Fine-grain high-purity tantalum plate and tantalum plate texture regulation and control method
Through multi-stage heat treatment, the grain and texture of high-purity tantalum plates are adjusted, and the problems of uneven texture and difficulty in fine crystallization of tantalum plates in the prior art are solved, and the fine crystallization and texture regulation of high-purity tantalum plates are realized, which is suitable for industrial production.
Patent Information
- Application Number
- CN202411796941.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-09
- Publication Date
- 2025-04-01
AI Technical Summary
During the preparation process of existing fine crystal high-purity tantalum plates, unidirectional rolling leads to a strong single texture in the tantalum plate, making it difficult to achieve uniform distribution and fine crystallization of the texture, and the process complexity and manufacturing cost are high, making it not suitable for industrial production.
Through multi-stage heat treatment, the deformed energy storage and internal dislocation interface structure of different deformed grains in high-purity tantalum plates can be adjusted, so as to achieve the refinement of grains and controllable adjustment of texture morphology. The specific steps include heat treatment at 400°C-800°C for 20 minutes-120 minutes, cooling and heat treatment again, and finally heating to 950°C-1050°C for 80 minutes-100 minutes to produce fine crystalline high-purity tantalum plates.
The fine crystallization and texture regulation of high-purity tantalum plates are achieved, with an average grain size of less than 23μm, and the contents of α texture and γ texture are independently 20%-50% respectively. They are simple to operate and low cost, and are suitable for industrial applications.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of tantalum plates, and in particular to a fine-grained high-purity tantalum plate and a tantalum plate texture control method. Background Art
[0002] High-purity tantalum has a high melting point, good conductivity, and stable chemical properties. It is widely used in electronics, electrical, energy and chemical, and aerospace fields. The performance of tantalum products is closely related to their grain size and texture. For example, high-quality, high-purity tantalum sputtering targets used in deep submicron integrated circuits must have both fine grains (average grain size less than 50μm) and weakened texture (single texture content does not exceed 50%); tantalum plates with excellent deep processing performance are one of the important materials for the manufacture of high-end tantalum capacitors. The grain size should not be less than level 8 (average grain size less than 23μm) and have a strong γ texture or uniformly distributed crystallographic orientation. Therefore, grain refinement and texture control are the key goals of high-purity tantalum plate forming and processing technology.
[0003] The forming processing method of fine-grained high-purity tantalum plates is usually to prepare high-purity tantalum ingots by electron beam melting, and then perform plastic processing such as forging and rolling on the high-purity tantalum ingots, and finally perform heat treatment on the finished product. The grain size of the high-purity tantalum ingot reaches the centimeter level. In order to fully break the grains, the forging and rolling strains in the preparation process of fine-grained high-purity tantalum plates are relatively large. However, large-strain unidirectional rolling will only form a strong single texture in the high-purity tantalum plate after annealing of the finished product. Changing the rolling strain path (such as cross rolling) or using asymmetric rolling to increase the additional shear force is beneficial to reducing the strength of the single texture, but it may increase the texture gradient of the tantalum plate along the thickness direction, while increasing the process complexity and manufacturing cost, which is not suitable for industrial production. Therefore, it is urgent to provide a solution to improve the above problems. Summary of the invention
[0004] The object of the present invention is to provide a fine-grained high-purity tantalum plate and a tantalum plate texture control method.
[0005] In a first aspect, the present invention provides a fine-grained high-purity tantalum plate, wherein the average grain size of the tantalum plate is less than 23 μm, and the contents of α texture and γ texture in the tantalum plate are independently 20%-50%.
[0006] In a second aspect, the present invention provides a method for controlling the texture of a tantalum plate, comprising: heat treating a high-purity tantalum plate at 400°C-800°C for 20min-120min, cooling the plate by 20°C-80°C and heat treating the plate for 50min-150min, heating the plate to 950°C-1050°C and heat treating the plate for 80min-100min, and cooling the plate to room temperature to obtain a fine-grained high-purity tantalum plate.
[0007] Optionally, the high purity tantalum plate is heat treated at 450° C.-550° C. for 30 min-50 min, and then cooled to 400° C.-500° C. and heat treated for 50 min-70 min.
[0008] Optionally, the sum of the heat treatment time of the high-purity tantalum plate at 450° C.-550° C. and the heat treatment time at 400° C.-500° C. is 90 min-110 min.
