Aluminum-titanium-zirconium-molybdenum-tin quinary intermediate alloy, preparation method thereof and preparation method of titanium alloy ingot

Abstract

A five-element master alloy of aluminum, titanium, zirconium, molybdenum, and tin comprises the following components: molybdenum: 35.0–40.0%, zirconium: 30.0–35.0%, tin: 5.0–10.0%, titanium: 5.0–10.0%, oxygen: 0.01–0.1%, nitrogen: 0.01–0.07%, iron: 0.01–0.18%, silicon: 0.01–0.15%, carbon: 0.01–0.05%, with the balance being aluminum. A method for preparing titanium alloy ingots is also provided, comprising: first, manufacturing an aluminum-zirconium-tin primary metal alloy; then, manufacturing an aluminum-zirconium-tin secondary metal alloy; then, manufacturing an aluminum-molybdenum-titanium primary metal alloy; melting the aluminum-molybdenum-titanium primary metal alloy to obtain an aluminum-molybdenum-titanium secondary metal alloy, and forming an alloy block; processing the alloy block raw material into a tertiary alloy ingot, crushing it to obtain an aluminum-titanium-zirconium-molybdenum-tin five-element master alloy; combining the aluminum-titanium-zirconium-molybdenum-tin five-element master alloy with sponge titanium, etc., to form an electrode block, and then combining it with an auxiliary electrode to form a consumable electrode; finally, forming the consumable electrode into a large-size titanium alloy ingot with high molybdenum and high zirconium content. This invention effectively improves the compositional uniformity.

Description

Technical Field

[0001] This invention relates to the field of metallurgy, and more particularly to titanium alloy processing technology, specifically a five-element master alloy of aluminum, titanium, zirconium, molybdenum and tin, its preparation method, and a method for preparing titanium alloy ingots. Background Technology

[0002] The uniformity of titanium alloy composition is a key foundation for its superior performance, directly affecting the material's mechanical properties, reliability, and service life. Inhomogeneity can lead to various serious defects, such as low-density segregation caused by the volatilization of low-melting-point elements and high-density inclusions due to incomplete alloying of high-melting-point elements. These defects can significantly reduce the material's performance and even cause failure, posing a significant risk to its use.

[0003] As representatives of multi-element near-α or martensitic α-β titanium alloys, the Ti-Al-Mo-Zr-Sn series of titanium alloys demonstrates significant application value in high-end industrial fields due to their unique composition design and excellent comprehensive performance. In the aerospace field, this series of alloys is used to manufacture high-temperature load-bearing components such as engine compressor disks and integral bladed disks, reducing structural weight by 40% and improving thrust-to-weight ratio. In marine engineering, tubing made from this material is widely used in ship heat exchangers, condensers, and deep-sea equipment structures; its resistance to crevice corrosion solves the failure problem of traditional materials in salt spray environments. The newly developed improved Ti-Al-Zr-Sn-Mo-Nb alloys (such as the Ti90 alloy) further expands applications in extreme environments; its lamellar basketweave structure increases fracture toughness by 35% and has been successfully used in the pressure hulls of deep-sea probes. For the Ti-Al-Mo-Zr-Sn series of titanium alloys, the compositional uniformity of the major elements aluminum, molybdenum, zirconium, and tin has a crucial impact on product quality and stability.

[0004] Master alloys are indispensable raw materials in modern vacuum arc remelting of titanium alloy ingots, playing an irreplaceable role. By optimizing element distribution, improving smelting processes, and controlling microstructure, they significantly enhance the compositional uniformity and overall performance of titanium alloys. With the continuous development of new materials and processes, the application of master alloys in titanium alloy preparation will become more widespread and in-depth, providing stronger support for the application of titanium alloys in aerospace, biomedicine, new energy, and other fields.

[0005] Chinese Patent Publication No. CN202111273823.8 discloses an aluminum-molybdenum-zirconium master alloy and its preparation method. The alloy comprises, by mass fraction, 41.0–45.0% Mo, 23.0–26.0% Zr, with Al as the balance. This patent, through control of elemental composition and content, achieves minimal component segregation in the aluminum-molybdenum-zirconium master alloy, preventing component segregation in TC19 titanium alloys. Furthermore, the low impurity content of this patented aluminum-molybdenum-zirconium master alloy contributes to the homogenization of the titanium alloy composition during TC19 titanium alloy smelting. The zirconium content is low, and tin is not involved. When applied to the preparation of high-molybdenum, high-zirconium Ti-Al-Mo-Zr-Sn series titanium alloys, to meet alloy composition requirements, it is still necessary to use more other master alloys or elemental metals to incorporate zirconium and tin, resulting in a zirconium content deviation of >0.1 wt% in different regions of large-size ingots.

