CN117684033A - High-performance TZM alloy foil and preparation method thereof - Google Patents
High-performance TZM alloy foil and preparation method thereof Download PDFInfo
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- 239000011888 foil Substances 0.000 title claims abstract description 90
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- 238000000137 annealing Methods 0.000 claims abstract description 70
- 238000005096 rolling process Methods 0.000 claims abstract description 49
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000498 ball milling Methods 0.000 claims abstract description 23
- 238000001125 extrusion Methods 0.000 claims abstract description 21
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- 238000005097 cold rolling Methods 0.000 claims abstract description 18
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005098 hot rolling Methods 0.000 claims abstract description 16
- 229910000048 titanium hydride Inorganic materials 0.000 claims abstract description 15
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000568 zirconium hydride Inorganic materials 0.000 claims abstract description 15
- 229910026551 ZrC Inorganic materials 0.000 claims abstract description 10
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims abstract description 10
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- 239000012535 impurity Substances 0.000 description 12
- 229910052750 molybdenum Inorganic materials 0.000 description 11
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- YUSUJSHEOICGOO-UHFFFAOYSA-N molybdenum rhenium Chemical compound [Mo].[Mo].[Re].[Re].[Re] YUSUJSHEOICGOO-UHFFFAOYSA-N 0.000 description 2
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Abstract
The thickness of the high-performance TZM alloy foil is 0.005-0.15 mm, and the dimensional deviation is +/-2 mu m; the tensile strength is more than or equal to 1400MPa, the yield strength is more than or equal to 1200MPa, and the elongation is more than or equal to 5%; the oxygen content is less than or equal to 30ppm, the nitrogen content is less than or equal to 20ppm, the microstructure characteristics comprise a lamellar fiber structure with long and thin grains in mutually overlapped and staggered mode, the fiber width-to-length ratio is 1% -20%, and the volume fraction of micro-scale and nano-scale second phases which are finely and uniformly dispersed is 0.1% -2%; the preparation method comprises the steps of carrying out degassing purification on high-purity molybdenum powder, carrying out ball milling and mixing with micron-sized titanium hydride or titanium carbide, zirconium hydride or zirconium carbide and graphite powder, preparing alloy pressed blanks, carrying out composite sintering, carrying out vacuum consumable arc melting, large-deformation extrusion cogging, cross hot rolling, cross warm rolling, hydrogen annealing, cross cold rolling, and finally carrying out stress relief annealing; the TZM alloy foil can be widely used in the fields of electric vacuum, electronics and medical treatment.
Description
Technical Field
The invention belongs to the technical field of refractory metal alloy preparation, and relates to a high-performance TZM alloy foil and a preparation method thereof.
Background
The TZM alloy is prepared by taking Mo as a matrix and doping trace Ti (0.40-0.55wt%), zr (0.06-0.12wt%) and C (0.01-0.04wt%) elements, and compared with pure molybdenum, a second phase generated by adding the alloy can prevent dislocation movement, so that the TZM alloy has more excellent room temperature plasticity, and meanwhile, the second phase can inhibit grain growth, improve the recrystallization temperature of the TZM alloy, so that the alloy has excellent high-temperature performance and stability, and becomes an alloy system which is very key in molybdenum alloy and has wider application. The improvement of the comprehensive performance of the TZM alloy greatly expands the high-end application scene of the TZM alloy, in particular to the TZM alloy foil, and the TZM alloy foil can be widely applied to the fields of electric vacuum, electronics and medical treatment, such as grid meshes of a traveling wave tube grid-control electron gun and action parts of a detector.
At present, the oxygen/nitrogen content of the conventional TZM alloy plate/sheet/foil is up to 300-2000 ppm or more, and oxygen/nitrogen is extremely easy to combine with titanium and zirconium elements, so that the inside of the material is mainly reinforced by oxide or nitride particles, the oxide or nitride has the characteristics of large size and large quantity, is easy to squeeze and pull to break in the subsequent deformation processing process, becomes a potential crack source, reduces interlayer interface combination, and is easy to generate layering and cracking phenomena in the processing process; meanwhile, oxygen/nitrogen deprives titanium, zirconium and carbon elements, so that the formation probability of carbide is seriously reduced, the material has poor room temperature strong plasticity, and the oxide and nitride have insufficient high temperature stability, so that the high temperature performance advantage of the material is not obvious. Due to limitation of TZM alloy foil thickness, larger-sized oxide and nitride second-phase particles in the material can enable the surface of the foil to be concave-convex and layered inside, even scratch the surface and cut through the body, so that layering, cracking and even fracture phenomena are easy to occur in the processing process, and the high-end scene requirement cannot be met. TZM alloy foil, especially foil with thickness of 0.1mm or less, is difficult to prepare, and the preparation of the TZM alloy foil with high strength, high interlayer combination and high air tightness and high performance is more difficult. The defect of the high-performance TZM alloy foil material forms a stopper for the development of devices with higher requirements and the subsequent shaping production guarantee.
Regarding TZM alloy foil and a method for preparing the same, chinese patent publication No. CN 114769593a proposes a method for preparing molybdenum and molybdenum alloy foil: (1) Reducing the conventional commercial molybdenum and molybdenum alloy powder by hydrogen at 600-1200 ℃, and then carrying out mixing treatment; (2) Adding PVB, dibutyl phthalate, absolute ethyl alcohol and other binder solutions into molybdenum and molybdenum alloy powder, and performing ball milling and mixing; (3) Casting the molybdenum and molybdenum alloy blank to form the molybdenum and molybdenum alloy blank with the thickness of 0.2-3 mm, and then performing hydrogen degumming treatment at the temperature of 400-800 ℃; (4) Sintering in an intermediate frequency induction sintering furnace at 1600-2200 ℃ to obtain molybdenum and molybdenum alloy slabs; (5) multipass cold rolling deformation and intermediate annealing treatment; (6) And (3) carrying out hydrogen or vacuum stress relief annealing treatment at 800-1200 ℃. Obtaining the molybdenum or molybdenum alloy foil with the thickness of 0.01-0.1 mm, the thickness tolerance of 2-5 mu m, the room temperature tensile strength of 830-1200 MPa and the yield strength of 700-1000 MPa. The alloy foil prepared by the method has relatively low strength, insufficient strong plastic matching property, high content of interstitial impurity elements such as oxygen/nitrogen and the like, second-phase particles such as oxides or nitrides with larger sizes are easy to form in the material, layering cracking phenomenon is easy to occur along the second-phase particles, and fracture failure is easy to occur in the subsequent part processing process.
