CN114769593A - Method for preparing molybdenum and molybdenum alloy foil - Google Patents
Method for preparing molybdenum and molybdenum alloy foil Download PDFInfo
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- CN114769593A CN114769593A CN202210637918.1A CN202210637918A CN114769593A CN 114769593 A CN114769593 A CN 114769593A CN 202210637918 A CN202210637918 A CN 202210637918A CN 114769593 A CN114769593 A CN 114769593A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
Abstract
The invention provides a method for preparing molybdenum and molybdenum alloy foils, which comprises the following steps: taking pure molybdenum powder or molybdenum alloy powder as a raw material, adding a binder solution into the raw material, and performing ball milling treatment to obtain slurry; carrying out tape casting on the slurry to obtain tape casting blanks, and then sequentially carrying out degumming treatment, sintering treatment, rolling treatment and annealing treatment to obtain molybdenum or molybdenum alloy foils; wherein the rolling treatment comprises multi-pass cold rolling deformation and intermediate annealing treatment, and the total rolling deformation is 40-99%. The molybdenum and molybdenum alloy foil prepared by the invention can meet the use requirements of application fields of consumer electronic devices, vacuum devices, catalytic materials and the like, the thickness of the foil is 0.01-0.1mm, the thickness tolerance is 2-5 mu m, and the flatness is less than or equal to 0.1 mm; the tensile strength at room temperature is 830-1200MPa, the yield strength is 700-1000MPa, and the elongation is 5-15%.
Description
Technical Field
The invention belongs to the technical field of refractory metals, and particularly relates to a method for preparing molybdenum and molybdenum alloy foils.
Background
The molybdenum and molybdenum alloy foil strips have good mechanical and thermal properties, so that the molybdenum and molybdenum alloy foil strips are widely applied to the fields of consumer electronics industry, grid mesh, cathodes, shielding cylinders and other electro-vacuum parts for grid-controlled pulse traveling wave tubes, electro-optical sources, medical industry and the like.
At present, the main suppliers at home and abroad adopt powder pressing process, sintering process, hot rolling process, cold rolling process, heat treatment, precision machining and the like to prepare pure molybdenum and molybdenum alloy strips and foils. Such as: the invention patent 2018114659385 discloses a molybdenum foil preparation method, which comprises the steps of using low-K low-W medium-particle-size molybdenum powder as a raw material, carrying out cold isostatic pressing to obtain a molybdenum pressed blank, carrying out composite sintering, low-temperature large-deformation cogging, low-temperature cross hot rolling, alkaline washing, grinding and shearing, carrying out warm rolling, hydrogen annealing, surface cleaning and shearing, cross cold rolling, surface oil removal, finally carrying out vacuum stress relief annealing, cutting, checking and preparing to obtain the molybdenum foil; the preparation method has long process, needs a plurality of intermediate control programs and leads to high cost.
The invention patent 2017104488427 discloses a method for preparing an extremely thin metal molybdenum foil, which comprises the steps of stacking a pure tungsten foil/a pure molybdenum foil/a pure tungsten foil, then placing the stacked materials into a heating furnace for heating, then carrying out cold rolling, then placing the rolled materials into the heating furnace for heating, then carrying out cold rolling, and repeating the heating and the cold rolling until the extremely thin molybdenum foil is obtained; according to the preparation method, the foil with thinner thickness is prepared by using pure molybdenum foil for stack rolling, but the controllability of the stack rolling process is poor, multiple times of heating and cold rolling are required, and the efficiency is not high.
The invention patent 2009100240004 discloses a processing method of molybdenum and molybdenum alloy narrow bands, firstly rolling molybdenum or molybdenum alloy wire materials by a rolling mill to obtain rolled narrow bands, and then drawing the rolled narrow bands by a wire drawing machine according to a cold drawing process to obtain finished narrow bands; according to the preparation method, the wire material is used as the raw material to roll to obtain the rolled narrow band, the damage to the roller is large, and the prepared rolled narrow band is easy to break.
The invention patent 2013100283398 discloses a preparation method of an ultrathin Mo-La alloy thin material, which comprises the steps of preparing a Mo-La alloy billet by a powder metallurgy method, then carrying out cutting, vacuum annealing and cold rolling to obtain an alloy plate blank, and carrying out rough machining (vacuum annealing and multi-pass cold rolling), machining (multi-pass cold rolling and vacuum annealing), finish machining (multi-pass cold rolling and vacuum annealing), finally carrying out multi-pass cold rolling and vacuum annealing to obtain an ultrathin Mo-La alloy foil; the preparation method needs a plurality of passes of rolling, then needs to cut scrap materials for a plurality of times, and has the problems of long production period, low efficiency and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing molybdenum and molybdenum alloy foils, the molybdenum and molybdenum alloy foils prepared by the method can meet the use requirements of application fields such as consumer electronic devices, vacuum devices, catalytic materials and the like, the thickness of the foils is 0.01-0.1mm, the thickness tolerance is 2-5 mu m, and the flatness is less than or equal to 0.1 mm; the tensile strength at room temperature is 830-1200MPa, the yield strength is 700-1000MPa, and the elongation is 5-15%.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing molybdenum and molybdenum alloy foil, which adopts the following technical scheme:
a method of making molybdenum and molybdenum alloy foils comprising: taking pure molybdenum powder or molybdenum alloy powder as a raw material, adding a binder solution into the raw material, and performing ball milling treatment to obtain slurry; carrying out tape casting on the slurry to obtain tape casting blanks, and then sequentially carrying out degumming treatment, sintering treatment, rolling treatment and annealing treatment to obtain molybdenum or molybdenum alloy foils;
the rolling treatment comprises multi-pass cold rolling deformation and intermediate annealing treatment (the intermediate annealing treatment is carried out between two adjacent cold rolling deformations), and the total rolling deformation is 40% -99% (such as 50%, 60%, 70%, 80%).
