CN111893325B - High-purity tantalum ingot and preparation method thereof - Google Patents
High-purity tantalum ingot and preparation method thereof Download PDFInfo
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000003723 Smelting Methods 0.000 claims abstract description 95
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000012535 impurity Substances 0.000 claims abstract description 22
- 238000010894 electron beam technology Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 230000007547 defect Effects 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 238000001514 detection method Methods 0.000 claims description 6
- 239000000498 cooling water Substances 0.000 claims description 5
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000005056 compaction Methods 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 238000003466 welding Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 9
- 238000004458 analytical method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000000930 thermomechanical effect Effects 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/24—Obtaining niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
- C22B9/22—Remelting metals with heating by wave energy or particle radiation
- C22B9/228—Remelting metals with heating by wave energy or particle radiation by particle radiation, e.g. electron beams
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- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
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- Plasma & Fusion (AREA)
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Abstract
The invention relates to a high-purity tantalum ingot and a preparation method thereof. The method is characterized by comprising the following steps of: (1) Forming tantalum powder with low impurity content of high-melting-point metal; (2) Sintering under vacuum at high temperature to obtain tantalum rod, tantalum strip or tantalum block, and preparing smelting electrode for vacuum electron beam smelting by tantalum wire with the same purity; (3) At least two times of smelting are carried out by adopting a vacuum electron beam smelting furnace, wherein the first smelting adopts a horizontal feeding mode or a vertical feeding mode, and the second smelting or the subsequent smelting adopts a vertical feeding mode; the electrode rotation is required during the electrode smelting of the second time or after the second time, and the rotation speed is controlled to be 0.3-0.8r/min. The purity of the smelted tantalum cast ingot is high, particularly the gap impurity element C, O, N, H is low, the hardness of the cast ingot is low, and defects such as air holes, looseness and shrinkage holes are few, so that the method is suitable for preparing high-end processing materials such as tantalum targets by pressure processing.
Description
Technical Field
The invention relates to a high-purity tantalum ingot and a preparation method thereof.
Background
Tantalum is an industrially important metal material, has high melting point and good corrosion resistance, is applied to a wide field, and is mainly used as tantalum powder and tantalum wires of a sintered anode of an electrolytic capacitor, and is used for manufacturing structural materials such as a heating element, a heat insulating layer and the like of a high-temperature vacuum furnace, and chemical anti-corrosion materials, high-temperature alloys, hard alloys and superalloys. Tantalum metal has excellent dielectric property, chemical stability, thermal conductivity and special corrosion resistance, so that the target material can be used as an electronic material, a sputtering film material and a corrosion resistant material, and is widely applied to the aspects of microelectronics industry, flat panel displays, optical discs, magnetic head discs and the like. The use of highly pure refractory metal Ta as a wiring material, sputtering target, etc. in large scale integrated circuits has attracted attention in various countries, and is considered to be a microelectronic material with great development prospects.
The preparation technology of the target material can be divided into two technical routes of smelting, thermomechanical treatment and powder sintering, thermomechanical treatment according to the main processing process, wherein the preparation of the tantalum target material mainly adopts a smelting, thermomechanical treatment method to forge, roll and heat treat tantalum cast ingots and other thermomechanical treatment technologies to control microstructure and form blanks. The high-purity tantalum foil is used for manufacturing the shell of the tantalum capacitor and is used for packaging the all-tantalum capacitor, and is mainly applied to high-reliability military tantalum capacitors, the stamping performance and the higher purity of the tantalum foil are required, and the defects that the tantalum foil is free of microcracks and the like are the primary requirements. At present, tantalum ingots are mainly produced by taking tantalum with different forms as smelting electrodes and smelting by one or a combination of several smelting modes of vacuum consumable arc, vacuum electron beam, vacuum plasma beam and plasma arc.
Whatever the smelting mode used, the casting quality of the ingot is the most critical. The production of high-quality tantalum ingots is a first link in metal pressure processing production and is an indispensable component part. It not only supplies the necessary raw material for the processing section-the ingot, but also influences to a great extent the quality and the process properties of the processed product afterwards. Therefore, the casting and ingot production is to provide high-quality ingots meeting the requirements of pressure processing production. The casting task mainly comprises the following steps of 1) obtaining metal with uniform chemical composition and purity meeting the use requirement, 2) casting into an ingot with a shape and a size suitable for pressure processing, wherein the processing resistance is small, the processing resistance is suitable for deformation processing 3) controlling the crystal structure, the shape and the distribution of the ingot, 4) the inside of the ingot is free of structural defects such as air holes, cracks and the like, and the crystal structure of the ingot is fine, so that the theoretical density can be achieved.