The Chinese patent publication No. CN 102041404A proposes a preparation method and application of a low-oxygen TZM alloy, which is prepared by mixing molybdenum powder with larger Fisher particle size with alloy additive elements, cold isostatic pressing, high-temperature hydrogen sintering, forging, and final stress relief annealing, and is mainly applied to an X-ray tube rotary anode target. The Chinese patent publication No. CN 110076212A proposes a preparation process of a large-size TZM alloy plate, wherein a TZM alloy plate blank is prepared by adopting powder metallurgy, a steel plate is welded and clad and rolled, and the fire is reduced to prepare the large-size TZM alloy plate with low impurity content and excellent performance; both patents are full-flow powder metallurgy preparation processes, and are not suitable for preparing ultra-low oxygen TZM alloy foil blanks. The Chinese patent publication No. CN 109848424A proposes a kind of grating pulse traveling wave tube molybdenum foil and its preparation method, utilize low K low W medium particle raw materials molybdenum powder, prepare through the refined molybdenum compact, compound sintering, then through the large deformation cogging of low temperature, low temperature cross rolling, later warm rolling, hydrogen annealing, cross cold rolling, finally vacuum stress relief annealing, prepare the high strength and toughness match, dimensional accuracy high, punching performance good molybdenum foil for grid; however, it does not relate to a molybdenum alloy system with higher deformation resistance. Chinese patent publication No. CN 103774020a discloses a method for preparing a molybdenum-rhenium alloy foil, in particular a process for preparing a foil with a thickness less than 0.1mm, using a powder metallurgy process to prepare a sintered compact, and sequentially performing hot rolling, warm rolling and cold rolling on the sintered compact to obtain a molybdenum-rhenium alloy foil with a required thickness; but it is a full flow powder metallurgy alloy billet preparation process and does not involve TZM alloy systems that predominate in second phase strengthening. Said invention does not provide comprehensive and clear performance requirements for TZM alloy foil material with high performance and its preparation method. Therefore, there is a need to develop a high-performance TZM alloy foil with high strength, high strength and toughness matching, high dimensional accuracy, and excellent high-temperature service stability, and a method for preparing the same.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a high-performance TZM alloy foil and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the first aspect of the invention provides a high-performance TZM alloy foil with the characteristics of high strength, high strength and toughness matching, high dimensional accuracy, excellent high-temperature service stability and the like, and the physical characteristics of the TZM alloy foil are as follows:
(1) TZM alloy foil with thickness of 0.005-0.15 mm and dimensional tolerance of + -2 μm;
(2) The tensile strength is more than or equal to 1400MPa, the yield strength is more than or equal to 1200MPa, and the elongation is more than or equal to 5%;
(3) The O content is less than or equal to 30ppm, and the N content is less than or equal to 20ppm;
(4) The microstructure features include: the grains are in a mutually overlapped and staggered layered fiber structure, the fiber width-to-length ratio is 1% -20%, and the volume fraction of the micro-scale and nano-scale second phases which are finely and uniformly dispersed is 0.1% -2%.
In the invention, tensile strength, yield strength, elongation, microstructure, chemical composition (oxygen nitrogen carbon titanium zirconium and the like), dimensional tolerance and the like can be characterized by adopting means and tools such as room temperature stretching, an optical microscope, a Field Emission Scanning Electron Microscope (FESEM), a Transmission Electron Microscope (TEM), an oxygen nitrogen hydrogen tester, a carbon sulfur tester, an inductively coupled plasma emission spectrum (ICP-AES), a high-precision digital display micrometer and the like.
In a second aspect, the present invention provides a method for preparing the TZM alloy foil according to the first aspect of the present invention, including the following steps:
(1) Purifying raw materials: hydrogen or high vacuum degassing and purifying of high-purity molybdenum powder raw materials;
(2) Ball milling and mixing: mixing the high-purity purified molybdenum powder with micron-sized high-purity titanium hydride (or titanium carbide), zirconium hydride (or zirconium carbide) and graphite powder by high-uniformity ball milling;
(3) Preparing a pressed blank: cold isostatic pressing of alloy powder, grinding and shaping of pressed billets to obtain refined pressed billets;
(4) And (3) composite sintering: carrying out low-temperature hydrogen presintering and high-temperature vacuum sintering on the alloy pressed compact subjected to cold isostatic pressing;
(5) Vacuum smelting: taking the alloy sintered blank with regular processing as a consumable electrode to carry out vacuum arc melting;
(6) Extrusion cogging: heating under the protection of hydrogen atmosphere, and extruding and cogging with larger deformation of the smelting alloy billet;
(7) Cross hot rolling: heating under the protection of hydrogen atmosphere, stretching the extruded slab along the width direction, and then carrying out cross hot rolling along the length direction;
(8) Cross warm rolling: heating the alloy hot rolled plate under the protection of hydrogen atmosphere, and then performing cross warm rolling;
(9) Hydrogen annealing: carrying out stress relief annealing on the alloy plate subjected to warm rolling under the protection of hydrogen atmosphere;
(10) Cross cold rolling: the first-pass cold rolling of the alloy sheet is carried out along the width direction, namely, the first-pass cold rolling is carried out, then the multi-pass cold rolling is carried out, and the stress relief annealing is carried out between passes until the alloy sheet with the thickness of a finished product is obtained;
(11) Stress relief annealing: carrying out hydrogen or vacuum stress relief annealing treatment on the alloy foil to obtain a high-strength TZM alloy foil;
(12) Test characterization: and carrying out dimensional accuracy, room temperature stretching, softened room temperature stretching, microstructure, chemical components (oxygen nitrogen carbon titanium zirconium and the like), second phase components and dimensional tests on the high-strength TZM alloy foil.