[0009] Optionally, the high-purity tantalum plate is heat treated at 500° C. for 40 minutes, and then cooled to 450° C. for heat treatment for 60 minutes.
[0010] Optionally, the high purity tantalum plate is heat treated at 450° C.-550° C. for 90 min-110 min, and then cooled to 400° C.-500° C. for heat treatment for 120 min-160 min.
[0011] Optionally, the sum of the heat treatment time of the high-purity tantalum plate at 450° C.-550° C. and the heat treatment time at 400° C.-500° C. is greater than or equal to 200 min.
[0012] Optionally, the high-purity tantalum plate is heat treated at 500° C. for 100 minutes, and then cooled to 450° C. and heat treated for 140 minutes.
[0013] Optionally, the high purity tantalum plate is heat treated at 650° C.-750° C. for 20 min-60 min, and then cooled to 600° C.-700° C. for heat treatment for 40 min-80 min.
[0014] Optionally, the high-purity tantalum plate is heat treated at 700° C. for 40 minutes, and then cooled to 650° C. for heat treatment for 60 minutes.
[0015] Optionally, the temperature is lowered to 450° C.-680° C. and heat treated for 50 min-150 min.
[0016] Optionally, the heat treatment is a constant temperature heat treatment.
[0017] Optionally, the purity of the high-purity tantalum plate is greater than or equal to 99.9%.
[0018] Optionally, the high-purity tantalum plate is plastically deformed in advance, including electron beam melting followed by 2-4 three-way forgings with a unidirectional reduction of 15-35% each time, annealing after forging and 2-3 unidirectional rolling with a reduction of 60%-95%. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 A flow chart of a tantalum plate texture control method provided by the present invention;
[0020] Figure 2 The distribution diagram of grain boundaries (orientation difference greater than 15°) of fine-grained high-purity tantalum plates obtained in Examples 1 to 3 of the present invention and Comparative Example 1;
[0021] Figure 3 This is a distribution diagram of different texture contents in the recrystallized structure of the fine-grained high-purity tantalum plates obtained in Examples 1 to 3 of the present invention and Comparative Example 1. DETAILED DESCRIPTION
[0022] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein should be the common meanings understood by people with general skills in the field to which the present invention belongs.
[0023] See also Figure 1 The present invention provides a method for controlling the texture of a tantalum plate, comprising the following steps:
[0024] S1. Heat treat the high purity tantalum plate at 400°C-800°C for 20min-120min;
[0025] S2, cooling down by 20℃-80℃ and heat treatment for 50min-150min;
[0026] S3, heating to 950℃-1050℃ for heat treatment for 80min-100min;
[0027] S4. Cool to room temperature to obtain a fine-grained high-purity tantalum plate.
[0028] In fact, the texture control method provided by the present invention can adjust the deformation energy storage and internal dislocation interface structure of different deformed grains in the high-purity tantalum plate by performing multi-stage heat treatment, thereby realizing the controllable adjustment of the grain refinement and texture morphology in the high-purity tantalum plate. Specifically, the average grain size of the fine-grained high-purity tantalum plate obtained by the texture control method provided by the present invention is less than 23μm, and the content of α texture and γ texture in the tantalum plate is independently 20%-50%.
[0029] In addition, the texture control method provided by the present invention is simple to operate, low in cost and easy to implement, which is conducive to large-scale industrial application and has important practical value for preparing high-quality high-purity tantalum sputtering targets and preparing high-purity tantalum plates with excellent deep processing performance.
[0030] In some embodiments, the high purity tantalum plate is heat treated at 450°C-550°C for 30-50 minutes in step S1, and then cooled to 400°C-500°C for 50-70 minutes in step S2. Specifically, the total heat treatment time of the high purity tantalum plate in step S1 and step S2 is controlled to be 90-110 minutes.
[0031] In some further embodiments, the high purity tantalum plate is heat treated at 500° C. for 40 minutes in step S1 , and then cooled to 450° C. and heat treated for 60 minutes in step S2 .
[0032] In some other embodiments, after the high purity tantalum plate is heat treated at 450°C-550°C for 90min-110min in step S1, the temperature is lowered to 400°C-500°C for heat treatment for 120min-160min in step S2. Specifically, the total heat treatment time of the high purity tantalum plate in step S1 and step S2 is controlled to be greater than or equal to 200min.
