder adhered to the surface of the sponge titanium particle, and prepare the sponge titanium particle with the alloy composition 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 at the upper part of the spray chamber 1 , and the vibrating table 2 is located at the lower part of the spray chamber 1 . Firstly, titanium sponge particles 8 with a particle diameter of 5-12.5 mm are placed on the vibrating table 2 located at the lower part of the spray chamber 1, and the vibrating table 2 is mechanically vibrated longitudinally, so that the titanium sponge particles 8 are formed under the mechanical vibration of the vibrating table 2. Throwing movement, and the throwing height is not less than 5cm.

Then, using a co-spraying technique, the spray liquid with spray powder adhered to the sponge titanium particles is sprayed to prepare the sponge titanium particles with alloy composition layers 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 a high speed to form a spray liquid atomizing cone 10, that is, a cone-shaped mist composed of countless small droplets of the spray liquid is formed. The spray powder 11 is sprayed into the spray liquid atomizing 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 to the spray powder are sprayed toward the titanium sponge particles 8 on the vibrating table 2 at high speed, and after hitting the surface of the titanium sponge particles 8, they spread on the surface of the titanium sponge particles 8 and are cooled and solidified to form an alloy composition layer, thereby Realize the co-injection process of solid-phase spray powder and liquid-phase spray liquid. During the co-spraying process, since the titanium sponge particles 8 maintain upward throwing motion, and the vibrating table 2 also moves laterally, the accessibility and uniformity of spraying are guaranteed.

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 injection chamber 1 is protected by argon gas.

The present invention adopts the co-spraying method to prepare the alloy composition layer on the surface of the sponge titanium particle 8, which has the following advantages: (1) the melting point of the spray liquid is low, which reduces the requirements for smelting equipment and nozzles; (2) reduces the requirement for spraying process parameters Requirements, it is easy to spray and deposit on the surface of sponge titanium particles to form a solid alloy composition layer; (3) Avoid the spray liquid composed of multi-alloy components reacting with the crucible at high temperature and pollute the spray liquid.

After the alloy composition layer is deposited on the surface of the titanium sponge particle 8, it is not only beneficial to the homogenization of the alloy composition of the titanium alloy ingot, but also conducive to pressing into an electrode block with high density and high strength. Because the alloy composition layer matrix deposited on the surface of the titanium sponge 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 the titanium sponge particles 8, and the titanium sponge particles are easy to move. Mutual bonding and occlusion are produced, which greatly increases the bonding strength between the particles, thereby greatly improving the strength of the electrode block, so the electrode block can be made larger, thereby reducing the number of subsequent solder joints and improving 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 composition layer deposited on the surface and the titanium sponge particles without the alloy composition layer deposited on the surface, and prepare a consumable electrode after mixing;

Since vacuum consumable arc melting can further promote the homogenization of the alloy composition of titanium alloy ingots, it is not required that all titanium sponge particles are deposited with alloy composition layers, that is, the alloy composition of titanium alloy is not required to be evenly distributed to all titanium sponge particles On the surface, only the titanium alloy alloy composition is required to be uniformly distributed on the surface of most of the sponge titanium particles to meet the requirement of high uniformity of the alloy composition of the titanium alloy ingot, which can reduce production costs. To balance the production cost and the homogenization effect of the alloy composition of the titanium alloy ingot, it is required that the spongy titanium particles with the alloy composition layer deposited on the surface account for 70% or more of the raw material ratio of the consumable electrode.

In this step, the titanium sponge particles with the alloy composition layer deposited on the surface and the titanium sponge particles without the alloy composition layer deposited on the surface are fully mixed as the consumable electrode raw material. Use a special mold to press the consumable electrode raw material into several smaller consumable electrode blocks under high pressure, and then weld several consumable electrode blocks to form the final consumable electrode.

Step 4: Vacuum consumable arc melting is carried out on the consumable electrodes to produce titanium alloy ingots.

Using the consumable electrode prepared in step 3 to conduct vacuum consumable arc melting for 1~2 times, 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 a titanium alloy ingot with a highly uniform alloy composition, comprising the following steps:

Step 1: Prepare spray powder with vanadium metal powder as raw material, and prepare spray liquid with aluminum as raw material;

Using vanadium metal powder with a purity greater than 99.95% as a raw material, the vanadium spray powder with a particle size of less than 10 microns is prepared by 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 melt the high-purity aluminum into an aluminum spray liquid. The temperature of the spray liquid in the graphite crucible melting furnace is maintained at 730~750 °C.