Disclosure of Invention
The invention aims to provide a high-purity metal tantalum cast ingot with large specification, high purity, low defect and low hardness, which is suitable for preparing tantalum targets for sputtering and tantalum processing materials for other special purposes.
A high-purity tantalum ingot consists of Ta and impurities, wherein the Ta is more than or equal to 99.999 percent by mass percent.
Wherein Nb is less than or equal to 2ppm, W is less than or equal to 1ppm, mo is less than or equal to 1ppm, U is less than or equal to 0.001ppm, th is less than or equal to 0.015ppm, si is less than or equal to 0.08ppm, C is less than or equal to 10ppm, O is less than or equal to 15ppm, N is less than or equal to 15ppm, H is less than or equal to 2ppm, and other unavoidable impurities, and the total metal impurities are not more than 10ppm except C, O, N, H gas impurities.
The hardness HV/9.8N of the cast ingot is less than or equal to 85.
Wherein the cast ingot is detected by ultrasonic flaw detection, the control interval is more than 50mm, and the wave height is more thanEquivalent, defect rate less than or equal to 1 percent
Wherein the density of the cast ingot is 16.5-16.6 g/cm 3 。
The preparation method of the high-purity tantalum ingot is characterized by comprising the following steps:
(1) Forming tantalum powder with low impurity content of high-melting-point metal;
(2) Sintering under vacuum at high temperature to obtain tantalum rod, tantalum strip or tantalum block, and preparing smelting electrode for vacuum electron beam smelting by tantalum wire with the same purity;
(3) At least two times of smelting are carried out by adopting a vacuum electron beam smelting furnace, wherein the first smelting adopts a horizontal feeding mode or a vertical feeding mode, and the second smelting or the subsequent smelting adopts a vertical feeding mode;
the electrode rotation is required during the electrode smelting of the second time or after the second time, and the rotation speed is controlled to be 0.3-0.8r/min.
In the step (3), the electron beam runs in a mode of interval scanning to ensure the melting of the melting electrode and the maintenance of a molten pool, wherein the control of the electron beam scanning track takes the center of a crucible as an origin, the scanning tracks with different sizes and the scanning residence time are controlled, the largest scanning track of a single gun is 9/10 of the radius of the crucible, and the scanning tracks are gradually decreased according to 1/10 of the radius of the crucible, so that 8 scanning tracks in the molten pool are formed, and the scanning residence time of the largest scanning track is 100-140ms.
The smelting electrode for preparing the vacuum electron beam smelting in the step (2) is specifically in a binding or welding mode.
The content of Nb in the tantalum powder with lower content of high-melting-point metal impurities in the step (1) is less than or equal to 0.001 percent, W is less than or equal to 0.0005 percent and Mo is less than or equal to 0.0005 percent.
In the step (1), isostatic compaction or compression molding is adopted for molding, and the molding pressure is controlled to be more than or equal to 200MPa.
In the step (2), the high-temperature sintering temperature is controlled to be more than or equal to 1800 ℃, the heat preservation time is controlled to be more than or equal to 6 hours, and the relative density after sintering is controlled to be more than or equal to 70 percent.
In the smelting process of the step (3), the vacuum degree of a smelting chamber is required to be more than or equal to 1.0x10 -2 Pa, the specific electric energy during smelting, namely the ratio of smelting power to smelting speed is more than or equal to 4, the cooling water temperature during smelting is controlled to be 20-30 ℃, and the tantalum ingot formed after smelting is cooled in a vacuum cooling chamber for more than or equal to 6 hours.
The high-purity tantalum ingot has the following advantages: the purity of the smelted tantalum cast ingot is high, particularly the gap impurity element C, O, N, H is low, the hardness of the cast ingot is low, and defects such as air holes, looseness and shrinkage holes are few, so that the method is suitable for preparing high-end processing materials such as tantalum targets by pressure processing.
Drawings
FIG. 1 is a flow chart of a production process of a high-purity tantalum ingot;
FIG. 2 is a schematic diagram of electron beam scanning trajectories of a high purity tantalum ingot molten pool.
Detailed Description
The invention is further illustrated by the following figures and examples.
The following examples were produced according to the process flow of fig. 1.