According to the invention, the slurry is obtained by adding the binder solution into the pure molybdenum powder or the molybdenum alloy powder and then performing ball milling treatment, and the mixing uniformity can be improved by the wet mixing treatment; then casting blank with controllable thickness is obtained through casting forming treatment, and then molybdenum and molybdenum alloy foil is obtained through degumming treatment, sintering treatment, rolling treatment and annealing treatment; the invention combines the tape casting with the cold rolling deformation, realizes the production of the cold rolling process with smaller deformation by changing the thickness of the tape casting blank, and compared with the hot rolling process of a thicker blank, the preparation method of the invention has the advantages of less rolling passes, high production efficiency and low production cost.
In the above method for producing molybdenum and molybdenum alloy foil, as a preferred embodiment, the pure molybdenum powder or molybdenum alloy powder contains, in mass%, 50 to 100% (e.g., 60%, 70%, 80%, 90%) of Mo, 0 to 47.5% (e.g., 5%, 10%, 20%, 45%) of Re, 0 to 1% (e.g., 0.2%, 0.4%, 0.6%, 0.8%) of Ti, 0 to 2% (e.g., 0.2%, 0.5%, 1.0%, 1.5%) of Zr, 0 to 3% (e.g., 0.5%, 1.0%, 1.5%, 2.0%) of Hf, 0 to 0.5% (e.g., 0.1%, 0.2%, 0.3%, 0.4%) of C, 0 to 3% (e.g., 0.5%, 1.0%, 1.5%, 2.0%) of Re (rare earth element); preferably, the RE is one or more of La, Y and Ce; more preferably, the molybdenum alloy powder is a molybdenum titanium zirconium alloy powder, and the molybdenum alloy powder comprises, by mass, 0.40 to 0.55% of Ti (e.g., 0.42%, 0.45%, 0.50%, 0.52%), 0.06 to 0.12% of Zr (e.g., 0.07%, 0.08%, 0.10%, 0.11%), 0.01 to 0.04% of C (e.g., 0.015%, 0.020%, 0.25%, 0.30%), and the balance of Mo; more preferably, the molybdenum alloy powder is molybdenum-rhenium alloy powder, wherein the molybdenum alloy powder comprises, by mass, 52.5-95% (such as 55%, 60%, 70%, 80%) of Mo, and 5-47.5% (such as 10%, 15%, 20%, 40%) of Re; preferably, the molybdenum powder, the rhenium source, the titanium source, the zirconium source, the hafnium source, the carbon powder and the powder containing rare earth elements are respectively weighed according to the mass percentage and mixed to obtain pure molybdenum powder or molybdenum alloy powder; more preferably, the mixing process is carried out in a V-type mixer at a speed of 30-90r/min (e.g. 40r/min, 60r/min, 80r/min) and for a time of 4-8h (e.g. 5h, 6h, 7 h).
In the method for preparing molybdenum and molybdenum alloy foil, as a preferred embodiment, the particle size of the molybdenum powder is 2.0-4.0 μm (such as 2.2 μm, 2.5 μm, 3.0 μm, 3.5 μm); preferably, the rhenium source is pure rhenium powder or ammonium rhenate powder; preferably, the titanium source is titanium hydride powder, the granularity is-150 meshes-400 meshes, and the purity is more than or equal to 99.5%; preferably, the zirconium source is zirconium hydride powder, the granularity is-150 meshes-400 meshes, and the purity is more than or equal to 99.5%; preferably, the source of hafnium is hafnium carbide; preferably, the granularity of the carbon powder is-150 meshes to 400 meshes, and the purity is more than or equal to 99.5 percent; preferably, when the raw material of the molybdenum alloy is one or more of ammonium rhenate powder, titanium hydride powder and zirconium hydride powder, before the mixing treatment, reduction treatment is carried out; preferably, the reduction treatment is carried out in a hydrogen atmosphere, the reduction temperature is 600-1200 ℃ (such as 800 ℃, 900 ℃, 1000 ℃) and the reduction time is 2-6h (such as 3h, 4h, 5 h); more preferably, the reduction temperature is 800-.
In the method for preparing molybdenum and molybdenum alloy foil, as a preferred embodiment, the binder solution is 10% to 50% (e.g., 20%, 30%, 40%) of the mass of the pure molybdenum powder or the molybdenum alloy powder; preferably, the binder solution comprises, in mass percent: 10% -30% (e.g. 15%, 20%, 25%) binder, 5% -10% (e.g. 7%, 8%, 9%) plasticizer, the balance solvent; more preferably, the binder is polyvinyl butyral (PVB), the plasticizer is dibutyl phthalate, and the solvent is one or both of water and ethanol.