[0006] Chinese Patent Publication No. CN202411235121.4 discloses an aluminum-titanium-tin-zirconium-molybdenum-silicon hexa-element master alloy, its preparation method, and its application. The hexa-element master alloy comprises the following components by weight percentage: titanium: 11%–15%, tin: 13%–16%, zirconium: 27%–30%, molybdenum: 13%–16%, silicon: 0.04%–0.06%; the balance being aluminum and unavoidable impurity elements. This hexa-element master alloy is designed for the preparation of titanium alloys such as Ti180 and TiA19. By strictly controlling the impurity content and employing a self-propagating process, the performance of the master alloy is ensured to be stable, effectively improving the alloying degree of Ti180 and TiA19, preventing component segregation and inclusions, thereby improving the performance of Ti180 and TiA19 titanium alloys. The alloy features a low molybdenum content and increased silicon incorporation. When used to prepare Ti-Al-Mo-Zr-Sn series titanium alloys with high molybdenum and high zirconium content, in order to meet the alloy composition requirements, it is still necessary to use more other intermediate alloys or elemental metals to incorporate molybdenum, resulting in a deviation of molybdenum content in different regions of large-size ingots >0.1wt%, and it cannot be applied to materials without silicon.

[0007] The current method for preparing large-sized titanium alloy ingots with high molybdenum and high zirconium content (Ti-Al-Mo-Zr-Sn series) involves mixing and stirring aluminum-molybdenum master alloys, aluminum-tin master alloys, elemental aluminum, elemental zirconium, titanium dioxide, and sponge titanium, pressing them into electrodes, and then splicing them together. These electrodes are then vacuum welded and vacuum arc remelted to produce titanium alloy ingots with diameters ranging from Ф600mm to Ф800mm. When the prepared ingot size is small (diameter ≤ Ф500mm), the existing preparation method can produce products with less segregation and higher compositional uniformity. However, for large-sized ingots with diameters exceeding Ф600mm, this leads to significant compositional deviations in different regions, with localized segregation of higher-content molybdenum and zirconium elements, thus affecting the quality and stability of the final product.

[0008] The different solid solubilities of zirconium and molybdenum in α-Ti and β-Ti lead to uneven distribution of composition in different phases. Molybdenum, in particular, has extremely low solid solubility in α-Ti, resulting in a more severe tendency for segregation. Furthermore, the low diffusion coefficients of zirconium and molybdenum in titanium alloys hinder the redistribution of solute elements, which is the fundamental mechanism behind the compositional inhomogeneity. For large-sized ingots, the large size significantly increases the difficulty of homogenizing the composition during smelting, and the greater weight also means that more raw materials are required. When the raw material composition or particle size is uneven, it will exacerbate the compositional segregation of the ingot. Summary of the Invention

[0009] To address the shortcomings of existing technologies, this invention provides a five-element master alloy of aluminum, titanium, zirconium, molybdenum, and tin, its preparation method, and a method for preparing titanium alloy ingots. By providing this five-element master alloy and using it as a raw material for vacuum consumable melting, this invention improves the compositional segregation phenomenon in large-size ingots of high-molybdenum and high-zirconium Ti-Al-Mo-Zr-Sn series titanium alloys with diameters of Ф600mm to Ф800mm, effectively enhancing the compositional uniformity.

[0010] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0011] This invention provides a five-element master alloy of aluminum, titanium, zirconium, molybdenum, and tin, which, by mass fraction, comprises the following components:

[0012] Molybdenum: 35.0%–40.0%

[0013] Zirconium: 30.0%–35.0%

[0014] Tin: 5.0%–10.0%

[0015] Titanium: 5.0–10.0%,

[0016] Oxygen: 0.01–0.1%,

[0017] Nitrogen: 0.01–0.07%,

[0018] Iron: 0.01–0.18%,

[0019] Silicon: 0.01–0.15%,

[0020] Carbon: 0.01–0.05%,

[0021] The balance is aluminum.

[0022] Furthermore, by mass fraction, the aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy comprises the following components:

[0023] Molybdenum: 38.0%–40.0%

[0024] Zirconium: 30.0%–32.0%

[0025] Tin: 5.0%–7.0%

[0026] Titanium: 8.0–10.0%,

[0027] Oxygen: 0.01–0.1%,

[0028] Nitrogen: 0.01–0.05%,

[0029] Iron: 0.01%–0.1%

[0030] Silicon: 0.01%–0.1%

[0031] Carbon: 0.01–0.02%,

[0032] The balance is aluminum.