In the preparation method of the invention, the purity is adopted: high-purity (more than or equal to 99.9 wt%) molybdenum powder with the Fisher particle size of 2-30 mu m, high-purity (more than or equal to 99.9 wt%) titanium hydride (or titanium carbide) and zirconium hydride (or zirconium carbide) powder with the Fisher particle size of 0.2-5 mu m and high-purity graphite powder with the Fisher particle size of 0.2-3 mu m (more than or equal to 99.95 wt%) with the O less than or equal to 500ppm are used as raw materials.
Preferably, the step (1) is adopted to carry out hydrogen or high vacuum heating degassing purification treatment on the high-purity molybdenum powder raw material, the dew point of the hydrogen is not higher than-40 ℃ or the vacuum degree is better than 8 multiplied by 10 -3 Pa, the temperature is 200-700 ℃, and the temperature is kept for 0.5-10 h.
Preferably, the high-purity molybdenum powder, titanium hydride (or titanium carbide) powder, zirconium hydride (or zirconium carbide) powder and graphite powder are mixed in the step (2), and high-purity low-abrasion wear-resistant grinding balls are adopted, wherein the weight ratio of the balls is (1-5): 1, ball milling is carried out for 1-10 hours, and the rotating speed is 100-500 r/min, so that the high-uniformity mixed powder is prepared.
Preferably, the mixed powder is subjected to cold isostatic pressing and shaping in the step (3), the pressure is 100-300 MPa, the pressing time is 1-30 min, the soft rubber mold is fixedly limited by a rigid sleeve, and the pressed compact is polished and shaped.
Preferably, in the step (4), the intermediate atmosphere of the low-temperature hydrogen pre-sintering and the high-temperature vacuum sintering is directly converted and completed in the same furnace; the low-temperature hydrogen presintering temperature is 1000-1500 ℃, and the sintering time is 1-8 hours; the high-temperature vacuum sintering temperature is 1800-2300 ℃, and the vacuum degree is 10 -2 ~10 -4 Pa, sintering time is 3-15 h.
Preferably, the steps of(5) The regular sintered alloy blank obtained in the last step is used as an electrode to be smelted in a vacuum consumable electrode arc furnace, the smelting current is 3-8 kA, the smelting voltage is 20-50V, and the vacuum degree is 1 multiplied by 10 4 ~1×10 -3 Pa, the steady arc magnetic field is 500-2000A/turn, and smelting is carried out for 1-3 times.
Preferably, in the step (6), the cogging temperature of the large deformation extrusion cogging is 1500-1800 ℃, the hydrogen atmosphere is heated, and the extrusion ratio is (2-5): 1.
Preferably, in the step (7), the relatively low-temperature cross-rolling is to heat the alloy blank to 1200-1400 ℃ under the protection of hydrogen atmosphere, broaden the width direction, namely, first cross-rolling, then rolling for 2-4 times along the original length direction of the alloy blank, wherein the total processing rate is 85-95%, and the roller is preheated to 300-500 ℃ during hot rolling.
Preferably, in the step (8), the warm rolling is performed at 700-1000 ℃, cutting is performed, reversing is performed once, and the rolling is performed for 3-5 times; heat preservation is carried out for 10-60 min at 800-1200 ℃ between fires; the total processing rate is 75-85%.
Preferably, in the step (9), the hydrogen annealing temperature is 800-1200 ℃ and the annealing time is 10-60 min.
Preferably, in the step (10), the cold rolling is performed at the room temperature of 100-300 ℃, cutting is performed, reversing is performed once, and the rolling is performed for 3-12 times; and (3) heat-preserving for 10-60 min at 700-1150 ℃ in a hot room or performing vacuum annealing, and processing to obtain the final finished product with the thickness of 0.005-0.15 mm.
Preferably, in the step (11), the alloy foil is subjected to stress relief annealing, the dew point of hydrogen is not higher than-40 ℃ or the vacuum degree is 10 -2 ~10 -4 Pa, the annealing temperature is 600-1000 ℃, the temperature field uniformity is +/-10 ℃, and the annealing time is 10-60 min.
Preferably, in the step (12), the test mode includes a tensile test, a microscopic structure, a chemical component (such as oxygen nitrogen carbon titanium zirconium), a sampling test for a destructive test of a second phase component and a dimension, or a full test for a nondestructive test of a dimension accuracy.
The preparation method of the invention is different from the conventional process in that the purity is adopted: molybdenum powder with O less than or equal to 500ppm (Fisher particle size of 2-30 mu m) is used as a raw material; for the conventional raw material molybdenum powder on the market, the content of oxygen impurity element is usually higher, the oxygen content is generally 1000-3000 ppm, and the high oxygen impurity content forms a large-size oxide second phase in the sintering process, is inherited along with the rolling process, and finally affects the tissue property of the TZM alloy foil product. Meanwhile, the size of the second phase formed can be reduced from the source by adopting titanium hydride (or titanium carbide), zirconium hydride (or zirconium carbide) and graphite powder with small Fisher particle size and high purity, the dispersion strengthening effect of the second phase is enhanced, and the subsequent processability and the final finished product performance are improved.
In the preparation method, the method is different from the conventional process in that the step (1) is adopted to carry out hydrogen or high vacuum degassing purification on the molybdenum powder raw material. As a metal having ductile-brittle transition characteristics, reducing the content of impurity elements, particularly oxygen/nitrogen content, is an effective way to improve the brittleness of the TZM slab in a sintered state, i.e., to improve workability. The low-temperature degassing and purifying are carried out under the condition of hydrogen or high vacuum, so that the impurity element content of the molybdenum powder is reduced, and the sintering and processing performances can be improved.
The preparation method of the invention is different from the conventional process in that the cold isostatic pressing alloy billet is subjected to compound sintering in the step (2). Presintering at low temperature in hydrogen atmosphere, and reducing the oxide film on the surface of the molybdenum powder particles in the pressed compact in reducing atmosphere to effectively reduce the oxygen content from hundreds of ppm to less than or equal to hundreds of ppm; at 10 -2 ~10 -4 The high-temperature sintering under Pa high vacuum can deeply deoxidize/nitrogen, the quantity of second phases of oxide and nitride can be obviously reduced, and the subsequent processing performance is improved; meanwhile, a plurality of impurities with saturated vapor pressure higher than the residual pressure in the vacuum furnace can be volatilized and discharged from the sintered compact rapidly, and the high vacuum plays a role in purifying the alloy sintered compact; finally, TZM alloy slab with low impurity content is obtained. The low-temperature hydrogen pre-sintering and the high-temperature high-vacuum sintering in the composite sintering step can be completed in one furnace, and the composite sintering method has the advantages of two sintering modes, and is high in efficiency, energy-saving and consumption-reducing.