Example 1:
weighing 500Kg of tantalum powder with low content of high-melting-point metal impurities, meeting the requirement of FTa-1 in the tantalum powder industry standard YS/T259-2012, wherein the tantalum powder is provided by Ningxia eastern tantalum industry Co., ltd, loading the tantalum powder into a rubber sleeve, sealing, pressing and forming in a cold isostatic press, and forming pressure is 200Mpa.
The formed tantalum rod is sintered at high temperature under vacuum, and the sintering process is shown in table 1. Binding sintered tantalum rods with tantalum wires with the same purity to prepare smelting electrodes, wherein a smelting crucible is adoptedThe primary smelting adopts a horizontal feeding smelting mode, the smelting power is 500kw, the smelting speed is 85Kg/h, the secondary smelting adopts a vertical feeding mode, the smelting power is 520kw, the smelting speed is 80Kg/h, and the vacuum degree of a smelting chamber is more than or equal to 1.0x10 in the smelting process -2 Pa. The cooling water temperature during smelting is controlled at 26 ℃, and the tantalum ingot formed after smelting is cooled for more than 6 hours in a vacuum cooling chamber.
The electrode rotation is required during secondary electrode smelting, the rotation speed is 0.6r/min, and the smelting scanning track control is shown in Table 2.
The analysis results of specific high purity tantalum ingots are shown in tables 3 and 4. Flaw detection is carried out according to the ultrasonic flaw detection and quality grading method of the steel castings, and the equivalent value of the flaw is measuredThe continuous length of the defects is less than or equal to 50mm, and the detectable defect rate is lower than 1%.
Table 1 tantalum rod sintering process
| Step (a) | Heating condition |
| 1 | Room temperature to 700-800 deg.c for 2 hr to reach and heat preservation for 2 hr |
| 2 | Raising the temperature to 700-800-1600-1700 ℃ for 3h, and preserving the heat for 3h. |
| 3 | 1600-1700 deg.C to 1900 deg.C, 3h up to, heat-insulating 7h |
| 4 | Vacuum cooling or argon filling cooling to room temperature in power failure |
Table 2 smelting scan trajectory control
TABLE 3 analysis results of high purity tantalum ingot gas impurities
(the gap impurity element of the high-purity tantalum ingot is lower, the hardness is low, the processing of high-end products such as targets is easy to carry out, and the abnormal discharge of the targets in the sputtering process can be effectively prevented by the low impurity element, so that the quality of the sputtered film is ensured
TABLE 4 high purity tantalum ingot GDMS analysis results
| Determination of elements | Measurement results/ppm (wt) | Determination of elements | Measurement results/ppm (wt) |
| Li | ＜0.003 | Pd | ＜0.005 |
| Be | ＜0.003 | Ag | ＜0.005 |
| B | ＜0.005 | Cd | ＜0.005 |
| C | -- | In | ＜0.005 |
| N | -- | Sn | ＜0.005 |
| o | -- | Sb | ＜0.005 |
| F | ＜0.5 | Te | ＜0.005 |
| Na | ＜0.005 | I | ＜0.005 |
| Mg | ＜0.005 | Cs | ＜0.005 |
| Al | ＜0.005 | Ba | ＜0.005 |
| Si | ＜0.06 | La | ＜0.005 |
| P | ＜0.005 | Ce | ＜0.005 |
| S | ＜0.015 | Pr | ＜0.005 |
| Cl | ＜0.03 | Nd | ＜0.005 |
| K | 0.006 | Sm | ＜0.005 |
| Ca | ＜0.005 | Eu | ＜0.005 |
| Sc | ＜0.003 | Gd | ＜0.005 |
| Ti | ＜0.005 | Tb | ＜0.005 |
| V | ＜0.003 | Dy | ＜0.005 |
| Cr | ＜0.005 | Ho | ＜0.005 |
| Mn | ＜0.003 | Er | ＜0.005 |
| Fe | ＜0.005 | Tm | ＜0.005 |
| Co | ＜0.003 | Yb | ＜0.005 |
| Ni | ＜0.005 | Lu | ＜0.005 |
| Cu | ＜0.005 | Hf | ＜0.005 |
| Zn | ＜0.005 | Ta | Matrix |
| Ga | ＜0.005 | W | 0.023 |
| Ge | ＜0.005 | Re | ＜0.005 |
| As | ＜0.005 | Os | ＜0.005 |
| Se | ＜0.03 | Ir | ＜0.005 |
| Br | ＜0.005 | Pt | ＜0.05 |
| Rb | ＜0.005 | Au | ＜0.05 |
| Sr | ＜0.005 | Hg | ＜0.005 |
| Y | ＜0.003 | Tl | ＜0.005 |
| Zr | ＜0.005 | Pb | ＜0.005 |
| Nb | 0.44 | Bi | ＜0.01 |
| Mo | 0.015 | Th | ＜0.001 |
| Ru | ＜0.005 | U | ＜0.001 |
| Rh | ＜0.005 |
(the purity of the tantalum cast ingot reaches more than 5N, most elements reach the lower limit of the GDMS analysis method, the requirement of the high-purity tantalum cast ingot for a sputtering target is completely met, and necessary conditions are provided for preparing the high-purity tantalum target)
Example 2:
weighing 250Kg of tantalum powder with low impurity content of high-melting metal, and meeting the requirements of FTa-1 in the tantalum powder industry standard YS/T259-2012. (tantalum powder is supplied by Ningxia eastern tantalum industry Co., ltd.) tantalum powder is put into a steel molding press-bar-shaped device, and is subjected to press molding by an oil pressure device under a molding pressure of 180MPa, and the molded bar can be moved without breaking.