[0033] The present invention also provides a method for preparing the aforementioned aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy, comprising the following steps:

[0034] Step S1: Zirconium dioxide powder, tin dioxide powder, aluminum powder, reaction regulator and combustion accelerator are added to the binder solution and thoroughly mixed, then heated to carry out an aluminothermic reaction to produce an aluminum-zirconium-tin primary metal alloy. The mass ratio of zirconium dioxide powder, tin dioxide powder, aluminum powder, reaction regulator and combustion accelerator is (25.09~25.19):(4.82~4.92):(1.55~1.65):(3.11~3.21):1;

[0035] Step S2: Place the aluminum-zirconium-tin primary metal alloy in a crucible and perform vacuum induction melting to obtain an aluminum-zirconium-tin secondary metal alloy.

[0036] Step S3: Molybdenum trioxide powder, titanium dioxide powder, aluminum powder, reaction regulator and combustion accelerator are added to the binder solution and thoroughly mixed, then heated to carry out an aluminothermic reaction to produce an aluminum-molybdenum-titanium primary metal alloy. The mass ratio of molybdenum trioxide powder, titanium dioxide powder, aluminum powder, reaction regulator and combustion accelerator is (25.53~25.63):(4.38~4.48):(1.26~1.36):(3.08~3.18):1;

[0037] Step S4: Place the aluminum-molybdenum-titanium primary metal alloy in a crucible and perform vacuum induction melting to obtain an aluminum-molybdenum-titanium secondary metal alloy.

[0038] Step S5: Crush the aluminum-zirconium-tin secondary metal alloy and the aluminum-molybdenum-titanium secondary metal alloy respectively to make aluminum-zirconium-tin metal alloy blocks and aluminum-molybdenum-titanium metal alloy blocks.

[0039] Step S6: Place the raw materials of the aluminum-zirconium-tin alloy block and the aluminum-molybdenum-titanium alloy block into a vacuum induction furnace in the order of "aluminum-zirconium-tin metal-aluminum-molybdenum-titanium metal" and melt and cast them. After cooling, a three-stage alloy ingot is obtained. The mass ratio of the aluminum-molybdenum-titanium alloy block to the aluminum-zirconium-tin alloy block is (1.25~1.35):1.

[0040] Step S7: Refine and crush the three-stage alloy ingots to obtain an aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy with a particle diameter between 1-6 mm through fine selection.

[0041] Preferably, in steps S1 and S3, the combustion aid is KCLO3 powder, the reaction regulator is Na3AlF6 powder, and the binder solution is a polyvinyl alcohol solution.

[0042] Preferably, in step S1, the particle size of the aluminum powder, the zirconium dioxide powder, and the tin dioxide powder is less than or equal to 2 mm; the aluminothermic reaction temperature is 2250℃~2350℃, and the reaction time is 45s~55s.

[0043] Preferably, in step S3, the particle size of the aluminum powder, the molybdenum trioxide powder, and the titanium dioxide powder is less than or equal to 2 mm; the aluminothermic reaction temperature is 2200℃~2300℃, and the reaction time is 40s~50s.

[0044] Preferably, in steps S2, S4, and S6, vacuum induction melting includes melting and refining, with a melting power of 80kW to 90kW, a refining power of 100kW to 110kW, and a vacuum degree of ≤5Pa in the melting environment; in steps S2, S4, and S6, helium cooling is used after melting is completed.

[0045] This invention also provides a method for preparing titanium alloy ingots, comprising the following steps:

[0046] Step P1: Place the aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy into a closed cavity for baking;

[0047] Step P2: According to the composition requirements of the ingot, the aluminum-titanium-zirconium-molybdenum-tin five-element intermediate alloy, other raw materials and sponge titanium are stirred and mixed and then pressed into electrode blocks with a diameter of Ф300mm to Ф500mm.

[0048] Step P3: After connecting the electrode block with the auxiliary electrode, place it in a plasma welding furnace and manufacture a consumable electrode by vacuum welding.

[0049] Step P4: Place the aforementioned consumable electrode into a crucible and perform vacuum consumable melting more than three times to produce large-scale ingots of high-molybdenum and high-zirconium content Ti-Al-Mo-Zr-Sn series titanium alloys with diameters of Ф600mm~Ф800mm.

[0050] Step P5: Finish the ingot and take samples for inspection.

[0051] Preferably, in step P2, the other raw materials are aluminum-molybdenum-silicon master alloys, titanium-tungsten master alloys, or aluminum-silicon master alloys.

[0052] Preferably, in step P1, the baking temperature is 60℃~100℃; in step P3, the vacuum degree inside the plasma welding furnace during vacuum welding is 5Pa~10Pa; in step P4, during the final vacuum arc stabilization melting, the vacuum degree during the arc stabilization stage is ≤5Pa, the melting temperature is 1600℃~1700℃, and the melting rate is 15kg / min~25kg / min; in step P4, the deviation of molybdenum and zirconium content in different regions of the large-size ingots of high-molybdenum and high-zirconium Ti-Al-Mo-Zr-Sn series titanium alloys is ≤0.1wt%.