Step 2: Spraying aluminum spray liquid with vanadium spray powder adhered to the surface of titanium sponge particles to prepare titanium sponge particles with aluminum-vanadium alloy composition layers deposited on the surface;

Sponge titanium particles with a particle size of 5-12.5mm are placed on a vibrating table, and the aluminum spray liquid with vanadium spray powder adhered to the surface of the sponge titanium particles is sprayed with a spray device, that is, through the co-spray technology, the surface is prepared with aluminum-vanadium alloy deposited on the surface. Composed of layers of sponge titanium particles. Argon is used as the gas for the atomized aluminum spray liquid, and the pressure of the argon is 3.0MPa; the distance from the nozzle to the vibrating table is 300mm. The ratio of the flow rate (g/min) of aluminum spray liquid sprayed from the nozzle to the flow rate (g/min) of vanadium spray powder 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 upwards under the mechanical vibration of the vibrating table, and the throwing height of the titanium sponge particles is controlled at 5-10cm. During the spraying process, the vibrating table also moves left and right at a speed of 0.6mm/s. After spraying, a layer of aluminum-vanadium alloy composition is deposited on the surface of the sponge titanium particles.

Step 3: Thoroughly mix titanium sponge particles with an aluminum-vanadium alloy composition layer deposited on the surface with titanium sponge particles without an aluminum-vanadium alloy composition layer deposited on the surface, press and assemble and weld a consumable electrode after mixing.

Fully mix titanium sponge particles with an aluminum-vanadium alloy composition layer deposited on the surface with titanium sponge particles without an aluminum-vanadium alloy composition layer deposited on the surface as raw materials for consumable electrodes, wherein the sponge with an aluminum-vanadium alloy composition layer deposited on the surface The mass of titanium particles accounted for 70%, and the mass of titanium sponge particles without aluminum-vanadium alloy layer deposited on the surface accounted for 30%. Then the consumable electrode raw materials were put into the mold and pressed into several electrode blocks. The blocks are welded into a consumable electrode.

Step 4: Vacuum consumable arc melting is carried out on the consumable electrodes to produce titanium alloy ingots.

The TA18 titanium alloy ingot with highly uniform composition was prepared by two vacuum consumable arc melting.

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

The head section of the titanium alloy ingot is cut along the radial direction to obtain the head section. The 9-point sampling method shown in Figure 3 is used to sample at 9 points (TP1~TP9) on the head section, and the TP1 to TP9 points are measured. chemical composition. R in Fig. 3 represents the radius of the ingot profile.

The longitudinal chemical composition of the obtained titanium alloy ingot is shown in Table 1, and the chemical composition of nine points on the end face of the titanium alloy ingot head 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 by this method is good, the content deviation of Al and V in the longitudinal alloy composition of the ingot is not more than 0.03% (wt.%, the same below), and the impurity elements Fe, O, 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 The chemical composition of 9 points on the end face of the titanium alloy ingot head in Example 1

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

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 a titanium alloy ingot with a highly uniform alloy composition, comprising the following steps:

Step 1: Prepare spray powder with manganese metal powder as raw material, and prepare spray liquid with aluminum as raw material;

Manganese metal powder with a purity greater than 99.95% is used as a raw material, and manganese spray powder with a particle size of less than 10 microns is prepared by 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 melt the high-purity aluminum into an aluminum spray liquid. The temperature of the spray liquid in the graphite crucible melting furnace is maintained at 730~750 °C.

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

Titanium sponge particles with a particle size of 5-12.5mm are placed on a vibrating table, and the aluminum spray liquid with manganese spray powder adhered to the titanium sponge particles is sprayed by a spraying device, that is, through co-spraying technology, the aluminum-manganese alloy component deposited on the surface is prepared. layer of titanium sponge particles. Argon is used as the gas for the atomized aluminum spray liquid, and the pressure of the argon is 3.0MPa; the distance from the nozzle to the vibrating table is 300mm. The ratio of the flow rate (g/min) of aluminum spray liquid sprayed from the nozzle to the flow rate (g/min) of manganese spray powder 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 upwards under the mechanical vibration of the vibrating table, and the throwing height of the titanium sponge particles is controlled at 5-10cm. During the spraying process, the vibrating table also moves left and right at a speed of 0.6mm/s. After spraying, a layer of aluminum-manganese alloy composition is deposited on the surface of the sponge titanium particles.