In the preparation method of the invention, the preparation method is different from the conventional process in that the step (5) is adopted to take the regular alloy sintered rod blank as an electrode for vacuum consumable arc melting. On one hand, the oxygen/nitrogen content in the material can be effectively reduced by smelting, and the second phases of the oxide and the nitride with large size are greatly reduced; on the other hand, the method can realize higher reaction temperature, accelerate the solid solution of alloy elements into a matrix, then separate out uniform and fine dispersed carbide second phases through the cooling process, fully exert the solid solution strengthening and the precipitation strengthening effects of the second phases, and remarkably improve the subsequent processing performance and the yield.
In the preparation method, the method is different from the conventional process in that the step (6) is adopted to carry out large-deformation extrusion cogging on the regular smelting alloy ingot, compared with hot rolling cogging, extrusion has stronger three-way compressive stress, the potential plasticity of TZM alloy is fully exerted, the processability of subsequent rolling is improved, and meanwhile, extrusion has higher cogging efficiency and large-grain ingot cogging yield.
The TZM alloy foil prepared by the method has the advantages of high strength, high toughness, low oxygen/nitrogen content, uniform and fine dispersion of the second phase, high dimensional accuracy, stable high-temperature performance and the like due to the adoption of the process treatment. Meanwhile, the TZM alloy foil preparation method disclosed by the invention is high in process controllability, good in product consistency and easy to realize large-scale production.
In a third aspect, the invention provides a TZM alloy foil prepared by the preparation method in the second aspect, and the TZM alloy foil is applied to the fields of electric vacuum, electronics and medical treatment, such as a grid of a traveling wave tube grid-controlled electron gun and an action part of a detector.
The invention is further illustrated by the following figures and detailed description.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a 500-fold photograph of the rolled surface metallographic structure of the TZM alloy foil in example 1.
FIG. 3 is a schematic diagram of statistical analysis of a significant amount of second phases dispersed within the TZM alloy foil material of example 1.
FIG. 4 is a photograph of 500 times the metallographic structure of the rolled section of the TZM alloy foil in example 1.
Fig. 5 is a photograph of 500 times of a transverse cross-sectional metallographic structure of the TZM alloy foil in example 1.
FIG. 6 is a transmission electron micrograph of a nanoscale carbide second phase of the TZM alloy foil of example 1.
FIG. 7 is a transmission electron diffraction speckle photograph and composition analysis of the nanoscale carbide second phase of the TZM alloy foil of example 1.
Detailed Description
Embodiments of the present invention are described in detail below.
The TZM alloy foil preparation process flow is shown in a figure 1, and comprises the following steps: 1. purifying molybdenum powder raw materials; 2. high-uniformity ball milling and mixing of alloy powder; 3. preparing a refined alloy pressed compact; 4. composite sintering; 5. vacuum arc melting; 6. extruding and cogging with large deformation; 7. cross hot rolling; 8, cross warm rolling; 9. annealing by hydrogen; 10. cross cold rolling; 11. stress relief annealing; 12. cutting and checking; finally, the high-performance TZM alloy foil with high strength, high toughness matching, low oxygen/nitrogen content, uniform and fine dispersion of the second phase, high dimensional accuracy and stable high-temperature performance is obtained.
The TZM alloy foil prepared by the preparation method of the invention takes molybdenum powder (99.9 wt%) with the purity of O less than or equal to 500ppm and the average Fisher particle size of 2-30 mu m, titanium hydride or titanium carbide powder with the average Fisher particle size of 0.2-5 mu m, zirconium hydride or zirconium carbide powder (the purity of not less than 99.9 wt%) and graphite powder with the average Fisher particle size of 0.2-3 mu m (the purity of not less than 99.95 wt%) as raw materials, and the preparation method comprises the specific steps of purifying the raw materials of the molybdenum powder, mixing the alloy powder by high uniform ball milling, preparing a refined alloy compact, composite sintering, vacuum arc melting, extrusion cogging with large deformation, cross hot rolling, hydrogen annealing, cross cold rolling, stress relief annealing and cutting inspection:
(1) Purifying raw materials: the high-purity molybdenum powder raw material is subjected to hydrogen or high-vacuum heating degassing purification treatment, the dew point of the hydrogen is not higher than-40 ℃ or the vacuum degree is better than 8 multiplied by 10 -3 Pa, the temperature is 200-700 ℃, and the temperature is kept for 0.5-10 h;
(2) Ball milling and mixing: ball milling and mixing the purified high-purity molybdenum powder, high-purity titanium hydride, zirconium hydride and graphite powder, and adopting a high-purity low-abrasion wear-resistant grinding ball with a ball-material ratio of (1-5): 1, performing ball milling for 1-10 hours, and preparing high-uniformity mixed alloy powder at a rotating speed of 100-500 r/min;
(3) Preparing a refined alloy pressed compact: the cold isostatic pressing pressure of the alloy powder is 100-300 MPa, and the pressing time is 1-30 min; the soft rubber mold is fixed and limited by a rigid sleeve, and a pressed blank is polished and shaped;
(4) And (3) composite sintering: intermediate atmosphere of low-temperature hydrogen pre-sintering and high-temperature vacuum sintering is directly converted and completed in the same furnace; the low-temperature hydrogen pre-sintering temperature is 1000-1500 ℃, and the sintering time is 1-8 hours; the high-temperature vacuum sintering temperature is 1800-2300 ℃, and the vacuum degree is 10 -2 ~10 -4 Pa, sintering time is 3-15 h;
(5) Vacuum smelting: smelting the obtained regular sintered alloy blank in a vacuum consumable arc furnace as a consumable electrode, wherein the smelting current is 3-8 kA, the smelting voltage is 20-50V, and the vacuum degree is 1 multiplied by 10 4 ~1×10 -3 Pa, an arc stabilizing magnetic field of 500-2000A/turn, smelting for 1-3 times;
(6) Large deformation extrusion cogging: the cogging temperature is 1500-1800 ℃, the hydrogen atmosphere is heated, and the cogging extrusion ratio is (2-5): 1.