[0053] In the manufacturing method described in this invention: Steps S1 to S7 illustrate a method for preparing an aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy, and this alloy is used in steps P1 to P4 to manufacture large-scale ingots of Ti-Al-Mo-Zr-Sn series titanium alloys with high molybdenum and high zirconium content, so as to improve its compositional segregation phenomenon.

[0054] The aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy of this invention is manufactured through multiple vacuum induction melting processes to promote better homogenization of element distribution. The addition of this pentagonal master alloy transforms the segregation morphology of zirconium and molybdenum in titanium alloy ingots from discrete clusters to a nanoscale dispersed distribution, thereby effectively improving compositional uniformity. Aluminum, titanium, and tin can all balance the differences in solubility of zirconium and molybdenum in different phases, while tin can also reduce the diffusion activation energy of molybdenum to promote uniform compositional distribution and form a short-range ordered structure with zirconium, reducing compositional fluctuations.

[0055] Furthermore, the aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy described in this invention has the characteristics of multiple elemental components and high zirconium and molybdenum content. When applied to the preparation of large-size ingots of high-molybdenum and high-zirconium Ti-Al-Mo-Zr-Sn series titanium alloys, only a very small amount or even no other raw materials are needed. The titanium electrodes pressed for smelting will have a more uniform particle size, better composition control capability, and easier quality control in the manufacturing process, thereby achieving precise control of the composition and reducing deviations in various regions.

[0056] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0057] Large-scale Ti-Al-Mo-Zr-Sn series titanium alloy ingots with diameters ranging from Ф600mm to Ф800mm, prepared using existing technologies, exhibit significant variations in elemental content across different regions. Molybdenum content can reach 0.4wt% to 0.7wt% or even higher, and zirconium content can reach 0.3wt% to 0.5wt% or even higher. This invention provides a five-element master alloy of aluminum, titanium, zirconium, molybdenum, and tin and applies it to vacuum arc remelting, resulting in ingots with molybdenum and zirconium content variations ≤0.1wt% across different regions, thus effectively improving compositional uniformity. Attached Figure Description

[0058] Figure 1 A schematic diagram of cross-sectional sampling of the chemical composition of the titanium alloy ingot in this invention.

[0059] Figure 2 A schematic diagram of longitudinal sampling of the chemical composition of the titanium alloy ingot in this invention. Detailed Implementation

[0060] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings.

[0061] The main parameters and analysis and test results of the embodiments and comparative examples of this invention are shown in Table 1.

[0062] Example 1

[0063] A Ti-6Al-6Mo-4Zr-2Sn titanium alloy ingot has an outer diameter of approximately Φ750mm and a height of approximately 3000mm. The main metallic element composition requirements are: aluminum: 5.5wt%~6.5wt%, zirconium: 3.6wt%~4.4wt%, molybdenum: 5.5wt%~6.5wt%, and tin: 1.8wt%~2.2wt%.

[0064] First, the preparation steps of the aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy raw material are as follows:

[0065] Step S1: Zirconium dioxide powder, tin dioxide powder, aluminum powder, KClO3 (potassium chlorate) powder, and Na3AlF6 (cryolite) powder are added to a polyvinyl alcohol solution, thoroughly mixed, and then heated to carry out an aluminothermic reaction to produce an aluminum-zirconium-tin primary metal alloy. The mass ratio of zirconium dioxide powder, tin dioxide powder, aluminum powder, reaction regulator, and combustion aid is 25.11:4.90:1.61:3.15:1.

[0066] Step S2: Place the aluminum-zirconium-tin primary metal alloy in a crucible and perform vacuum induction melting to obtain an aluminum-zirconium-tin secondary metal alloy.

[0067] Step S3: Molybdenum trioxide powder, titanium dioxide powder, aluminum powder, KClO3 (potassium chlorate) powder, and Na3AlF6 (cryolite) powder are added to a polyvinyl alcohol solution, thoroughly mixed, and then heated to carry out an aluminothermic reaction to produce an aluminum-molybdenum-titanium primary metal alloy. The mass ratio of molybdenum trioxide powder, titanium dioxide powder, aluminum powder, reaction regulator, and combustion accelerant is 25.61:4.40:1.30:3.14:1.

[0068] Step S4: Place the aluminum-molybdenum-titanium primary metal alloy in a crucible and perform vacuum induction melting to obtain an aluminum-molybdenum-titanium secondary metal alloy.

[0069] Step S5: Crush the aluminum-zirconium-tin secondary metal alloy and the aluminum-molybdenum-titanium secondary metal alloy respectively to make aluminum-zirconium-tin metal alloy blocks and aluminum-molybdenum-titanium metal alloy blocks.