The binding agent polyvinyl butyral (PVB) used in the invention has good binding performance with pure molybdenum powder or molybdenum alloy powder, has weak toxicity and is easy to dissolve in ethanol.
In the method for preparing molybdenum and molybdenum alloy foil, as a preferred embodiment, the rotation speed of the ball milling treatment is 50-100r/min (such as 60r/min, 80r/min and 90r/min), and the ball milling time is 8-16h (such as 10h, 12h and 14 h).
In the method for preparing molybdenum and molybdenum alloy foil, as a preferred embodiment, the tape casting process is specifically to load the slurry into an automatic feeding chamber of a tape casting machine, start a tape casting device, and heat the slurry flowing onto the carrier belt through a sectional drying box to obtain a tape casting blank; preferably, the heating temperature is 20-100 deg.C (such as 30 deg.C, 50 deg.C, 70 deg.C), and the heating time is 30-60 min (such as 35min, 40min, 50 min); preferably, the thickness of the cast ingot is 0.2-3mm (e.g. 0.7mm, 1mm, 2 mm).
The thickness of the casting blank obtained by the casting molding treatment is 0.2-3mm, and the density is lower and is less than 50%. The heating by the sectional drying oven is aimed at removing the solvent from the binder solution.
In the method for preparing molybdenum and molybdenum alloy foil, as a preferred embodiment, the degumming treatment is carried out in hydrogen atmosphere, and the hydrogen flow is more than or equal to 3m3The degumming temperature is 400-800 ℃ (such as 500 ℃, 600 ℃ and 700 ℃) and the degumming time is 1-2h (such as 1.2h, 1.5h and 1.8 h).
In the method for preparing molybdenum and molybdenum alloy foils, as a preferred embodiment, the sintering treatment is carried out in a hydrogen atmosphere, the sintering temperature is 1600-.
In the method for preparing molybdenum and molybdenum alloy foil, as a preferred embodiment, in the rolling treatment, the rolling speed is 0.5-2.5m/s (such as 0.8m/s, 1.5m/s, 2.3 m/s); preferably, the preheating is carried out before the first cold rolling deformation, the preheating temperature is 100-300 ℃ (such as 150 ℃, 200 ℃ and 250 ℃), and the preheating time is 0.5-3h (such as 0.8h, 1.0h and 1.5 h); preferably, the intermediate annealing treatment is carried out in a hydrogen atmosphere, the intermediate annealing temperature is 700-1300 ℃ (such as 800 ℃, 900 ℃, 1200 ℃), and the intermediate annealing time is 1-2h (such as 1.2h, 1.5h, 1.8 h).
The rolling treatment comprises multi-pass cold rolling deformation and intermediate annealing treatment, and preheating is carried out before the first cold rolling deformation, so that cracking is avoided; and performing intermediate annealing treatment between the intermediate cold rolling deformation of each pass, cooling the rolled piece subjected to the intermediate annealing treatment to room temperature, performing the next cold rolling deformation, obtaining molybdenum and molybdenum alloy foil after the rolling is finished, and performing annealing treatment on the molybdenum and molybdenum alloy foil to obtain a molybdenum and molybdenum alloy foil finished product.
In the above method for preparing molybdenum and molybdenum alloy foil, as a preferred embodiment, the annealing treatment is performed under a hydrogen atmosphere or under vacuum, the annealing temperature is 800-.
The second aspect of the invention provides molybdenum and molybdenum alloy foils prepared by the preparation method; preferably, the foil has a thickness of 0.01 to 0.1mm (such as 0.05mm, 0.06mm, 0.07mm, 0.08mm), a thickness tolerance of 2 to 5 μm (such as 3 μm, 4 μm, 4.5 μm), a flatness ≦ 0.1 mm; preferably, the foil has room temperature tensile strength of 830-1200MPa (such as 850MPa, 900MPa and 1100MPa), yield strength of 700-1000MPa (such as 800MPa, 900MPa and 920MPa), and elongation of 5-15% (such as 7%, 10% and 12%).
Compared with the prior art, the invention has the following beneficial effects:
(1) the molybdenum or molybdenum alloy foil provided by the invention has excellent properties of uniform structure, high strength, high elongation and the like;
(2) according to the invention, the slurry is obtained by adding the binder solution into the pure molybdenum powder or the molybdenum alloy powder and then performing ball milling treatment, and the mixing uniformity can be improved by the wet mixing treatment; the invention combines the tape casting with the cold rolling deformation, realizes the cold rolling mode production with smaller deformation by changing the thickness of the tape casting blank, and has the advantages of less rolling passes, high production efficiency and low production cost compared with the hot rolling process of thicker blanks.
(3) The molybdenum and molybdenum alloy foil prepared by the method is uniform in material, the thickness of the foil is 0.01-0.1mm, the thickness tolerance is 2-5 mu m, the flatness is less than or equal to 0.1mm, the utilization rate of the powder raw material (the weight of a finished product/the weight of the raw material) is more than 85% (due to the fact that cold rolling deformation rolling passes are few, cut-off leftover materials are few, the utilization rate of the powder raw material is high), and the defects that the surface is free of scratches, convex pits and the like are overcome, compared with a powder compression molding process (the utilization rate of the raw material is less than or equal to 70%) in the prior art, the powder utilization rate can be improved, and the cost is reduced.