Step 3: Thoroughly mix titanium sponge particles with an aluminum-manganese alloy composition layer deposited on the surface with titanium sponge particles without an aluminum-manganese alloy composition layer deposited on the surface, press and assemble and weld a consumable electrode after mixing.

Fully mix titanium sponge particles with aluminum-manganese alloy composition layers deposited on the surface and titanium sponge particles without aluminum-manganese alloy composition layers deposited on the surface as raw materials for consumable electrodes, wherein the sponge with aluminum-vanadium alloy composition layers deposited on the surface The mass of titanium particles accounted for 75%, and the mass of titanium sponge particles without aluminum-vanadium alloy layer deposited on the surface accounted for 25%. The blocks are welded into a consumable electrode.

Step 4: Vacuum consumable arc melting is carried out on the consumable electrodes to produce titanium alloy ingots.

A TC1 titanium alloy ingot with highly uniform composition was prepared by one vacuum consumable arc melting.

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

The head section of the titanium alloy ingot is cut along the radial direction to obtain the head section. The 9-point sampling method shown in Figure 2 is used to sample at 9 points (TP1~TP9) on the head section, and the TP1 to TP9 points are measured. chemical composition.

The longitudinal chemical composition of the obtained titanium alloy ingot is shown in Table 3, and the chemical composition of 9 points on the end face of the titanium alloy ingot head 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 uniformity of the TC1 ingot prepared by this method is good, the deviation of each alloy element Al and Mn in the longitudinal direction of the ingot is not more than 0.03% (wt.%, the same below), and the impurity elements Fe, O, C , N, and H element contents meet the control range requirements of less than or equal to 0.3%, 0.15%, 0.10%, 0.05%, and 0.012%.

Table 4 The chemical composition of 9 points on the end face of the titanium alloy ingot head in Example 2

It can be seen from Table 4 that the composition of the ingot has good uniformity, and the deviations of the alloy elements Al and Mn in the analysis results of 9 points on the end face of the head are not more than 0.04% and 0.03% (wt.%, the same below), and the content of the impurity element Fe Meet the control range requirements 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 a titanium alloy ingot with a highly uniform alloy composition, comprising the following steps:

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

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

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

Titanium sponge particles with a particle size of 5-12.5 mm are placed on a vibrating table, and the titanium sponge particles are sprayed with aluminum-tin spray liquid with zirconium-molybdenum spray powder adhered to them by a spraying device, that is, through co-spraying technology, aluminum deposited on the surface is prepared. - Titanium sponge particles layered with a tin-zirconium-molybdenum alloy composition. Argon is used as the gas for atomizing the aluminum-tin spray liquid, and the pressure of the argon is 3.0MPa; the distance from the nozzle to the vibrating table is 300mm. The ratio of the flow rate (g/min) of aluminum-tin spray liquid sprayed from the nozzle to the flow rate (g/min) of zirconium-molybdenum spray powder 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 upwards under the mechanical vibration of the vibrating table, and the throwing height of the titanium sponge particles is controlled at 5-10cm. During the spraying process, the vibrating table also moves left and right at a speed of 0.6mm/s. After spraying, a layer of aluminum-tin-zirconium-molybdenum alloy composition layer 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, press and weld after mixing to form a self- Consumes electrodes.

Fully mix the sponge titanium particles with aluminum-tin-zirconium-molybdenum alloy composition layers deposited on the surface and the sponge titanium particles without aluminum-tin-zirconium-molybdenum alloy composition layers deposited on the surface as raw materials for consumable electrodes, wherein the surface is deposited with The mass of titanium sponge particles with 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%. Put it into a mold and press it into several electrode blocks, and finally weld several electrode blocks into a consumable electrode.