The formed tantalum strip is sintered at high temperature under vacuum, and the sintering process is shown in table 1. Binding sintered tantalum strips with tantalum wires with the same purity to prepare smelting electrodes, wherein a smelting crucible is adoptedThe primary smelting adopts a horizontal feeding smelting mode, the smelting power is 420kw, the smelting speed is 80Kg/h, the secondary smelting adopts a vertical feeding mode, the smelting power is 440kw, and the smelting speed is 75 Kg-h, the vacuum degree of the smelting chamber required in the smelting process is more than or equal to 1.0x10 -2 Pa. The temperature of the input cooling water is controlled at 26 ℃ during smelting, and the tantalum ingot formed after smelting is cooled for more than 5 hours in a vacuum cooling chamber.
TABLE 5 smelting scan trajectory control
TABLE 6 analysis results of high purity tantalum ingot gas impurities
The electrode rotation is required during secondary electrode smelting, the rotation speed is 0.5r/min, and the smelting scanning track control is shown in Table 5.
TABLE 7 high purity tantalum ingot GDMS analysis results
| Determination of elements | Measurement results/ppm (wt) | Determination of elements | Measurement results/ppm (wt) |
| Li | ＜0.001 | Pd | ＜0.005 |
| Be | ＜0.003 | Ag | ＜0.005 |
| B | ＜0.005 | Cd | ＜0.005 |
| C | -- | In | ＜0.005 |
| N | -- | Sn | ＜0.005 |
| O | -- | Sb | ＜0.005 |
| F | ＜0.5 | Te | ＜0.005 |
| Na | 0.008 | 1 | ＜0.005 |
| Mg | ＜0.005 | Cs | ＜0.005 |
| Al | ＜0.005 | Ba | ＜0.005 |
| Si | ＜0.06 | La | ＜0.005 |
| P | ＜0.005 | Ce | ＜0.005 |
| S | ＜0.015 | Pr | ＜0.005 |
| C1 | 0.044 | Nd | ＜0.005 |
| K | 0.012 | Sm | ＜0.005 |
| Ca | ＜0.005 | Eu | ＜0.005 |
| Sc | ＜0.003 | Gd | ＜0.005 |
| Ti | ＜0.005 | Tb | ＜0.005 |
| v | ＜0.001 | Dy | ＜0.005 |
| Cr | ＜0.005 | Ho | ＜0.005 |
| Mn | ＜0.001 | Er | ＜0.005 |
| Fe | ＜0.005 | Tm | ＜0.005 |
| Co | ＜0.003 | Yb | ＜0.005 |
| Ni | ＜0.005 | Lu | ＜0.005 |
| Cu | 0.021 | Hf | ＜0.005 |
| Zn | ＜0.005 | Ta | Matrix |
| Ga | ＜0.005 | W | 0.83 |
| Ge | ＜0.005 | Re | ＜0.005 |
| As | ＜0.005 | Os | ＜0.005 |
| Se | ＜0.03 | Ir | ＜0.005 |
| Br | ＜0.005 | Pt | ＜0.05 |
| Rb | ＜0.005 | Au | ＜0.05 |
| Sr | ＜0.005 | Hg | ＜0.005 |
| Y | ＜0.003 | Tl | ＜0.005 |
| zr | ＜0.005 | Pb | ＜0.005 |
| Nb | 0.82 | Bi | ＜0.01 |
| Mo | 0.18 | Th | ＜0.001 |
| Ru | ＜0.005 | U | ＜0.001 |
| Rh | ＜0.005 |
The analysis results of specific high purity tantalum ingots are shown in tables 6 and 7. Flaw detection is carried out according to the ultrasonic flaw detection and quality grading method of the steel castings, and the equivalent value of the flaw is measuredThe continuous length of the defects is less than or equal to 50mm, and the detectable defect rate is lower than 1%.