Drawings
FIG. 1 is a metallographic structure photograph (along the rolling direction) of a pure molybdenum foil obtained in example 1 of the present invention;
FIG. 2 is a metallographic structure photograph (along the rolling direction) of a Mo-Ti-Zr alloy foil produced in example 2 of the present invention;
FIG. 3 is a metallographic structure photograph (along the rolling direction) of a Mo-Re alloy foil obtained in example 3 of the present invention;
FIG. 4 is a photograph of the metallographic structure (along the rolling direction) of the Mo-La alloy foil obtained in example 4 of this invention.
Detailed Description
The method for preparing molybdenum and molybdenum alloy foil according to the present invention is described below with reference to the accompanying drawings and examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. It should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the appended claims.
The test methods in the following examples are all conventional methods unless otherwise specified, and can be performed according to techniques or conditions described in literature in the art or according to product specifications. The starting materials described in the following examples are all commercially available from the public.
The specific embodiment of the invention provides a method for preparing molybdenum and molybdenum alloy foils, which comprises the following steps:
(1) preparing pure molybdenum powder or molybdenum alloy powder: respectively weighing 50-100% of Mo, 0-47.5% of Re, 0-1% of Ti, 0-2% of Zr, 0-3% of Hf, 0-0.5% of C and 0-3% of RE (rare earth element) in the pure molybdenum powder or the molybdenum alloy powder according to the mass percentage of the pure molybdenum powder or the molybdenum alloy powder; mixing materials in a V-shaped mixer at the rotating speed of 30-90r/min for 4-8h to obtain pure molybdenum powder or molybdenum alloy powder;
(2) preparing slurry: adding a binder solution which accounts for 10% -50% of the mass of the pure molybdenum powder or the molybdenum alloy powder into the pure molybdenum powder or the molybdenum alloy powder obtained in the step (1), wherein the binder solution comprises the following components in percentage by mass: 10% -30% of PVB, 5% -10% of dibutyl phthalate and the balance of solvent; performing ball milling treatment in a ball milling mixer at the rotating speed of 50-100r/min for 8-16h to obtain slurry;
(3) preparing a casting blank: loading the slurry obtained in the step (2) into an automatic feeding chamber of a casting machine, starting a casting device, heating the slurry on a carrier belt through a sectional drying box at the heating temperature of 20-100 ℃ for 30-60 min to obtain casting blanks with the thickness of 0.2-3 mm;
(4) degumming treatment: carrying out degumming treatment on the casting blank obtained in the step (3) in an intermittent degumming furnace in hydrogen atmosphere, wherein the hydrogen flow is more than or equal to 3m3The degumming temperature is 400-800 ℃, and the degumming time is 1-2h, so as to obtain the degumming blank.
(5) Sintering treatment: sintering the degummed blank obtained in the step (4) in a medium-frequency induction sintering furnace in a hydrogen atmosphere at the sintering temperature of 1600-2300 ℃ for 2-6h to obtain a molybdenum or molybdenum alloy sintered blank;
(6) rolling treatment: performing multi-pass cold rolling deformation treatment and intermediate annealing treatment on the sintered blank obtained in the step (5), wherein the rolling speed is 0.5-2.5 m/s; the total rolling deformation is 40-99%; preheating before the first cold rolling deformation, wherein the preheating temperature is 100-300 ℃, the preheating time is 0.5-3h, intermediate annealing treatment is carried out between the intermediate cold rolling deformations in the hydrogen atmosphere, the intermediate annealing temperature is 700-1300 ℃, and the intermediate annealing time is 1-2 h; obtaining molybdenum or molybdenum alloy foil;
(7) annealing treatment: and (4) annealing the molybdenum or molybdenum alloy foil obtained in the step (6) in a hydrogen atmosphere or under a vacuum condition, wherein the annealing temperature is 800-1200 ℃, and the annealing time is 1-2h, so as to obtain a molybdenum or molybdenum alloy foil finished product.
The present invention will be described in further detail with reference to specific examples.
Example 1 a method of making a pure molybdenum foil, comprising:
(1) preparing pure molybdenum powder: weighing 18Kg of molybdenum powder with Fisher's particle size of 3.4 mu m, and loading into a V-shaped mixer for mixing at a rotation speed of 50r/min for 4h to obtain uniformly mixed pure molybdenum powder.
(2) Preparing pure molybdenum slurry: adding 5.4Kg of binder solution into the pure molybdenum powder obtained in the step (1), wherein the binder solution comprises 1.6Kg of PVB, 0.4Kg of dibutyl phthalate and 3.4Kg of absolute ethyl alcohol, then putting the mixture into a ball milling mixer for ball milling treatment, adding 4Kg of stainless steel balls at the rotating speed of 60r/min for mixing for 8 hours, and obtaining 23Kg of pure molybdenum slurry.