[0070] Step S6: Place the aluminum-zirconium-tin alloy block and the aluminum-molybdenum-titanium alloy block raw materials into a vacuum induction furnace in the order of "aluminum-zirconium-tin metal-aluminum-molybdenum-titanium metal" and melt and cast them. After cooling, a three-stage alloy ingot is obtained, wherein the mass ratio of the aluminum-molybdenum-titanium alloy block to the aluminum-zirconium-tin alloy block is 1.28:1.

[0071] Step S7: Refine and crush the three-stage alloy ingots to obtain an aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy with 1-6 mm particles through fine selection.

[0072] Secondly, the process of manufacturing titanium alloy ingots using the aforementioned aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy includes the following steps:

[0073] Step P1: Place the aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy with a particle diameter between 1 and 6 mm into a closed cavity for baking;

[0074] Step P2: The aluminum-titanium-zirconium-molybdenum-tin pentagonal intermediate alloy, aluminum wire and sponge titanium are stirred and mixed and then pressed into an electrode block with a diameter of Ф450mm.

[0075] Step P3: After connecting the electrode block with the auxiliary electrode, place it in a plasma welding furnace and manufacture a consumable electrode by vacuum welding.

[0076] Step P4: Place the aforementioned consumable electrode into a crucible and perform vacuum consumable melting more than three times to produce a Ti-6Al-6Mo-4Zr-2Sn titanium alloy ingot with a diameter of Ф750mm.

[0077] Step P5: Finish the ingot and take samples for inspection.

[0078] Example 2

[0079] A certain Ti-6.5Al-4Mo-4Zr-2Sn-1.0W-0.2Si titanium alloy ingot has an outer diameter of approximately Φ660mm and a height of approximately 2500mm. The main metallic element composition requirements are: aluminum: 6.0wt%~7.0wt%, zirconium: 3.6wt%~4.4wt%, molybdenum: 3.6wt%~4.4wt%, and tin: 1.8wt%~2.2wt%.

[0080] Step S1: Zirconium dioxide powder, tin dioxide powder, aluminum powder, KClO3 (potassium chlorate) powder, and Na3AlF6 (cryolite) powder are added to a polyvinyl alcohol solution, thoroughly mixed, and then heated to carry out an aluminothermic reaction to produce an aluminum-zirconium-tin primary metal alloy. The mass ratio of zirconium dioxide powder, tin dioxide powder, aluminum powder, reaction regulator, and combustion accelerant is 25.17:4.87:1.60:3.16:1.

[0081] Step S2: Place the aluminum-zirconium-tin primary metal alloy in a crucible and perform vacuum induction melting to obtain an aluminum-zirconium-tin secondary metal alloy.

[0082] Step S3: Molybdenum trioxide powder, titanium dioxide powder, aluminum powder, KClO3 (potassium chlorate) powder, and Na3AlF6 (cryolite) powder are added to a polyvinyl alcohol solution, thoroughly mixed, and then heated to carry out an aluminothermic reaction to produce an aluminum-molybdenum-titanium primary metal alloy. The mass ratio of molybdenum trioxide powder, titanium dioxide powder, aluminum powder, reaction regulator, and combustion accelerant is 25.58:4.43:1.31:3.13:1.

[0083] Step S4: Place the aluminum-molybdenum-titanium primary metal alloy in a crucible and perform vacuum induction melting to obtain an aluminum-molybdenum-titanium secondary metal alloy.

[0084] Step S5: Crush the aluminum-zirconium-tin secondary metal alloy and the aluminum-molybdenum-titanium secondary metal alloy respectively to make aluminum-zirconium-tin metal alloy blocks and aluminum-molybdenum-titanium metal alloy blocks.

[0085] Step S6: Place the aluminum-zirconium-tin alloy block and the aluminum-molybdenum-titanium alloy block raw materials into a vacuum induction furnace in the order of "aluminum-zirconium-tin metal-aluminum-molybdenum-titanium metal" and melt and cast them. After cooling, a three-stage alloy ingot is obtained, wherein the mass ratio of the aluminum-molybdenum-titanium alloy block and the aluminum-zirconium-tin alloy block is 1.30:1.

[0086] Step S7: Refine and crush the three-stage alloy ingots to obtain an aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy with a particle diameter between 1 and 6 mm through fine selection.

[0087] Secondly, the process of manufacturing ingots using the aforementioned aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy includes the following steps:

[0088] Step P1: Place the aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy into a closed cavity for baking;

[0089] Step P2: The aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy, aluminum-silicon master alloy, titanium-tungsten master alloy and sponge titanium are stirred and mixed and then pressed into an electrode block with a diameter of Ф340mm.

[0090] Step P3: After connecting the electrode block with the auxiliary electrode, place it in a plasma welding furnace and manufacture a consumable electrode by vacuum welding.

[0091] Step P4: Place the aforementioned consumable electrode into a crucible and perform vacuum consumable melting more than three times to produce a Ti-6.5Al-4Mo-4Zr-2Sn-1.0W-0.2Si titanium alloy ingot with a diameter of Ф660mm.