Claims (6)
1. A high-purity tantalum ingot consists of Ta and impurities, wherein the Ta is more than or equal to 99.999 percent by mass percent; wherein Nb is less than or equal to 2ppm, W is less than or equal to 1ppm, mo is less than or equal to 1ppm, U is less than or equal to 0.001ppm, th is less than or equal to 0.015ppm, si is less than or equal to 0.08ppm, C is less than or equal to 10ppm, O is less than or equal to 15ppm, N is less than or equal to 15ppm, H is less than or equal to 2ppm, and other unavoidable impurities, and the total metal impurities are not more than 10ppm except C, O, N, H gas impurities; the hardness HV/9.8N of the cast ingot is less than or equal to 85; wherein, the cast ingot is detected by ultrasonic flaw detection, the control interval is more than 50mm, the wave height is more than phi 2mm equivalent, and the defect rate is less than or equal to 1%; wherein the density of the cast ingot is 16.5-16.6 g/cm 3 ；
The preparation method of the high-purity tantalum ingot comprises the following steps:
(1) Forming tantalum powder with low impurity content of high-melting-point metal;
(2) Sintering under vacuum at high temperature to obtain tantalum rod, tantalum strip or tantalum block, and preparing smelting electrode for vacuum electron beam smelting by tantalum wire with the same purity;
(3) At least two times of smelting are carried out by adopting a vacuum electron beam smelting furnace, wherein the first smelting adopts a horizontal feeding mode or a vertical feeding mode, and the second smelting or the subsequent smelting adopts a vertical feeding mode;
during the second or subsequent electrode smelting, the electrode is required to rotate, and the rotation speed is controlled to be 0.3-0.8 r/min;
the electron beam in the step (3) runs in a mode of interval scanning, so that melting of a melting electrode and maintenance of a molten pool are ensured, wherein the control of an electron beam scanning track takes the center of a crucible as an origin, scanning tracks with different sizes and scanning residence time are controlled, the largest scanning track of a single gun is 9/10 of the radius of the crucible, and the largest scanning track is gradually decreased according to 1/10 of the radius of the crucible, so that 8 scanning tracks in the molten pool are formed, and the scanning residence time of the largest scanning track is 100-140ms;
in the smelting process of the step (3), the vacuum degree of a smelting chamber is required to be more than or equal to 1.0x10 -2 Pa, the specific electric energy during smelting, namely the ratio of smelting power to smelting speed is more than or equal to 4, the cooling water temperature during smelting is controlled to be 20-30 ℃, and the tantalum ingot formed after smelting is cooled in a vacuum cooling chamber for more than or equal to 6 hours.
2. The method for preparing a high purity tantalum ingot according to claim 1, comprising the steps of:
(1) Forming tantalum powder with low impurity content of high-melting-point metal;
(2) Sintering under vacuum at high temperature to obtain tantalum rod, tantalum strip or tantalum block, and preparing smelting electrode for vacuum electron beam smelting by tantalum wire with the same purity;
(3) At least two times of smelting are carried out by adopting a vacuum electron beam smelting furnace, wherein the first smelting adopts a horizontal feeding mode or a vertical feeding mode, and the second smelting or the subsequent smelting adopts a vertical feeding mode;
during the second or subsequent electrode smelting, the electrode is required to rotate, and the rotation speed is controlled to be 0.3-0.8 r/min;
the electron beam in the step (3) runs in a mode of interval scanning, so that melting of a melting electrode and maintenance of a molten pool are ensured, wherein the control of an electron beam scanning track takes the center of a crucible as an origin, scanning tracks with different sizes and scanning residence time are controlled, the largest scanning track of a single gun is 9/10 of the radius of the crucible, and the largest scanning track is gradually decreased according to 1/10 of the radius of the crucible, so that 8 scanning tracks in the molten pool are formed, and the scanning residence time of the largest scanning track is 100-140ms;
in the smelting process of the step (3), the vacuum degree of a smelting chamber is required to be more than or equal to 1.0x10 -2 Pa, the specific electric energy during smelting, namely the ratio of smelting power to smelting speed is more than or equal to 4, the cooling water temperature during smelting is controlled to be 20-30 ℃, and the tantalum ingot formed after smelting is cooled in a vacuum cooling chamber for more than or equal to 6 hours.