(7) Cross hot rolling: heating the alloy blank to 1200-1400 ℃ under the protection of hydrogen, performing width-direction widening, namely first cross rolling, and then rolling for 2-4 times along the original length direction of the alloy blank, wherein the total processing rate is 85-95%, and the roller is preheated to 300-500 ℃ during hot rolling;
(8) Cross warm rolling: cutting and reversing once at the warm rolling temperature of 700-1000 ℃ and rolling for 3-5 times; heat preservation is carried out for 10-60 min at 800-1200 ℃ between fires, and the total processing rate is 75-85%;
(9) Hydrogen annealing: the hydrogen annealing temperature is 800-1200 ℃, and the annealing time is 10-60 min;
(10) Cross cold rolling: the heating temperature of the cross cold-rolled alloy sheet is 100-300 ℃, 3-12 times are included, heat preservation is carried out for 10-60 min at 700-1150 ℃ between the times, hydrogen or vacuum annealing is carried out, and multi-roll precision cold rolling is utilized to reach the final thickness of a finished product of 0.005-0.15 mm;
(11) Stress relief annealing: the stress relief annealing is performed after each heat of cold rolling process, the dew point of hydrogen is not higher than-40 ℃ or the vacuum degree is 10 -2 ~10 -4 Pa, the annealing temperature is 600-1000 ℃, the temperature field uniformity is within +/-10 ℃, and the annealing time is 10-60 min;
(12) Test characterization: the test mode comprises tensile test, microscopic structure, chemical composition (oxygen nitrogen carbon titanium zirconium and the like), second phase composition, size and other destructive test sampling test or size precision and other nondestructive test full test.
Example 1
The low O content (480 ppm) molybdenum powder with the Fisher size of 5 μm is subjected to hydrogen heating, degassing and purifying, the dew point of the hydrogen is minus 40 ℃, the temperature is 600 ℃, and the temperature is kept for 4 hours. The purified molybdenum powder, titanium hydride, zirconium hydride and graphite powder with the Fisher particle size of 0.5 mu m are subjected to ball milling and mixing, yttrium stabilized zirconia grinding balls with the sphere material ratio of phi 3mm of 3:1 are placed in a ball mill for ball milling for effective time of 4 hours, and the rotating speed is 300r/min, so that the high-uniformity mixed alloy powder is prepared. The alloy powder is evenly put into a soft rubber mold which is fixed and limited by a rigid sleeve, and is subjected to cold isostatic pressing for 15min under 200 MPa; grinding and shaping the pressed compact, presintering for 4 hours at 1300 ℃ under the hydrogen atmosphere, and then directly converting the hydrogen atmosphere into 10 -3 Sintering at high temperature of 2100 ℃ in a vacuum environment of Pa for 6 hours to obtain a low-impurity refined sintered alloy rod blank with uniform density; processing the regular sintered rod blank into an electrode, and carrying out vacuum consumable arc melting with a melting current of 5kA, a melting voltage of 35V and a vacuum degree of 1 multiplied by 10 -2 Pa, the steady arc magnetic field is 1500A/turn, smelting for 2 times; carrying out large-deformation extrusion cogging on the regular alloy smelting ingot at 1600 ℃, wherein the extrusion ratio is 3:1; the TZM alloy plate blank which is bloomed in the stretching direction is heated to 1300 ℃ under the protection of hydrogen, the first cross rolling is carried out along the original length direction of the alloy plate blank, then 3 times of rolling are carried out along the original length direction of the alloy plate blank, the total processing rate is 92 percent, and the roller is preheated to 400 ℃ during the hot rolling; after the hot rolled alloy blank is subjected to surface alkaline washing, hot water washing, defect grinding and shearing, heating to 800 ℃ under the protection of hydrogen, cutting, reversing once, and rolling for 4 times; heat-insulating for 30min at 900 deg.C and hydrogen annealing, and its total processing rate82%; annealing the alloy plate blank after warm rolling under the protection of hydrogen at the annealing temperature of 1000 ℃ for 30min; heating the alloy sheet to 250 ℃, rolling for 6 times, annealing in hydrogen atmosphere between the times, and preserving heat for 30min at the annealing temperature of 800 ℃ to obtain a foil with the thickness of 0.08 mm; vacuum stress relief annealing of alloy foil to vacuum degree of 10 -2 Pa, annealing temperature of 800 ℃, uniformity of temperature field within +/-10 ℃ and annealing time of 30min. And then cutting the alloy foil to the required size and inspecting the quality to finally obtain the high-performance TZM alloy foil material with the thickness of 0.08mm, the dimensional deviation of +/-2 mu m, the O content of 26ppm, the tensile strength of 1547MPa at room temperature, the yield strength of 1463MPa and the elongation of 7.5%.
The metallographic structure photographs of the alloy foil rolled surface, the rolled cross section and the transverse cross section in three dimensions are shown in figures 2-5. It can be seen that the microstructure of the rolling plane (figure 2) is mainly elongated strip grains, fine equiaxed grains are auxiliary grains and are uniformly interwoven with the elongated strip grains, wherein a considerable amount of second phases are dispersed in the material, and the sizes of the second phases are distributed at 1 mu m or less through statistical analysis (figure 3); the microstructure of the rolled section (figure 4) presents a distinct and slender lamellar fiber structure, and the aspect ratio of single-layer fibers is very large; the microstructure of the vertical rolled section (fig. 5) is different from the rolled direction, and although the microstructure is a relatively obvious layered structure, the aspect ratio of grains in a single layer is obviously reduced, and the grains are mutually overlapped and staggered. And (3) synthesizing a metallographic structure with three dimensions, judging that the crystal grains of the alloy foil are in a layered fiber structure which is overlapped and staggered with each other, taking the slender fibrous crystal grains as the main material and the tiny equiaxed crystal grains as the auxiliary material and uniformly interweaving the two, and dispersing a considerable amount of second phases with the size of about 1 mu m in the material. Meanwhile, the second phases of the nano-scale zirconium carbide and the titanium carbide with the size of 50-100 nm are found in the material through analysis of a transmission electron microscope (figures 6 and 7).