(3) Preparing a casting blank: and (3) filling the pure molybdenum slurry obtained in the step (2) into an automatic feeding chamber of a casting machine, setting the casting thickness to be 2mm, starting the casting equipment, allowing the slurry to flow onto a carrier band, and drying through a sectional heating drying box to obtain a pure molybdenum casting blank, wherein the drying temperature is RT-80 ℃, and the drying time is 30 min.
(4) Degumming treatment: putting the pure molybdenum casting blank obtained in the step (3) into an intermittent degumming furnace to carry out degumming treatment in hydrogen atmosphere with the hydrogen flow rate of 3m3And h, degumming at 400 ℃ for 1h to obtain a degummed pure molybdenum plate blank with the thickness of 1.2 mm.
(5) Sintering treatment: and (5) placing the degummed pure molybdenum plate blank obtained in the step (4) into a medium-frequency sintering furnace to carry out hydrogen atmosphere sintering treatment, wherein the sintering temperature is 1900 ℃, and the heat preservation time is 4h, so that a pure molybdenum sintering blank with the thickness of 0.8mm is obtained.
(6) Rolling treatment: and (3) carrying out multi-pass cold rolling deformation and intermediate annealing treatment on the pure molybdenum sintering blank obtained in the step (5), preheating before the first cold rolling deformation, wherein the preheating temperature is 250 ℃, the preheating time is 45min, the deformation of each pass of the intermediate pass is 5-30%, the total deformation is 90%, the rolling speed is 1.2m/s, and the annealing system of the intermediate pass is 750 ℃ multiplied by 1h (under the hydrogen condition), so that a pure molybdenum foil with the thickness of 0.08mm is obtained, and the thickness tolerance is +/-3 mu m.
(7) And (3) annealing treatment: and (5) annealing the pure molybdenum foil obtained in the step (6) in a hydrogen atmosphere at the annealing temperature of 850 ℃ for 1h, removing stress and forming the plate to obtain a finished product of the pure molybdenum foil.
Fig. 1 is a metallographic structure photograph of a finished product of the pure molybdenum foil prepared in this example, where the utilization rate of the powder raw material of the pure molybdenum foil obtained in example 1 is greater than 85%, the flatness is less than or equal to 0.1mm, and the surface of the pure molybdenum foil has no defects such as scratches, protrusions, pits, and the like.
Embodiment 2 a method of making a molybdenum titanium zirconium alloy foil, comprising:
(1) preparing molybdenum titanium zirconium alloy powder: weighing 29.81Kg of molybdenum powder with Fisher's particle size of 3.0 mu m, 150g of-300-mesh titanium hydride powder with the purity of more than or equal to 99.5%, 30g of-320-mesh zirconium hydride powder with the purity of more than or equal to 99.5% and 12g of-350-mesh carbon powder with the purity of more than or equal to 99.5%, and then carrying out reduction treatment in a sintering furnace under hydrogen atmosphere at the temperature of 1000 ℃ for 4 hours; and then putting the mixture into a V-shaped mixer for mixing at the rotating speed of 40r/min for 8 hours to obtain 30Kg of molybdenum-titanium-zirconium alloy powder.
(2) Preparing molybdenum-titanium-zirconium alloy slurry: adding 12Kg of binder solution into the molybdenum titanium zirconium alloy powder obtained in the step (1), wherein the binder solution is 3Kg of PVB, 1Kg of dibutyl phthalate and 8Kg of absolute ethyl alcohol, then putting the mixture into a ball milling mixer for ball milling treatment, adding 7Kg of stainless steel balls, the rotating speed is 70r/min, and the mixing time is 14h, thus obtaining 40Kg of molybdenum titanium zirconium alloy slurry.
(3) Preparing a molybdenum-titanium-zirconium alloy casting blank: and (3) loading the molybdenum titanium zirconium alloy slurry obtained in the step (2) into an automatic feeding chamber of a casting machine, setting the casting thickness to be 1.5mm, starting casting equipment, enabling the slurry to flow onto a carrier belt, and drying through a sectional heating drying box to obtain a molybdenum titanium zirconium alloy casting blank, wherein the drying temperature is RT-90 ℃, and the drying time is 45 min.
(4) Degumming treatment: will be provided withPutting the molybdenum titanium zirconium casting blank obtained in the step (3) into an intermittent degumming furnace to carry out degumming treatment in hydrogen atmosphere at the hydrogen flow rate of 4m3And h, the degumming temperature is 600 ℃, and the heat preservation time is 1.5h, so that the degumming molybdenum titanium zirconium alloy casting blank with the thickness of 0.9mm is obtained.
(5) Sintering treatment: and (4) putting the casting blank of the degummed molybdenum titanium zirconium alloy obtained in the step (4) into a medium-frequency induction sintering furnace for hydrogen atmosphere sintering treatment, wherein the sintering temperature is 2100 ℃, and the heat preservation time is 6 hours, so that the molybdenum titanium zirconium alloy sintering blank with the thickness of 0.6mm is obtained.
(6) Rolling treatment: and (3) carrying out multi-pass cold rolling deformation and intermediate annealing treatment on the molybdenum-titanium-zirconium alloy sintered blank obtained in the step (5), preheating before the first cold rolling deformation, wherein the preheating temperature is 300 ℃, the preheating time is 1h, the deformation of each pass of the intermediate pass is 5-30%, the total deformation is 90%, the annealing schedule of the intermediate pass is 900-1000 ℃ multiplied by 1h (under the hydrogen condition), the rolling speed is 1.0m/s, and the molybdenum-titanium-zirconium alloy foil with the thickness of 0.06mm is obtained, and the thickness tolerance is +/-2 mu m.