Step 4: Vacuum consumable arc melting is carried out on the consumable electrodes to produce titanium alloy ingots.

The TC19 titanium alloy ingot with highly uniform composition was prepared by two vacuum consumable arc melting.

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

The head section of the titanium alloy ingot is cut along the radial direction to obtain the head section. The 9-point sampling method shown in Figure 2 is used to sample at 9 points (TP1~TP9) on the head section, and the TP1 to TP9 points are measured. chemical composition.

The longitudinal chemical composition of the obtained titanium alloy ingot is shown in Table 5, and the chemical composition of 9 points on the end face of the titanium alloy ingot head 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 by this method is good, and the deviation of each alloy element Al, Sn, Zr and Mo in the longitudinal direction of the ingot is not more than 0.03% (wt.%, the same below), 0.03%, 0.02% and 0.05%. And the contents of impurity elements Fe, Si, O, C, N, and H elements meet 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 The chemical composition of 9 points on the end face of the titanium alloy ingot head in Example 3

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

The basic principles, main features and advantages of the present invention have been shown and described above. Those skilled in the industry should understand that the above-mentioned embodiments do not limit the present invention in any form, and all technical solutions obtained by means of equivalent replacement 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 content of the embodiments. For those skilled in the art, various changes and modifications can be made within the scope of the technical solutions of the present invention, and any changes and modifications made are within the protection scope of the present invention.

Claims (9)

1. The preparation method of the titanium alloy cast ingot with the highly homogenized alloy components is characterized by comprising the following steps:

step 1: preparing spray powder by taking alloy components with melting points higher than 1000 ℃ in the titanium alloy as raw materials, and preparing spray liquid by taking alloy components with melting points lower than 1000 ℃ in the titanium alloy as raw materials;

step 2: spraying liquid adhered with spraying powder on the surface of the titanium sponge particles to prepare titanium sponge particles with alloy component layers deposited on the surface;

step 3: fully mixing the titanium sponge particles with the alloy component layers deposited on the surfaces and the titanium sponge particles without the alloy component layers deposited on the surfaces, and preparing the self-consuming electrode after mixing;

step 4: and carrying out vacuum consumable arc melting on the consumable electrode to prepare the titanium alloy cast ingot.

2. The method for producing a titanium alloy ingot having a highly uniform alloy composition according to claim 1, wherein the spray liquid to which the spray powder is adhered is sprayed onto the titanium sponge particles by a co-spraying method.

3. The method for producing a titanium alloy ingot having a highly uniform alloy composition according to claim 2, wherein the titanium sponge particles are placed on a vibrating table while spraying the spray liquid adhering the spray powder to the surface of the titanium sponge particles, and the titanium sponge particles are kept in an upward-throwing motion on the vibrating table.

4. The method for preparing a titanium alloy ingot with highly uniform alloy components according to any one of claims 1-3, wherein the spraying process of spraying the spraying liquid adhered with the spraying powder on the surface of the sponge titanium particles is performed in a spraying chamber, a spraying head is arranged at the upper part of the spraying chamber, a vibrating table is arranged below the spraying head, and the spraying chamber is protected by inert gas.

5. The method for producing a titanium alloy ingot having a highly homogenized alloy composition according to claim 1, wherein the consumable electrode has a surface on which a layer of titanium sponge particles of an alloy composition is deposited in a mass percentage of 70% or more.

6. The method for producing a titanium alloy ingot having a highly homogenized alloy composition according to any one of claims 1 to 3 and 5, characterized in that the particle size of the spray powder is less than 10 μm and the particle size of the titanium sponge particles is 5 to 12.5mm.

7. The method for producing a titanium alloy ingot having a highly uniform alloy composition according to claim 4, wherein the titanium sponge particles have a rise height of not less than 5cm when a spray liquid to which spray powder adheres is sprayed onto the surfaces of the titanium sponge particles.

8. A method of producing a titanium alloy ingot having a highly homogenized alloy composition according to claim 2 or 3, characterized in that in said co-injection process, the injection powder is directly injected into an atomizing cone formed by the injection liquid.

9. A method of producing a titanium alloy ingot having a highly homogenized alloy composition in accordance with any of claims 1, 2, 5 and 7, wherein said vacuum consumable arc melting is performed no more than 2 times.