Example 2
The low O content (380 ppm) molybdenum powder with the Fisher particle size of 30 μm is subjected to hydrogen heating, degassing and purifying, the dew point of the hydrogen is minus 40 ℃, the temperature is 700 ℃, and the heat preservation is carried out for 0.5h. Ball-milling and mixing the purified molybdenum powder with titanium hydride, zirconium hydride and graphite powder with the Fisher particle size of 30 mu m, and collectingThe yttrium stabilized zirconia grinding balls with the diameter of 3mm are placed in a ball mill for ball milling for an effective time of 10 hours at a speed of 100r/min, and the high-uniformity mixed alloy powder is prepared. The alloy powder is evenly put into a soft rubber mold which is fixed and limited by a rigid sleeve, and is subjected to cold isostatic pressing for 1min under 300 MPa; grinding and shaping the pressed compact, presintering for 1h at 1500 ℃ under hydrogen atmosphere, and then directly converting the hydrogen atmosphere into 10 -3 Sintering the alloy rod blank for 15 hours at a high temperature of 2300 ℃ in a vacuum environment of Pa to obtain a low-impurity refined sintered alloy rod blank with uniform density; processing the regular sintered rod blank into an electrode, and carrying out vacuum consumable arc melting with a melting current of 8kA, a melting voltage of 50V and a vacuum degree of 1 multiplied by 10 -3 Pa, stabilizing arc magnetic field 2000A/turn, smelting 1 time; carrying out large-deformation extrusion cogging on the regular alloy smelting ingot at 1800 ℃, wherein the extrusion ratio is 2:1; the TZM alloy plate blank which is bloomed in the stretching direction is heated to 1200 ℃ under the protection of hydrogen, the first cross rolling is carried out along the original length direction of the alloy plate blank, then the alloy plate blank is rolled for 2 times along the original length direction of the alloy plate blank, the total processing rate is 85 percent, and the roller is preheated to 300 ℃ during the hot rolling; after the hot rolled alloy blank is subjected to surface alkaline washing, hot water washing, defect grinding and shearing, heating to 700 ℃ under the protection of hydrogen, cutting, reversing once, and rolling for 3 times; heat preservation is carried out for 10min under 1200 ℃ between the heat and the heat, and the total processing rate is 75%; annealing the alloy plate blank after warm rolling under the protection of hydrogen, wherein the annealing temperature is 800 ℃ and the annealing time is 60min; heating the alloy sheet to 100 ℃, rolling for 3 times, annealing in hydrogen atmosphere between the times, and preserving heat for 10min at the annealing temperature of 1150 ℃ to obtain a foil with the thickness of 0.15 mm; vacuum stress relief annealing of alloy foil to vacuum degree of 10 -3 Pa, annealing temperature 1000 ℃, temperature field uniformity within +/-10 ℃ and annealing time of 10min. Then cutting the alloy foil to the required size and inspecting the quality to finally obtain the high-performance TZM alloy foil material with the thickness of 0.15mm, the dimensional deviation of +/-2 mu m and the O content of 28ppm, wherein the tensile strength of the alloy foil material in the rolling direction at room temperature is 1297MPa, the yield strength of the alloy foil material is 1229MPa, and the elongation of the alloy foil material is 10.5%.
Example 3
The low O content (500 ppm) molybdenum powder with the Fisher size of 2 μm is subjected to hydrogen heating, degassing and purifying, the dew point of the hydrogen is minus 40 ℃, the temperature is 200 ℃,preserving heat for 10h. The purified molybdenum powder, titanium carbide with the Fisher particle size of 0.2 mu m, zirconium hydride and graphite powder are subjected to ball milling and mixing, yttrium stabilized zirconia grinding balls with the sphere material ratio of phi 3mm is adopted to be 1:1, and the mixture is placed in a ball mill for ball milling for effective time of 1h, and the rotating speed is 500r/min, so that the high-uniformity mixed alloy powder is prepared. The alloy powder is evenly put into a soft rubber mold which is fixed and limited by a rigid sleeve, and is subjected to cold isostatic pressing for 30min under 100 MPa; grinding and shaping the pressed compact, presintering for 8 hours at 1000 ℃ under hydrogen atmosphere, and then directly converting the hydrogen atmosphere into 10 -3 Sintering at a high temperature of 1800 ℃ for 3 hours in a vacuum environment of Pa to obtain a low-impurity refined sintered alloy rod blank with uniform density; processing the regular sintered rod blank into an electrode, and carrying out vacuum consumable arc melting with a melting current of 3kA, a melting voltage of 20V and a vacuum degree of 1 multiplied by 10 4 Pa, stabilizing arc magnetic field 500A/turn, smelting 3 times; carrying out large-deformation extrusion cogging on the regular alloy smelting ingot at 1800 ℃, wherein the extrusion ratio is 5:1; the TZM alloy plate blank which is bloomed in the stretching direction is heated to 1400 ℃ under the protection of hydrogen, the first cross rolling is carried out along the original length direction of the alloy plate blank, then the alloy plate blank is rolled for 4 times along the original length direction of the alloy plate blank, the total processing rate is 95 percent, and the roller is preheated to 500 ℃ during the hot rolling; after the hot rolled alloy blank is subjected to surface alkaline washing, hot water washing, defect grinding and shearing, heating to 1000 ℃ under the protection of hydrogen, cutting, reversing once, and rolling for 5 times; heat preservation is carried out for 60min at 800 ℃ between the fires, and the total processing rate is 85%; annealing the alloy plate blank after warm rolling under the protection of hydrogen, wherein the annealing temperature is 1200 ℃ and the annealing time is 10min; heating the alloy sheet to 300 ℃, rolling for 12 times, annealing in hydrogen atmosphere between the times, and preserving heat for 60min at the annealing temperature of 700 ℃ to obtain a foil with the thickness of 0.005 mm; vacuum stress relief annealing of alloy foil to vacuum degree of 10 -2 Pa, the annealing temperature is 600 ℃, the temperature field uniformity is within +/-10 ℃, and the annealing time is 60min. And then cutting the alloy foil to the required size and inspecting the quality to finally obtain the high-performance TZM alloy foil material with the thickness of 0.005mm, the dimensional deviation of +/-2 mu m and the O content of 25ppm, wherein the tensile strength of the alloy foil material is 1987MPa towards room temperature, the yield strength of 1909MPa and the elongation of 5.4 percent.