[0092] Step P5: Finish the ingot and take samples for inspection.

[0093] Comparative Example 1

[0094] A Ti-6Al-6Mo-4Zr-2Sn titanium alloy ingot has an outer diameter of approximately Φ750mm and a height of approximately 3000mm. The main metallic element composition requirements are: aluminum: 5.5wt%~6.5wt%, zirconium: 3.6wt%~4.4wt%, molybdenum: 5.5wt%~6.5wt%, and tin: 1.8wt%~2.2wt%.

[0095] Its manufacturing method includes the following steps:

[0096] Step P1: After mixing aluminum-molybdenum master alloy, aluminum wire, metallic zirconium, aluminum-tin master alloy and sponge titanium, press them into electrode blocks with a diameter of Ф450mm.

[0097] Step P2: After connecting the electrode block with the auxiliary electrode, place it in a plasma welding furnace and manufacture a consumable electrode by vacuum welding.

[0098] Step P3: Place the aforementioned consumable electrode into a crucible and perform vacuum consumable melting more than three times to produce a Ti-6Al-6Mo-4Zr-2Sn titanium alloy ingot with a diameter of Ф750mm.

[0099] Step P4: Finish the ingot and take samples for inspection.

[0100] Comparative Example 2

[0101] A certain Ti-6.5Al-4Mo-4Zr-2Sn-1.0W-0.2Si titanium alloy ingot has an outer diameter of approximately Φ660mm and a height of approximately 2500mm. The main metallic element composition requirements are: aluminum: 6.0wt%~7.0wt%, zirconium: 3.6wt%~4.4wt%, molybdenum: 3.6wt%~4.4wt%, and tin: 1.8wt%~2.2wt%.

[0102] Its manufacturing method includes the following steps:

[0103] Step P1: Mix aluminum-molybdenum-silicon master alloy, aluminum wire, metallic zirconium, aluminum-tin master alloy, titanium-tungsten master alloy and sponge titanium, and press them into electrode blocks with a diameter of Ф340mm.

[0104] Step P2: After connecting the electrode block with the auxiliary electrode, place it in a plasma welding furnace and manufacture a consumable electrode by vacuum welding.

[0105] Step P3: Place the aforementioned consumable electrode into a crucible and perform vacuum consumable melting at least three times to produce a Ti-6.5Al-4Mo-4Zr-2Sn-1.0W-0.2Si titanium alloy ingot with a diameter of Ф660mm.

[0106] Step P4: Finish the ingot and take samples for inspection.

[0107] Table 1

[0108]

[0109] As can be seen from the above examples and comparative examples in conjunction with Table 1, the titanium alloy ingots of "Comparative Example 1 and Example 1" and "Comparative Example 2 and Example 2" have the same composition requirements, outer diameter and height dimensions, and basic preparation process routes. However, the ingots of Comparative Example 1 and Comparative Example 2 did not contain an aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy and used 4 to 5 different raw materials, while Example 1 and Example 2 used an aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy and only used 2 to 3 different raw materials.

[0110] After analyzing and testing all the ingots manufactured in the comparative examples and embodiments, the Ti-6Al-6Mo-4Zr-2Sn titanium alloy ingot with a diameter of Ф660mm manufactured in Comparative Example 1, after being analyzed and tested according to... Figure 1 and Figure 2 Sampling and component analysis, such as Figure 1 As shown, samples were taken at 1 / 4 radius, 1 / 2 radius, 3 / 4 radius, and near the surface of the ingot cross-section, respectively. Figure 2 As shown, samples were taken from the head (upper end) and tail (lower end) of the ingot, respectively.

[0111] The Ti-6.5Al-4Mo-4Zr-2Sn-1.0W-0.2Si titanium alloy ingot with a diameter of Ф750mm manufactured in Comparative Example 1 was processed according to... Figure 1 and Figure 2 Sampling and composition analysis revealed that the zirconium content ranged from 3.96 wt% to 4.44 wt%, and the molybdenum content ranged from 5.88 wt% to 6.54 wt%. The zirconium content varied by up to 0.48 wt% in different regions, and the molybdenum content varied by up to 0.66 wt% in different regions.

[0112] The Ti-6.5Al-4Mo-4Zr-2Sn-1.0W-0.2Si titanium alloy ingot with a diameter of Ф660mm manufactured in Comparative Example 2 was processed according to... Figure 1 and Figure 2 Sampling and composition analysis revealed that the zirconium content ranged from 4.01 wt% to 4.38 wt%, and the molybdenum content ranged from 3.96 wt% to 4.45 wt%. The variation in zirconium content was as high as 0.37 wt% in different regions, and the variation in molybdenum content was as high as 0.49 wt% in different regions.