(7) And (3) annealing treatment: and (5) annealing the molybdenum titanium zirconium alloy foil obtained in the step (6) in a hydrogen atmosphere at the annealing temperature of 1100 ℃ for 1h, removing stress and forming a plate to obtain a finished product of the molybdenum titanium zirconium alloy foil.
Fig. 2 is a metallographic structure photograph of the molybdenum titanium zirconium alloy foil finished product prepared in this embodiment. The molybdenum titanium zirconium alloy foil obtained by the implementation 2 has the advantages that the utilization rate of the powder raw materials is more than 80%, the planeness is less than or equal to 0.1mm, and the surface has no defects such as scratches, convex pits and the like.
Example 3A method of preparing a molybdenum-rhenium alloy foil, comprising
(1) Preparing molybdenum-rhenium alloy powder: weighing 6.5Kg of molybdenum powder with Fisher granularity of 3.6 mu m and 3.5Kg of rhenium powder with the Fisher granularity of 3.2 mu m and the purity of 99.99 percent, and loading the mixture into a V-shaped mixer for mixing at the rotating speed of 60r/min for 6 hours to obtain 10Kg of molybdenum-rhenium alloy powder.
(2) Preparing molybdenum-rhenium alloy slurry: adding 3.5Kg of binder solution into the molybdenum-rhenium alloy powder obtained in the step (1), wherein the binder solution comprises 1Kg of PVB, 0.35Kg of dibutyl phthalate and 2.15Kg of absolute ethyl alcohol, then putting the mixture into a ball milling mixer for ball milling treatment, adding 2Kg of stainless steel balls, wherein the rotating speed is 80r/min, and the mixing time is 16h, thus obtaining 13Kg of molybdenum-rhenium alloy slurry.
(3) Preparing a molybdenum-rhenium alloy casting blank: and (3) loading the molybdenum-rhenium alloy slurry obtained in the step (2) into an automatic feeding chamber of a casting machine, setting the casting thickness to be 1.5mm, starting casting equipment, enabling the slurry to flow onto a carrier belt, and drying through a segmented heating drying box to obtain a molybdenum-rhenium alloy casting blank, wherein the drying temperature is RT-70 ℃, and the drying time is 50 min.
(4) Degumming treatment: putting the molybdenum-rhenium alloy casting blank obtained in the step (3) into an intermittent degumming furnace to carry out degumming treatment in hydrogen atmosphere at the hydrogen flow rate of 3m3And h, degumming at 500 ℃ for 2h to obtain a degummed molybdenum-rhenium alloy blank with the thickness of 1 mm.
(5) Sintering treatment: and (5) putting the degummed molybdenum-rhenium alloy casting blank obtained in the step (4) into a medium-frequency induction sintering furnace to carry out hydrogen atmosphere sintering treatment, wherein the sintering temperature is 2300 ℃, and the heat preservation time is 6 hours, so as to obtain a molybdenum-rhenium alloy sintering blank with the thickness of 0.6 mm.
(6) Rolling treatment: and (3) carrying out multi-pass cold rolling deformation and intermediate annealing treatment on the molybdenum-rhenium alloy sintering blank obtained in the step (5), preheating before the first cold rolling deformation, wherein the preheating temperature is 300 ℃, the preheating time is 1.5h, the deformation of each pass of the intermediate pass is 5-30%, the total deformation is 92%, the annealing temperature of the intermediate pass is 1000-1300 ℃ multiplied by 1h, and the rolling speed is 1.5m/s, so that the molybdenum-rhenium alloy foil with the thickness of 0.05mm is obtained, and the thickness tolerance is +/-4 mu m.
(7) Annealing treatment: and (5) annealing the molybdenum-rhenium alloy foil obtained in the step (6) in a hydrogen atmosphere at the annealing temperature of 1100 ℃ for 1h, removing stress and forming a plate to obtain a finished product of the molybdenum-rhenium alloy foil.
Fig. 3 is a metallographic structure photograph of the molybdenum-rhenium alloy foil finished product prepared in the embodiment. The molybdenum-rhenium alloy foil obtained in the embodiment 3 has the powder raw material utilization rate of more than 90 percent, the planeness of less than or equal to 0.1mm, and no defects such as scratches, convex pits and the like on the surface.