[0033] In some further embodiments, the high purity tantalum plate is heat treated at 500° C. for 100 min in step S1 , and then cooled to 450° C. and heat treated for 140 min in step S2 .
[0034] In some embodiments, after the high purity tantalum plate is heat treated at 650°C-750°C for 20min-60min in step S1, the temperature is lowered to 600°C-700°C for heat treatment for 40min-80min in step S2. Specifically, the heat treatment temperature in step S1 is 700°C and the heat treatment time is 40min, and the heat treatment temperature in step S2 is 650°C and the heat treatment time is 60min.
[0035] In some embodiments, in step S2, the temperature is lowered to 450°C-680°C and heat treated for 50min-150min.
[0036] In fact, the high-purity tantalum plate can be plastically deformed in advance, including: electron beam melting followed by 2-4 three-way forgings, with each forging having a unidirectional reduction of 15-35%, annealing after forging and 2-3 unidirectional rolling with a reduction of 60%-95%. Specifically, the texture control method provided by the present invention can control the internal grain size and texture without changing the plastic processing technology of the tantalum plate.
[0037] Specifically, the heat treatments performed in steps S1 to S4 are all isothermal heat treatments, and the temperature change rates during the heating and cooling processes are independently 1°C / min-10°C / min, and the purity of the high-purity tantalum plate used is greater than or equal to 99.9%.
[0038] Preparation Example 1
[0039] This preparation example 1 provides a preparation method for a high-purity tantalum plate, comprising: using electron beam melting to perform three-way forging of a high-purity tantalum ingot, and the reduction in each direction is independently 20%-30%, after the forged tantalum ingot is annealed at 1000°C for 60 minutes, and then the annealed forged tantalum ingot is subjected to three-way rolling, and the reduction in each rolling is controlled to be 80%, 80% and 90% respectively, and a high-purity tantalum plate is obtained after rolling.
[0040] Example 1
[0041] This embodiment 1 provides a method for controlling the texture of a tantalum plate, comprising the following steps:
[0042] S1. Place the high-purity tantalum plate in the furnace of a heat treatment furnace, introduce argon gas to replace the gas in the furnace, and then heat the heat treatment furnace to 500°C at a rate of 10°C / min and keep the temperature for 40 minutes;
[0043] S2, the heat treatment furnace is cooled down to 450°C at a rate of 10°C / min and kept at this temperature for 60min;
[0044] S3, the heat treatment furnace is heated to 1000°C at a rate of 10°C / min and then kept at this temperature for 90 minutes;
[0045] S4. After cooling to 150°C in the furnace, a fine-grained high-purity tantalum plate is obtained.
[0046] Example 2
[0047] This embodiment 2 provides a method for controlling the texture of a tantalum plate, comprising the following steps:
[0048] S1. Place the high-purity tantalum plate in the furnace of a heat treatment furnace, introduce argon gas to replace the gas in the furnace, and then heat the heat treatment furnace to 700°C at a rate of 10°C / min and keep the temperature for 40 minutes;
[0049] S2, the heat treatment furnace is cooled down to 650°C at a rate of 10°C / min and kept at this temperature for 60min;
[0050] S3, the heat treatment furnace is heated to 1000°C at a rate of 10°C / min and then kept at this temperature for 90 minutes;
[0051] S4. After cooling to 150°C in the furnace, a fine-grained high-purity tantalum plate is obtained.
[0052] Example 3
[0053] This embodiment 3 provides a method for controlling the texture of a tantalum plate, comprising the following steps:
[0054] S1. Place the high-purity tantalum plate in the furnace of a heat treatment furnace, introduce argon gas to replace the gas in the furnace, and then heat the heat treatment furnace to 500°C at a rate of 10°C / min and keep the temperature for 100 minutes;
[0055] S2, the heat treatment furnace is cooled down to 450°C at a rate of 10°C / min and kept at this temperature for 140min;
[0056] S3, the heat treatment furnace is heated to 1000°C at a rate of 10°C / min and then kept at this temperature for 90 minutes;
[0057] S4. After cooling to 150°C in the furnace, a fine-grained high-purity tantalum plate is obtained.