[0113] The Ti-6Al-6Mo-4Zr-2Sn titanium alloy ingot with a diameter of Ф750mm manufactured in Example 1 was processed according to... Figure 1 and Figure 2 Sampling and composition analysis revealed that the zirconium content ranged from 4.12 wt% to 4.20 wt%, and the molybdenum content ranged from 6.08 wt% to 6.17 wt%. The deviations in molybdenum and zirconium content in different regions were ≤0.1 wt%.

[0114] The Ti-6.5Al-4Mo-4Zr-2Sn-1.0W-0.2Si titanium alloy ingot with a diameter of Ф660mm manufactured in Example 2 was processed according to... Figure 1 and Figure 2 Sampling and composition analysis revealed that the zirconium content ranged from 4.14 wt% to 4.21 wt%, and the molybdenum content ranged from 4.08 wt% to 4.15 wt%. The deviation of molybdenum and zirconium content in different regions was ≤0.1 wt%.

[0115] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A five-element master alloy of aluminum, titanium, zirconium, molybdenum, and tin, characterized in that, The aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy comprises the following components by mass fraction: Molybdenum: 35.0%–40.0% Zirconium: 30.0%–35.0% Tin: 5.0%–10.0% Titanium: 5.0–10.0%, Oxygen: 0.01–0.1%, Nitrogen: 0.01–0.07%, Iron: 0.01–0.18%, Silicon: 0.01–0.15%, Carbon: 0.01–0.05%, The balance is aluminum; The aforementioned aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy is prepared by a method comprising the following steps: Step S1: Zirconium dioxide powder, tin dioxide powder, aluminum powder, reaction regulator and combustion accelerator are added to the binder solution and thoroughly mixed, then heated to carry out an aluminothermic reaction to produce an aluminum-zirconium-tin primary metal alloy. The mass ratio of zirconium dioxide powder, tin dioxide powder, aluminum powder, reaction regulator and combustion accelerator is (25.09~25.19):(4.82~4.92):(1.55~1.65):(3.11~3.21):1; The combustion aid is KCLO3 powder, the reaction regulator is Na3AlF6 powder, and the binder solution is polyvinyl alcohol solution; Step S2: Place the aluminum-zirconium-tin primary metal alloy in a crucible and perform vacuum induction melting to obtain an aluminum-zirconium-tin secondary metal alloy. Step S3: Molybdenum trioxide powder, titanium dioxide powder, aluminum powder, reaction regulator and combustion accelerator are added to the binder solution and thoroughly mixed, then heated to carry out an aluminothermic reaction to produce an aluminum-molybdenum-titanium primary metal alloy. The mass ratio of molybdenum trioxide powder, titanium dioxide powder, aluminum powder, reaction regulator and combustion accelerator is (25.53~25.63):(4.38~4.48):(1.26~1.36):(3.08~3.18):1; Step S4: Place the aluminum-molybdenum-titanium primary metal alloy in a crucible and perform vacuum induction melting to obtain an aluminum-molybdenum-titanium secondary metal alloy. Step S5: Crush the aluminum-zirconium-tin secondary metal alloy and the aluminum-molybdenum-titanium secondary metal alloy respectively to make aluminum-zirconium-tin metal alloy blocks and aluminum-molybdenum-titanium metal alloy blocks. Step S6: Place the raw materials of the aluminum-zirconium-tin alloy block and the aluminum-molybdenum-titanium alloy block into a vacuum induction furnace in the order of "aluminum-zirconium-tin metal-aluminum-molybdenum-titanium metal" and melt and cast them. After cooling, a three-stage alloy ingot is obtained. The mass ratio of the aluminum-molybdenum-titanium alloy block to the aluminum-zirconium-tin alloy block is (1.25~1.35):

1. Step S7: Refine and crush the three-stage alloy ingots to obtain an aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy with a particle diameter between 1-6 mm through fine selection.

2. The aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy according to claim 1, characterized in that, The aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy comprises the following components by mass fraction: Molybdenum: 38.0%–40.0% Zirconium: 30.0%–32.0% Tin: 5.0%–7.0% Titanium: 8.0–10.0%, Oxygen: 0.01–0.1%, Nitrogen: 0.01–0.05%, Iron: 0.01%–0.1% Silicon: 0.01%–0.1% Carbon: 0.01–0.02%, The balance is aluminum.