3. The method for preparing the high-purity tantalum ingot according to claim 2, wherein the method comprises the following steps: the smelting electrode for preparing the vacuum electron beam smelting in the step (2) is specifically in a binding or welding mode.
4. The method for preparing the high-purity tantalum ingot according to claim 2, wherein the method comprises the following steps: the content of Nb in the tantalum powder with lower content of high-melting-point metal impurities in the step (1) is less than or equal to 0.001 percent, W is less than or equal to 0.0005 percent and Mo is less than or equal to 0.0005 percent.
5. The method for preparing the high-purity tantalum ingot according to claim 2, wherein the method comprises the following steps: in the step (1), isostatic compaction or compression molding is adopted for molding, and the molding pressure is controlled to be more than or equal to 200MPa.
6. The method for preparing the high-purity tantalum ingot according to claim 2, wherein the method comprises the following steps: in the step (2), the high-temperature sintering temperature is controlled to be more than or equal to 1800 ℃, the sintering heat preservation time is controlled to be more than or equal to 6 hours, and the relative density after sintering is controlled to be more than or equal to 70 percent.
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| CN115572844B (en) * | 2022-10-27 | 2024-01-19 | 先导薄膜材料(安徽)有限公司 | Method for recovering tantalum from tantalum residual target |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5722034A (en) * | 1994-12-09 | 1998-02-24 | Japan Energy Corporation | Method of manufacturing high purity refractory metal or alloy |
| JP2005336617A (en) * | 2005-05-30 | 2005-12-08 | Hitachi Metals Ltd | Target for sputtering, its production method and high melting point metal powder material |
| CN102367568A (en) * | 2011-10-20 | 2012-03-07 | 宁波江丰电子材料有限公司 | Preparation method of high-purity tantalum target material |
| CN102382993A (en) * | 2011-10-09 | 2012-03-21 | 广东致远新材料有限公司 | Preparation method of target-grade ultrahigh-purity tantalum metal |
| KR20130030456A (en) * | 2011-09-19 | 2013-03-27 | 한국생산기술연구원 | Sputtering target ta sheet and manufacturing method of the same |
| KR20130129318A (en) * | 2011-11-16 | 2013-11-28 | 한국지질자원연구원 | Preparation of ultra-high purity cylindrical ingot of refractory metals by electron beam drip melting |
| CN110079719A (en) * | 2019-06-13 | 2019-08-02 | 西北有色金属研究院 | A kind of method of hafnium content in raising tantalum-tungsten alloy |
-
2020
- 2020-06-29 CN CN202010604800.XA patent/CN111893325B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5722034A (en) * | 1994-12-09 | 1998-02-24 | Japan Energy Corporation | Method of manufacturing high purity refractory metal or alloy |
| JP2005336617A (en) * | 2005-05-30 | 2005-12-08 | Hitachi Metals Ltd | Target for sputtering, its production method and high melting point metal powder material |
| KR20130030456A (en) * | 2011-09-19 | 2013-03-27 | 한국생산기술연구원 | Sputtering target ta sheet and manufacturing method of the same |
| CN102382993A (en) * | 2011-10-09 | 2012-03-21 | 广东致远新材料有限公司 | Preparation method of target-grade ultrahigh-purity tantalum metal |
| CN102367568A (en) * | 2011-10-20 | 2012-03-07 | 宁波江丰电子材料有限公司 | Preparation method of high-purity tantalum target material |
| KR20130129318A (en) * | 2011-11-16 | 2013-11-28 | 한국지질자원연구원 | Preparation of ultra-high purity cylindrical ingot of refractory metals by electron beam drip melting |
| CN110079719A (en) * | 2019-06-13 | 2019-08-02 | 西北有色金属研究院 | A kind of method of hafnium content in raising tantalum-tungsten alloy |
Non-Patent Citations (2)
| Title |
|---|
| 浅谈1200kW电子束炉熔炼工艺;谢建平;矿冶;第22卷(第04期);77-79+90 * |
| 真空电子束熔炼制备超高纯钽锭工艺研究;任志东等;湖南有色金属;第36卷(第06期);53-55 * |
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