Example 4
For Fisher's particleMolybdenum powder with low O content (470 ppm) and 8 μm is subjected to hydrogen heating, degassing and purifying, the dew point of hydrogen is minus 40 ℃, the temperature is 400 ℃, and the temperature is kept for 8 hours. The purified molybdenum powder, titanium hydride with the Fisher particle size of 1 mu m, zirconium carbide and graphite powder are subjected to ball milling and mixing, yttrium stabilized zirconia grinding balls with the sphere material ratio of phi 3mm are adopted, the balls are placed in a ball mill for ball milling for an effective time of 6 hours, and the rotating speed is 200r/min, so that the high-uniformity mixed alloy powder is prepared. The alloy powder is evenly put into a soft rubber mold which is fixed and limited by a rigid sleeve, and is subjected to cold isostatic pressing for 20min under 150 MPa; grinding and shaping the pressed compact, presintering for 5h at 1200 ℃ under hydrogen atmosphere, and then directly converting the hydrogen atmosphere into 10 -3 Sintering the alloy rod blank in a vacuum environment of Pa at a high temperature of 2200 ℃ for 5 hours to obtain a low-impurity refined sintered alloy rod blank with uniform density; processing the regular sintered rod blank into an electrode, and carrying out vacuum consumable arc melting with a melting current of 5kA, a melting voltage of 30V and a vacuum degree of 1 multiplied by 10 -3 Pa, stabilizing arc magnetic field 1000A/turn, smelting 2 times; large deformation extrusion cogging is carried out on the regular alloy smelting ingot at 1700 ℃, and the extrusion ratio is 4:1; the TZM alloy plate blank which is bloomed in the stretching direction is heated to 1350 ℃ under the protection of hydrogen, the first cross rolling is carried out along the original length direction of the alloy plate blank, then 3 times of rolling are carried out along the original length direction of the alloy plate blank, the total processing rate is 92 percent, and the roller is preheated to 400 ℃ during the hot rolling; after the hot rolled alloy blank is subjected to surface alkaline washing, hot water washing, defect grinding and shearing, heating to 900 ℃ under the protection of hydrogen, cutting, reversing once, and rolling for 5 times; heat preservation is carried out for 20min at 1100 ℃ between the fires, and the total processing rate is 85%; annealing the alloy plate blank after warm rolling under the protection of hydrogen at the annealing temperature of 1000 ℃ for 10min; heating the alloy sheet to 250 ℃, rolling for 10 times, annealing in hydrogen atmosphere between the times, and preserving heat for 20min at the annealing temperature of 800 ℃ to obtain a foil with the thickness of 0.01 mm; vacuum stress relief annealing of alloy foil to vacuum degree of 10 -2 Pa, annealing temperature 700 ℃, temperature field uniformity within +/-10 ℃ and annealing time 40min. Cutting the alloy foil to the required size and inspecting the quality to finally obtain the high-performance TZM alloy with the thickness of 0.01mm, the dimensional deviation of +/-2 mu m, the O content of 25ppm, the tensile strength of 1867MPa to room temperature, the yield strength of 1789MPa and the elongation of 6.2 percentGold foil material.
Comparative example 1
The conventional commercial molybdenum powder with the Fisher particle size of 35 mu m, the commercial titanium hydride, zirconium hydride and graphite powder with the particle size of 10 mu m are subjected to ball milling and mixing, the ball-to-material ratio is 1:1, and the ball milling is carried out for 2 hours, wherein the rotating speed is 300r/min. Filling the alloy powder into a soft rubber mold, and performing cold isostatic pressing for 10min under 200 MPa; sintering for 6 hours at a high temperature of 1900 ℃ in a hydrogen atmosphere to obtain a sintered alloy plate blank; example 2 was repeated except that the molybdenum powder, titanium hydride, zirconium hydride, and graphite powder raw materials, alloy billets, cold isostatic pressing, sintering process, and vacuum consumable arc melting process used were different from example 2. Finally, TZM alloy foil material with thickness of 0.15mm, dimensional deviation of +/-8 mu m, O content of 330ppm, room temperature tensile strength of 975MPa, yield strength of 903MPa and elongation of 1.8% is obtained. The processing process is easy to crack and delaminate, and the yield is obviously lower than that of the embodiment 2.
As can be seen from the results of the above examples and comparative examples, the TZM alloy foil prepared by the invention has the advantages of high strength, high toughness, low oxygen/nitrogen content, uniform and fine dispersion of the second phase, high dimensional accuracy, stable high-temperature performance and the like. Meanwhile, the TZM alloy foil preparation method disclosed by the invention is high in process controllability, good in product consistency and easy to realize large-scale production.
Claims (10)
1. A TZM alloy foil with high performance is characterized in that: the thickness of the TZM alloy foil is 0.005-0.15 mm, and the dimensional tolerance is +/-2 mu m; the tensile strength is more than or equal to 1400MPa, the yield strength is more than or equal to 1200MPa, and the elongation is more than or equal to 5%; the oxygen content is less than or equal to 30ppm, the N content is less than or equal to 20ppm, and the microstructure characteristics comprise a lamellar fiber structure with long and thin grains in mutually overlapped and staggered mode, the fiber width-to-length ratio is 1% -20%, and the volume fraction of micro-scale and nano-scale second phases which are finely and uniformly dispersed is 0.1% -2%.