3. A method for preparing the aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy according to claim 1, characterized in that, Includes the following steps: Step S1: Zirconium dioxide powder, tin dioxide powder, aluminum powder, reaction regulator and combustion accelerator are added to the binder solution and thoroughly mixed, then heated to carry out an aluminothermic reaction to produce an aluminum-zirconium-tin primary metal alloy. The mass ratio of zirconium dioxide powder, tin dioxide powder, aluminum powder, reaction regulator and combustion accelerator is (25.09~25.19):(4.82~4.92):(1.55~1.65):(3.11~3.21):1; The combustion aid is KCLO3 powder, the reaction regulator is Na3AlF6 powder, and the binder solution is polyvinyl alcohol solution; Step S2: Place the aluminum-zirconium-tin primary metal alloy in a crucible and perform vacuum induction melting to obtain an aluminum-zirconium-tin secondary metal alloy. Step S3: Molybdenum trioxide powder, titanium dioxide powder, aluminum powder, reaction regulator and combustion accelerator are added to the binder solution and thoroughly mixed, then heated to carry out an aluminothermic reaction to produce an aluminum-molybdenum-titanium primary metal alloy. The mass ratio of molybdenum trioxide powder, titanium dioxide powder, aluminum powder, reaction regulator and combustion accelerator is (25.53~25.63):(4.38~4.48):(1.26~1.36):(3.08~3.18):1; Step S4: Place the aluminum-molybdenum-titanium primary metal alloy in a crucible and perform vacuum induction melting to obtain an aluminum-molybdenum-titanium secondary metal alloy. Step S5: Crush the aluminum-zirconium-tin secondary metal alloy and the aluminum-molybdenum-titanium secondary metal alloy respectively to make aluminum-zirconium-tin metal alloy blocks and aluminum-molybdenum-titanium metal alloy blocks. Step S6: Place the raw materials of the aluminum-zirconium-tin alloy block and the aluminum-molybdenum-titanium alloy block into a vacuum induction furnace in the order of "aluminum-zirconium-tin metal-aluminum-molybdenum-titanium metal" and perform vacuum induction melting and casting. After cooling, a third-grade alloy ingot is obtained, wherein the mass ratio of the aluminum-molybdenum-titanium alloy block and the aluminum-zirconium-tin alloy block is (1.25~1.35):

1. Step S7: Refine and crush the three-stage alloy ingots to obtain an aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy with a particle diameter between 1-6 mm through fine selection.

4. The method for preparing an aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy according to claim 3, characterized in that: In the preparation process, in step S1, the particle size of the aluminum powder, the zirconium dioxide powder, and the tin dioxide powder is less than or equal to 2 mm; the aluminothermic reaction temperature is 2250℃~2350℃, and the reaction time is 45s~55s.

5. The method for preparing an aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy according to claim 3, characterized in that: In step S3, the particle size of the aluminum powder, the molybdenum trioxide powder, and the titanium dioxide powder is less than or equal to 2 mm; the aluminothermic reaction temperature is 2200℃~2300℃, and the reaction time is 40s~50s.

6. The method for preparing an aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy according to claim 3, characterized in that: In steps S2, S4, and S6, vacuum induction melting includes melting and refining. The melting power is 80kW to 90kW, the refining power is 100kW to 110kW, and the vacuum degree of the melting environment is ≤5Pa. In steps S2, S4, and S6, helium cooling is used after melting is completed.

7. A method for preparing a titanium alloy ingot, characterized in that, Includes the following steps: Step P1: Place the aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy as described in claim 1 or 2 into a closed cavity for baking; Step P2: According to the composition requirements of the ingot, the aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy, aluminum wire and sponge titanium are stirred and mixed and then pressed into electrode blocks with a diameter of Ф300mm to Ф500mm; or the aluminum-titanium-zirconium-molybdenum-tin pentagonal master alloy, titanium-tungsten master alloy, aluminum-silicon master alloy and sponge titanium are stirred and mixed and then pressed into electrode blocks with a diameter of Ф300mm to Ф500mm. Step P3: After connecting the electrode block with the auxiliary electrode, place it in a plasma welding furnace and manufacture a consumable electrode by vacuum welding. Step P4: Place the aforementioned consumable electrode into a crucible and perform vacuum consumable melting more than three times to produce Ti-Al-Mo-Zr-Sn titanium alloy ingots or Ti-Al-Mo-Zr-Sn-W-Si titanium alloy ingots with a diameter of Ф600mm~Ф800mm. Step P5: Finish the ingot and take samples for inspection.

8. The method for preparing titanium alloy ingots according to claim 7, characterized in that: In step P1, the baking temperature is 60℃~100℃; in step P3, the vacuum degree inside the plasma welding furnace during vacuum welding is 5Pa~10Pa; in step P4, during the final vacuum arc stabilization melting, the vacuum degree during the arc stabilization stage is ≤5Pa, the melting temperature is 1600℃~1700℃, and the melting rate is 15kg / min~25kg / min; in step P4, the content of molybdenum and zirconium in Ti-Al-Mo-Zr-Sn titanium alloy ingots or Ti-Al-Mo-Zr-Sn-W-Si titanium alloy ingots varies by ≤0.1wt% in different regions.

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