Example 4 a method of making a molybdenum lanthanum alloy foil, comprising:
(1) preparing molybdenum-lanthanum alloy powder: weighing 19.4Kg of molybdenum powder and 0.6Kg of lanthanum oxide powder; mixing materials in a V-shaped mixer at the rotating speed of 60min for 6h to obtain 20Kg of molybdenum-lanthanum alloy powder;
(2) preparing slurry: adding 9Kg of binder solution into the molybdenum-lanthanum alloy powder obtained in the step (1), wherein the binder solution comprises: 2.7Kg of PVB, 0.9Kg of dibutyl phthalate and 5.4Kg of absolute ethyl alcohol; then the mixture is put into a ball milling mixer for ball milling treatment, 2Kg of stainless steel balls are added, the rotating speed is 60r/min, and the ball milling time is 10 hours, thus obtaining 28.5Kg of slurry;
(3) preparing a casting blank: loading the slurry obtained in the step (2) into an automatic feeding chamber of a casting machine, setting the casting thickness to be 2.0mm, starting casting equipment, enabling the slurry to flow onto a carrier belt, and drying the slurry through a sectional heating drying box at the temperature of RT-90 ℃ for 50min to obtain a casting blank;
(4) degumming treatment: carrying out degumming treatment on the casting blank obtained in the step (3) in an intermittent degumming furnace in a hydrogen atmosphere, wherein the hydrogen flow is 4m3And h, degumming temperature is 500 ℃, degumming time is 1h, and degumming blank with the thickness of 1.5mm is obtained.
(5) Sintering treatment: sintering the degummed blank obtained in the step (4) in a medium-frequency induction sintering furnace in a hydrogen atmosphere at the sintering temperature of 1800 ℃ for 4 hours to obtain a 1.2mm molybdenum alloy sintered blank;
(6) rolling treatment: preheating before the first cold rolling deformation, wherein the preheating temperature is 300 ℃, the preheating time is 2h, the deformation of each pass of the intermediate pass is 5-30%, the total deformation is 96%, the annealing temperature of the intermediate pass is 1000-1300 ℃ multiplied by 1h (under the condition of hydrogen), the rolling speed is 1.5m/s, and the molybdenum-lanthanum alloy foil with the thickness of 0.05mm is obtained, and the thickness tolerance is +/-4 mu m;
(7) annealing treatment: and (4) annealing the molybdenum-lanthanum alloy foil obtained in the step (6) in a hydrogen atmosphere, wherein the annealing temperature is 1100 ℃, the annealing time is 1h, and removing stress and forming a plate material to obtain a molybdenum-lanthanum alloy foil finished product.
Fig. 4 is a metallographic structure photograph of the molybdenum-lanthanum alloy foil finished product prepared in the embodiment. The molybdenum-lanthanum alloy foil obtained in the embodiment 4 has the powder raw material utilization rate of more than 90 percent, the planeness of less than or equal to 0.1mm, and no defects such as scratches, bulges, pits and the like on the surface.
Comparative example 1 a method of preparing a pure molybdenum foil, comprising:
(1) preparing pure molybdenum powder: weighing 18Kg of molybdenum powder with Fisher's particle size of 3.4 mu m, and loading the molybdenum powder into a V-shaped mixer for mixing at the rotating speed of 50r/min for 4h to obtain uniformly mixed pure molybdenum powder.
(2) And (3) cold isostatic pressing treatment: carrying out cold isostatic pressing treatment on the pure molybdenum powder, wherein the pressing pressure is 200MPa, and the pressing time is 5 minutes, so as to obtain a pure molybdenum green compact with the thickness of 40 mm;
(3) sintering and forming treatment: putting the pure molybdenum green compact into an intermediate frequency sintering furnace to carry out hydrogen atmosphere sintering treatment, wherein the sintering temperature is 1900 ℃, and the heat preservation time is 4 hours, so that a pure molybdenum green compact with the thickness of 33mm is obtained;
(4) rolling treatment: and (3) carrying out multi-pass hot rolling deformation and intermediate annealing treatment on the pure molybdenum sintered blank, wherein the initial rolling temperature is 1350 ℃, the deformation of each pass of the intermediate pass is 15-30%, the total deformation is more than 99%, the annealing system of the intermediate pass is 700-900 ℃ multiplied by 0.5-2 h, the rolling speed is 1.5m/s, and the pure molybdenum foil with the thickness of 0.08mm is obtained, and the thickness tolerance is +/-4 mu m.
(5) Annealing treatment: annealing the pure molybdenum foil obtained in the step (4) under a vacuum condition, wherein the annealing temperature is 900 ℃, and the annealing time is 1h
(6) Surface cleaning and shearing: and (5) cleaning the surface of the product obtained in the step (5) and shearing to obtain a pure molybdenum foil finished product.
Comparative example 1 the utilization rate of the powder raw material for preparing the pure molybdenum foil is 70 percent, and the planeness is less than or equal to 0.1mm
And (3) performance testing:
the pure molybdenum and molybdenum alloy foil finished products prepared in the embodiments 1-4 and the comparative example 1 of the invention are subjected to performance tests, and tensile tests are carried out according to GB/T13239-.
Table 1 shows the performance results of the pure molybdenum and molybdenum alloy foil products obtained in examples 1-4 of the present invention and comparative example 1
| Tensile strength/MPa | Yield strength/MPa | Elongation/percent | |
| Example 1 | 852 | 727 | 8 |
| Example 2 | 1130 | 990 | 7 |
| Example 3 | 945 | 872 | 12 |
| Example 4 | 1028 | 954 | 5 |
| Comparative example 1 | 830 | 700 | 6 |
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for preparing molybdenum and molybdenum alloy foils is characterized by comprising the following steps: taking pure molybdenum powder or molybdenum alloy powder as a raw material, adding a binder solution into the raw material, and performing ball milling treatment to obtain slurry; carrying out tape casting treatment on the slurry to obtain tape casting blanks, and then sequentially carrying out degumming treatment, sintering treatment, rolling treatment and annealing treatment to obtain molybdenum or molybdenum alloy foils;
wherein the rolling treatment comprises multi-pass cold rolling deformation and intermediate annealing treatment, and the total rolling deformation is 40-99%.
