CN115466893A - High-density molybdenum-tungsten alloy material and preparation method thereof - Google Patents
High-density molybdenum-tungsten alloy material and preparation method thereof Download PDFInfo
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- CN115466893A CN115466893A CN202211136848.8A CN202211136848A CN115466893A CN 115466893 A CN115466893 A CN 115466893A CN 202211136848 A CN202211136848 A CN 202211136848A CN 115466893 A CN115466893 A CN 115466893A
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- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910001080 W alloy Inorganic materials 0.000 title claims abstract description 103
- 239000000956 alloy Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims description 27
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 57
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims description 68
- 238000002156 mixing Methods 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000001513 hot isostatic pressing Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 238000011049 filling Methods 0.000 claims description 17
- 238000007872 degassing Methods 0.000 claims description 16
- 238000003754 machining Methods 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 9
- 238000004806 packaging method and process Methods 0.000 claims description 9
- 238000003466 welding Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 claims description 2
- 238000005476 soldering Methods 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 abstract description 7
- 239000010937 tungsten Substances 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 238000010923 batch production Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910001182 Mo alloy Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005098 hot rolling Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000005477 sputtering target Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000009694 cold isostatic pressing Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- 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
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
-
- 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
- B22F3/24—After-treatment of workpieces or articles
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
-
- 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
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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
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a high-density molybdenum-tungsten alloy material which is prepared from the following raw materials in parts by weight: 30-80% of molybdenum powder and 20-70% of tungsten powder; the density of the high-density molybdenum-tungsten alloy material is 11.26-15.23 g/cm 3 . The tungsten content in the high-density molybdenum-tungsten alloy material provided by the invention can reach 70% at most. The microscopic crystal grains are fine and uniform, the use requirements of the fields of industrial high-temperature furnaces, electronic light sources and LCD display coating films are completely met, andthe method is simple, low in cost and convenient for batch production.
Description
Technical Field
The invention belongs to the field of preparation of high-temperature refractory metal materials, and relates to a molybdenum-tungsten alloy material, in particular to a high-density molybdenum-tungsten alloy material and a preparation method thereof.
Background
The molybdenum-tungsten alloy material has the characteristics of high melting point, low resistivity, good high-temperature strength, good toughness and the like, and is widely applied to the fields of heating bodies, heat shields, lamp filaments of electronic tubes, current-carrying protective coatings and the like of high-temperature furnaces. In the field of hot galvanizing, molybdenum-tungsten alloy has excellent corrosion resistance to liquid zinc, high thermal conductivity, low expansion coefficient, thermal shock resistance and the like, and is used for manufacturing inner liners of stirrers, pipelines, containers and the like in the zinc smelting industry. In addition, thanks to rapid development of display technology and photovoltaic industry, molybdenum-tungsten alloy has lower resistivity and superior taper processability compared to conventional metallic materials Al and Cr, can avoid delay of gate pulse, and can shorten wiring interval and wiring width, thus being used as an electrode or wiring material for flat panel displays, solar cells, semiconductor elements, and the like.
The preparation method of the molybdenum-tungsten alloy blank is mainly a powder metallurgy method, and the molybdenum-tungsten alloy blank has the characteristics of higher melting point, lower resistivity, better high-temperature strength and toughness and the like along with the increase of tungsten content, and has wider application fields. But the increase of the content of the molybdenum and tungsten alloy can also increase the recrystallization temperature, and the molybdenum and tungsten alloy is more difficult to compact; in the prior art, in order to improve the relative density of the tungsten-molybdenum alloy, the content of tungsten in the tungsten-molybdenum alloy is usually not more than 30%, the relative density is difficult to exceed 98% after the tungsten-molybdenum alloy is sintered by a hydrogen sintering furnace, and the tungsten-molybdenum alloy needs to be further densified by high-temperature rolling.
CN 111254396A discloses a preparation method of a molybdenum-tungsten alloy sputtering target, which comprises the following steps: firstly, taking molybdenum powder, tungsten powder and tungsten trioxide powder in a certain ratio, carrying out ball milling and mixing under a protective atmosphere, and uniformly mixing; step two, performing rubber sleeve powder packing on the uniformly mixed materials, and then performing cold isostatic pressing to obtain a blank body; step three, sintering the blank in a hydrogen protective atmosphere in a two-stage mode to obtain a sintered blank; heating the sintered blank under the protection of hydrogen or argon, then carrying out hot rolling and leveling, and finally annealing under hydrogen or vacuum to obtain a molybdenum-tungsten alloy plate blank; and fifthly, carrying out machining such as grinding on the molybdenum-tungsten alloy plate blank according to the requirement to obtain a molybdenum-tungsten alloy product.