[0058] Comparative Example 1
[0059] This comparative example 1 provides a method for controlling the texture of a tantalum plate, comprising the following steps: placing a high-purity tantalum plate in the furnace of a heat treatment furnace, introducing argon gas to replace the gas in the furnace, heating the heat treatment furnace to 1000°C at a rate of 10°C / min and keeping the temperature for 90 minutes, and then cooling the furnace to 150°C to obtain a fine-grained high-purity tantalum plate.
[0060] Characterization analysis
[0061] The rolled surfaces of the fine-grained high-purity tantalum plates obtained in Examples 1 to 3 and Comparative Example 1 were characterized by electron backscatter diffraction analysis. Figure 2 As shown in a to d in the figure, the average grain size and texture composition are analyzed, as shown in Figure 2 and Figure 3 As shown. Figure 1 It can be seen that the average grain size of the tantalum plate in Examples 1 to 3 has increased, but none of them exceeds 22 μm. Figure 3 It can be seen that the content of γ texture and α texture in the tantalum plate in Examples 1 to 3 is similar, and the content is less than 50%, while the content of grains with other crystallographic orientations is 17.9-23.8%. In Comparative Example 1, the content of γ texture reaches 74.1%, and the content of α texture and other crystallographic orientation grains is only 17.5% and 8.4%, respectively. The above results show that multi-stage pre-recovery treatment before crystallization annealing can significantly weaken the γ texture in the recrystallized structure of the high-purity tantalum plate and achieve uniform distribution of texture components.
[0062] Although the embodiments of the present invention are described in detail above, it is obvious to those skilled in the art that various modifications and variations can be made to these embodiments. However, it should be understood that such modifications and variations are within the scope and spirit of the present invention as described in the claims. Moreover, the present invention described herein may have other embodiments and may be implemented or realized in a variety of ways.
Claims
1. A fine-grained high-purity tantalum plate, characterized in that: The average grain size of the tantalum plate is less than 23 μm, and the contents of α texture and γ texture in the tantalum plate are independently 20%-50%.
2. A method for controlling the texture of a tantalum plate, characterized in that: include: The high purity tantalum plate is heat treated at 400-800°C for 20-120 minutes, then cooled by 20-80°C and heat treated for 50-150 minutes, heated to 950-1050°C and heat treated for 80-100 minutes, and then cooled to room temperature to obtain a fine grain high purity tantalum plate.
3. The texture control method according to claim 2, characterized in that: The high purity tantalum plate is heat treated at 450°C-550°C for 30min-50min, and then cooled to 400°C-500°C for heat treatment for 50min-70min; preferably, the sum of the heat treatment time of the high purity tantalum plate at 450°C-550°C and the heat treatment time at 400°C-500°C is 90min-110min.
4. The texture control method according to claim 3, characterized in that: The high purity tantalum plate was heat treated at 500° C. for 40 minutes, and then cooled to 450° C. for heat treatment for 60 minutes.
5. The texture control method according to claim 2, characterized in that: The high purity tantalum plate is heat treated at 450°C-550°C for 90min-110min, and then cooled to 400°C-500°C for heat treatment for 120min-160min; preferably, the sum of the heat treatment time of the high purity tantalum plate at 450°C-550°C and the heat treatment time at 400°C-500°C is greater than or equal to 200min.
6. The texture control method according to claim 5, characterized in that: The high purity tantalum plate was heat treated at 500° C. for 100 minutes, and then cooled to 450° C. for 140 minutes.
7. The texture control method according to claim 2, characterized in that: The high purity tantalum plate is heat treated at 650° C.-750° C. for 20 min-60 min, then cooled to 600° C.-700° C. and heat treated for 40 min-80 min.
8. The texture control method according to claim 7, characterized in that: The high purity tantalum plate was heat treated at 700° C. for 40 minutes, and then cooled to 650° C. for 60 minutes.
9. The texture control method according to claim 2, characterized in that: Cool down to 450℃-680℃ and heat treat for 50min-150min.
10. The texture control method according to any one of claims 2 to 9, characterized in that: The heat treatment is a constant temperature heat treatment; and / or, the purity of the high purity tantalum plate is greater than or equal to 99.9%; and / or, the high purity tantalum plate is plastically deformed in advance, including electron beam melting followed by 2-4 three-way forgings, with each forging having a unidirectional reduction of 15-35%, annealing after forging and 2-3 unidirectional rolling with a reduction of 60%-95%.