2. The method of claim 1, wherein the pure molybdenum powder or molybdenum alloy powder comprises, by mass, 50-100% of Mo, 0-47.5% of Re, 0-1% of Ti, 0-2% of Zr, 0-3% of Hf, 0-0.5% of C, and 0-3% of RE; preferably, the RE is one or more of La, Y and Ce;
more preferably, the molybdenum alloy powder is molybdenum titanium zirconium alloy powder, and the mass percentage of Ti is 0.40-0.55%, Zr is 0.06-0.12%, C is 0.01-0.04%, and the balance is Mo;
more preferably, the molybdenum alloy powder is molybdenum-rhenium alloy powder, and the molybdenum alloy powder comprises, by mass, 52.5-95% of Mo and 5-47.5% of Re;
preferably, the molybdenum powder, the rhenium source, the titanium source, the zirconium source, the hafnium source, the carbon powder and the powder containing rare earth elements are respectively weighed according to the mass percentage and mixed to obtain pure molybdenum powder or molybdenum alloy powder;
more preferably, the mixing treatment is carried out in a V-shaped mixer, the rotating speed is 30-90r/min, and the mixing time is 4-8 h.
3. The method of claim 2, wherein the molybdenum powder has a particle size of 2.0-4.0 μm; preferably, the rhenium source is pure rhenium powder or ammonium rhenate powder; preferably, the titanium source is titanium hydride powder, the granularity is-150 meshes-400 meshes, and the purity is more than or equal to 99.5%; preferably, the zirconium source is zirconium hydride powder, the granularity is-150 meshes-400 meshes, and the purity is more than or equal to 99.5%; preferably, the hafnium source is hafnium carbide; preferably, the granularity of the carbon powder is-150 meshes-400 meshes, and the purity is more than or equal to 99.5 percent; preferably, when the raw material of the molybdenum alloy is one or more of ammonium rhenate powder, titanium hydride powder and zirconium hydride powder, before the mixing treatment, reduction treatment is carried out; preferably, the reduction treatment is carried out in a hydrogen atmosphere, the reduction temperature is 600-1200 ℃, and the reduction time is 2-6 h; more preferably, the reduction temperature is 800-1000 ℃, and the reduction time is 4-6 h.
4. The method for preparing molybdenum and molybdenum alloy foils according to any one of claims 1 to 3, wherein the binder solution is 10 to 50% by mass of the pure molybdenum powder or molybdenum alloy powder; preferably, the binder solution comprises, in mass percent: 10-30% of binder, 5-10% of plasticizer and the balance of solvent; more preferably, the binder is polyvinyl butyral, the plasticizer is dibutyl phthalate, and the solvent is one or both of water and ethanol.
5. The method for preparing molybdenum and molybdenum alloy foil according to any one of claims 1 to 4, wherein the rotation speed of the ball milling treatment is 50 to 100r/min, and the ball milling time is 8 to 16 h; preferably, the tape-casting treatment specifically includes that slurry is filled into an automatic feeding chamber of a tape-casting machine, tape-casting equipment is started, and the slurry flows onto a carrier tape and is heated through a sectional drying box to obtain a tape-casting blank; preferably, the heating temperature is 20-100 ℃, and the heating time is 30-60 min; preferably, the thickness of the casting blank is 0.2 to 3 mm.
6. The method for preparing molybdenum and molybdenum alloy foil according to any one of claims 1 to 5, wherein the degumming treatment is carried out in a hydrogen atmosphere with a hydrogen flow rate of 3m or more3The degumming temperature is 400-.
7. The method for preparing molybdenum and molybdenum alloy foil according to any one of claims 1 to 6, wherein the sintering treatment is performed in a hydrogen atmosphere at a sintering temperature of 1600-.
8. The method for preparing molybdenum and molybdenum alloy foil according to any one of claims 1 to 7, wherein in the rolling treatment, the rolling speed is 0.5 to 2.5 m/s; preferably, preheating is carried out before the first cold rolling deformation, the preheating temperature is 100-300 ℃, and the preheating time is 0.5-3 h; preferably, the intermediate annealing treatment is carried out in a hydrogen atmosphere, the intermediate annealing temperature is 700-1300 ℃, and the intermediate annealing time is 1-2 h.
9. The method for preparing molybdenum and molybdenum alloy foil according to any one of claims 1-8, wherein the annealing treatment is performed in a hydrogen atmosphere or under vacuum at an annealing temperature of 800-1200 ℃ for 1-2 h.
10. A molybdenum and molybdenum alloy foil produced by the production method according to any one of claims 1 to 9; preferably, the thickness of the foil is 0.01-0.1mm, the thickness tolerance is 2-5 μm, and the planeness is less than or equal to 0.1 mm; preferably, the tensile strength at room temperature of the foil is 830-1200MPa, the yield strength is 700-1000MPa, and the elongation is 5-15%.
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