CN 103255379A discloses a molybdenum-tungsten alloy sputtering target for a flat panel display and a preparation method thereof, the molybdenum-tungsten alloy sputtering target for the flat panel display is prepared from 80-96.5% of molybdenum powder and 3.5-20% of tungsten powder, and the preparation method comprises: preparing materials, preparing powder, mechanically alloying, filling a die, performing cold isostatic pressing, sintering, hot rolling, vacuum annealing and machining.
The molybdenum-tungsten alloy material is obtained by adopting a mode of combining sintering and hot rolling, but the preparation method has the disadvantages of complex process and high cost, and is difficult to realize industrial mass production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a high-density molybdenum-tungsten alloy material and a preparation method thereof. The method can obtain the molybdenum-tungsten alloy material with the equivalent density of 100 percent and the maximum tungsten content of 70 percent by improving the granularity, the alloying degree, the sintering method and the like of the metal powder. The microscopic crystal grains are fine and uniform, the use requirements in the fields of industrial high-temperature furnaces, electronic light sources and LCD display coating films are completely met, and the method is simple, low in cost and convenient for batch production.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a high-density molybdenum-tungsten alloy material, which is prepared from the following raw materials in parts by weight: 30-80% of molybdenum powder and 20-70% of tungsten powder;
the density of the high-density molybdenum-tungsten alloy material is 11.26-15.23 g/cm 3 It may be, for example, 11.26g/cm 3 、12g/cm 3 、13g/cm 3 、14g/cm 3 、15g/cm 3 Or 15.23g/cm 3 But are not limited to the recited values, and other values within the numerical range not recited are equally applicable.
The molybdenum powder may be present in an amount of, for example, 30 to 80%, for example, 30%, 40%, 50%, 60%, 70% or 80%, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
The content of the tungsten powder is 20 to 70%, and for example, it may be 20%, 30%, 40%, 50%, 60% or 70%, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The tungsten content of the high-density molybdenum-tungsten alloy material provided by the invention can reach 70% at most, and the high-density molybdenum-tungsten alloy material has fine and uniform microscopic crystal grains, and completely meets the use requirements of the fields of industrial high-temperature furnaces, electronic light sources and LCD display coating.
The relative density of the high-density molybdenum-tungsten alloy material provided by the invention can reach up to 100%.
Preferably, the molybdenum powder has an average particle size of 1 to 3 μm, which may be, for example, 1 μm, 1.5 μm, 2 μm, 2.5 μm or 3 μm, but is not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preferably, the molybdenum powder has a Mo content of 99.96% or more, which may be, for example, 99.96%, 99.97%, 99.98% or 99.99%, but is not limited to the values listed, and other values not listed within the range of values are equally applicable.
Preferably, the tungsten powder has an average particle size of 1 to 3 μm, which may be, for example, 1 μm, 1.5 μm, 2 μm, 2.5 μm or 3 μm, but is not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preferably, the W content of the tungsten powder is 99.96% or more, and may be, for example, 99.96%, 99.97%, 99.98%, or 99.99%, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
In a second aspect, the present invention provides a method for preparing the high-density molybdenum-tungsten alloy material according to the first aspect, wherein the method comprises the following steps:
(1) Ball-milling and mixing molybdenum powder and tungsten powder according to the weight ratio of the raw materials, and then sequentially carrying out die filling and degassing to obtain a molybdenum-tungsten sheath;
(2) Sequentially carrying out hot isostatic pressing and heat treatment on the molybdenum-tungsten sheath obtained in the step (1) to obtain a molybdenum-tungsten alloy blank;
(3) And (3) carrying out post-treatment on the molybdenum-tungsten alloy blank obtained in the step (2) to obtain the high-density molybdenum-tungsten alloy material.
The preparation method is simple, and the high-density molybdenum-tungsten alloy material can be obtained without a hot rolling process.