2. A method for preparing the high-performance TZM alloy foil of claim 1, characterized by: the method comprises the following steps:
(1) Purifying raw materials: hydrogen or high vacuum degassing and purifying of high-purity molybdenum powder raw materials;
(2) Ball milling and mixing: the purified high-purity molybdenum powder is mixed with micron-grade high-purity titanium hydride, zirconium hydride and graphite powder by high-uniformity ball milling;
(3) Preparing a refined alloy pressed compact: cold isostatic pressing of alloy powder, grinding and shaping of pressed billets to obtain refined pressed billets;
(4) And (3) composite sintering: carrying out low-temperature hydrogen presintering and high-temperature vacuum sintering on the alloy pressed compact subjected to cold isostatic pressing;
(5) Vacuum smelting: taking the alloy sintered blank as an electrode to perform vacuum consumable arc melting;
(6) Large deformation extrusion cogging: heating under the protection of hydrogen atmosphere, and extruding and cogging the alloy billet with larger deformation;
(7) Cross hot rolling: heating under the protection of hydrogen atmosphere, stretching and cogging along the width direction, and then carrying out cross rolling along the length direction;
(8) Cross warm rolling: heating the alloy plate blank under the protection of hydrogen, and then performing cross warm rolling;
(9) Hydrogen annealing: heating the alloy plate blank subjected to warm rolling under the protection of hydrogen to anneal;
(10) Cross cold rolling: heating the alloy sheet and then performing cross cold rolling to obtain an alloy foil with the required thickness;
(11) Stress relief annealing: carrying out stress relief annealing treatment on the alloy foil to obtain a high-performance TZM alloy foil;
(12) Test characterization: and carrying out tensile test, microstructure, chemical components (oxygen nitrogen carbon titanium zirconium and the like), second phase components, size and other destructive detection sampling inspection or size precision and other nondestructive detection full inspection on the high-performance TZM alloy foil.
3. The method for preparing the TZM alloy foil according to claim 2, characterized in that: the method is characterized in that O is less than or equal to 500ppm, the purity of high-purity 99.9wt% molybdenum powder with the Fisher particle size of 2-30 mu m, the purity of high-purity titanium hydride or titanium carbide with the Fisher particle size of 0.2-5 mu m, the purity of zirconium hydride or zirconium carbide powder is not less than 99.9wt%, and the purity of graphite powder with the Fisher particle size of 0.2-3 mu m is not less than 99.95wt% are adopted as raw materials.
4. The method for preparing the TZM alloy foil according to claim 2, characterized in that: in the step (1), the high-purity molybdenum powder raw material is subjected to hydrogen or high-vacuum heating degassing purification treatment, the dew point of the hydrogen is not higher than-40 ℃ or the vacuum degree is better than 8 multiplied by 10 - 3 Pa, the temperature is 200-700 ℃, and the temperature is kept for 0.5-10 h.
5. The method for preparing the TZM alloy foil according to claim 2, characterized in that: and (2) mixing the purified high-purity molybdenum powder with high-purity titanium hydride or titanium carbide powder, zirconium hydride or zirconium carbide powder and graphite powder, and adopting a high-purity low-abrasion wear-resistant grinding ball with a ball-material ratio of (1-5): 1, and performing ball milling for an effective time of 1-10 hours at a rotating speed of 100-500 r/min to prepare the high-uniformity mixed alloy powder.
6. The method for preparing the TZM alloy foil according to claim 2, characterized in that: the cold isostatic pressing pressure of the alloy powder in the step (3) is 100-300 MPa, and the pressing time is 1-30 min; the soft rubber mold is fixed and limited by a rigid sleeve.
7. The method for preparing the TZM alloy foil according to claim 2, characterized in that: the intermediate atmosphere of the low-temperature hydrogen pre-sintering and the high-temperature vacuum sintering in the step (4) is directly converted and completed in the same furnace time; the low-temperature hydrogen pre-sintering temperature is 1000-1500 ℃, and the sintering time is 1-8 hours; the high-temperature vacuum sintering temperature is 1800-2300 ℃, and the vacuum degree is 10 -2 ~10 -4 Pa, sintering time is 3-15 h.
8. The method for preparing the TZM alloy foil according to claim 2, characterized in that: smelting the sintered alloy blank obtained in the last step in a vacuum consumable arc furnace as a consumable electrode, wherein the smelting current is 3-8 kA, the smelting voltage is 20-50V, and the vacuum degree is 1 multiplied by 10 4 ~1×10 -3 Pa, the steady arc magnetic field is 500-2000A/turn, and smelting is carried out for 1-3 times.
9. The method for preparing the TZM alloy foil according to claim 2, characterized in that:
the cogging temperature of the large deformation extrusion cogging in the step (6) is 1500-1800 ℃, the cogging extrusion is (2-5) 1;
the cross rolling in the step (7) is to heat the alloy blank to 1200-1400 ℃ under the protection of hydrogen, expand in the width direction, namely, the first cross rolling is performed, then the alloy blank is rolled for 2-4 times along the original length direction of the alloy blank, the total processing rate is 85-95%, and the roller is preheated to 300-500 ℃ during the hot rolling;
the warm rolling temperature in the step (8) is 700-1000 ℃, cutting is carried out, reversing is carried out for one time, and rolling is carried out for 3-5 times; heat is preserved for 10-60 min at 800-1200 ℃ between the times of heating, and the total processing rate is about 75-85%;
in the step (9), the hydrogen annealing temperature is 800-1200 ℃ and the annealing time is 10-60 min;
in the step (10), the heating temperature of the cross cold-rolled alloy sheet is 100-300 ℃, 3-12 times of fire are included, heat preservation is carried out for 10-60 min at 700-1150 ℃ between the fires, hydrogen or vacuum annealing is carried out, and multi-roller precision cold rolling is utilized to reach the final thickness of a finished product of 0.005-0.15 mm;
the TZM alloy foil stress relief annealing in the step (11) is carried out after each fire of the cold rolling process, and the dew point of hydrogen is not higher than-40 ℃ or the vacuum degree is 10 -2 ~10 -4 Pa, the annealing temperature is 600-1000 ℃, the temperature field uniformity is within +/-10 ℃, and the annealing time is 10-60 min;
the inspection mode in the step (12) comprises tensile test, microstructure, chemical component oxygen nitrogen carbon titanium zirconium, second phase component and size and other destructive inspection sampling inspection or size precision and other nondestructive inspection full inspection.
10. A TZM alloy foil prepared by a preparation method according to any one of claims 2-9, characterized in that: the method is applied to the fields of electric vacuum, electronics and medical treatment.
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