Preferably, the ball milling and mixing in the step (1) comprises a pre-mixing ball milling and a final mixing ball milling which are sequentially carried out.
Preferably, the pre-mix ball mill is: mixing tungsten powder and part of molybdenum powder, and performing ball milling to obtain a premix;
preferably, the part of the molybdenum powder accounts for 30-70 wt% of the total mass of the molybdenum powder; for example, it may be 30%, 40%, 50%, 60% or 70%, but is not limited to the recited values, and other values not recited within the numerical range are equally applicable.
Preferably, the time of the premixed ball milling is 10 to 30 hours, for example, 10 hours, 14 hours, 18 hours, 22 hours, 26 hours or 30 hours, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the final ball mill is: and mixing the rest molybdenum powder with the obtained premix for ball milling at least twice.
Preferably, the final ball milling time is 10 to 30 hours, for example, 10 hours, 14 hours, 18 hours, 22 hours, 26 hours or 30 hours, but not limited to the recited values, and other values not recited in the range of values are also applicable.
According to the invention, the molybdenum powder and the tungsten powder are mixed by adopting a two-step mixing method, so that the ball milling time is further prolonged, the particle agglomeration of the molybdenum-tungsten alloy powder is reduced due to the prolonging of the ball milling time, the surface energy of the alloy powder is increased, and the subsequent hot isostatic pressing and heat treatment can be favorably carried out.
Preferably, the density of the mold in step (1) is 65% or more, for example 65%, 70%, 75%, 80%, 85%, 90%, 95% or 99%, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the step (1) is performed with soldering and packaging after the mold is filled.
Preferably, the degassing temperature in step (1) is 300-700 ℃, for example 300 ℃, 400 ℃, 500 ℃, 600 ℃ or 700 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the degassing in step (1) is terminated at a degree of vacuum of ≦ 1E-3Pa in the jacket, which may be, for example, 1E-3Pa, 1.5E-3Pa, 2E-3Pa, 2.5E-3Pa, 3E-3Pa, 4E-3Pa or 5E-3Pa, but is not limited to the values recited, and other values not recited within the range of values may be equally applicable.
The mould filling and degassing process specifically comprises the following steps: putting the prepared molybdenum-tungsten alloy powder into a sheath welded by stainless steel, and compacting while die filling; and then welding and packaging the molybdenum-tungsten spindle subjected to die filling by argon arc welding, putting the welded stainless steel sheath into a resistance furnace, connecting the stainless steel sheath to a molecular pump through a degassing pipe, wherein the degassing temperature is 300-700 ℃, closing a valve and stopping heat preservation when the molecular pump displays that the vacuum degree in the sheath is less than 1E-3Pa, and then sealing the degassing pipe by argon arc welding to ensure that the sheath is in a high vacuum state.
Preferably, the hot isostatic pressing in step (2) is carried out at a temperature of 1000 to 1400 ℃, for example 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃ or 1400 ℃, but not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the hot isostatic pressing in step (2) is carried out at a pressure of 180 to 200MPa, such as 180MPa, 185MPa, 190MPa, 195MPa or 200MPa, but not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the hot isostatic pressing in step (2) is carried out for 4 to 6 hours, for example, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, 5 hours, 5.2 hours, 5.4 hours, 5.6 hours, 5.8 hours or 6 hours, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the hot isostatic pressing in step (2) further comprises a cooling and depressurizing process.
Preferably, the temperature of the heat treatment in step (2) is 1200 to 1400 ℃, for example 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃ or 1400 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the time of the heat treatment in the step (2) is 2 to 6 hours, for example, 2 hours, 2.4 hours, 2.8 hours, 3.2 hours, 3.6 hours, 4 hours, 4.4 hours, 4.8 hours, 5.2 hours, 5.6 hours or 6 hours, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
The purpose of the heat treatment is to remove the stress of the product, so that the microstructure is further homogenized, and the material is better used.
The temperature of the heat treatment is 1200-1400 ℃, and the microstructure of the alloy material is coarse and uneven due to overhigh temperature, so that the performance of the alloy is influenced; if the internal stress of the alloy material is too low, the internal stress of the alloy material is not obviously removed, and the alloy material is easy to deform and cannot be used after being prepared into a thin plate.
Preferably, the post-treatment of step (3) comprises cutting and machining in sequence.
The size of the obtained molybdenum-tungsten alloy material is adjustable through cutting and machining, and the use requirements in the fields of industrial high-temperature furnaces, electronic light sources and LCD display coating films are further met.
As a preferred technical solution of the present invention, the preparation method of the high-density molybdenum-tungsten alloy material provided by the second aspect of the present invention comprises the following steps:
(1) Ball-milling and mixing molybdenum powder and tungsten powder according to the weight ratio of the raw materials, then filling the mixture into a die, welding and packaging the mixture, and degassing the mixture at the temperature of 300-700 ℃ until the vacuum degree in the sheath is less than or equal to 1E-3Pa to obtain a molybdenum-tungsten sheath;
wherein the ball milling and mixing comprises premixing ball milling and final mixing ball milling which are sequentially carried out; the premixed ball milling comprises the following steps: mixing tungsten powder and part of molybdenum powder, and performing ball milling for 10-30 h to obtain a premix; the part of molybdenum powder accounts for 30-70 wt% of the total mass of the molybdenum powder; the final mixing ball milling comprises the following steps: the rest molybdenum powder is divided into at least two times to be mixed with the obtained premix for ball milling for 10 to 30 hours;
the density of the die filling is more than or equal to 65 percent;
(2) Carrying out hot isostatic pressing on the molybdenum-tungsten sheath obtained in the step (1) at the temperature of 1000-1400 ℃ and under the pressure of 180-200 MPa for 4-6 h, then cooling and depressurizing, and then carrying out heat treatment at the temperature of 1200-1400 ℃ for 2-6 h to obtain a molybdenum-tungsten alloy blank;
(3) And (3) sequentially cutting and machining the molybdenum-tungsten alloy blank obtained in the step (2) to obtain the high-density molybdenum-tungsten alloy material.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) The relative density of the high-density molybdenum-tungsten alloy material provided by the invention can reach up to 100%, wherein the content of metal tungsten can reach up to 70%;
(2) The high-density molybdenum-tungsten alloy material provided by the invention has fine and uniform microscopic grains, and can completely meet the use requirements in the fields of industrial high-temperature furnaces, electronic light sources and LCD display coating films;
(3) The high-density molybdenum-tungsten alloy material provided by the invention is simple in preparation method, low in cost and convenient for batch production.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a high-density molybdenum-tungsten alloy material, which is prepared from the following raw materials in parts by weight: 30% of molybdenum powder and 70% of tungsten powder;
the density of the high-density molybdenum-tungsten alloy material is 15.23g/cm 3 。
The preparation method of the high-density molybdenum-tungsten alloy material comprises the following steps:
(1) Ball-milling and mixing molybdenum powder and tungsten powder according to the weight ratio of the raw materials, then filling the mixture into a die, welding and packaging the mixture, and degassing the mixture at the temperature of 500 ℃ until the vacuum degree in the sheath is less than or equal to 1E-3Pa to obtain a molybdenum-tungsten sheath;
wherein the ball milling and mixing comprises premixing ball milling and final mixing ball milling which are sequentially carried out; the premixed ball milling comprises the following steps: mixing tungsten powder and 70wt% of molybdenum powder, and performing ball milling for 24 hours to obtain a premix; the final mixing ball milling comprises the following steps: dividing the rest molybdenum powder into 3 times, mixing with the obtained premix, and ball-milling for 24h;
the density of the die filling is more than or equal to 65 percent;
(2) Hot isostatic pressing the molybdenum-tungsten sheath obtained in the step (1) at 1250 ℃ under 190MPa for 5h, then cooling and depressurizing, and then heat treating at 1300 ℃ for 4.5h to obtain a molybdenum-tungsten alloy blank;
(3) And (3) sequentially cutting and machining the molybdenum-tungsten alloy blank obtained in the step (2) to obtain the high-density molybdenum-tungsten alloy material.
Example 2
The embodiment provides a high-density molybdenum-tungsten alloy material, which is prepared from the following raw materials in parts by weight: 50% of molybdenum powder and 50% of tungsten powder;
the density of the high-density molybdenum-tungsten alloy material is 14.75g/cm 3 。
The preparation method of the high-density molybdenum-tungsten alloy material comprises the following steps:
(1) Ball-milling and mixing molybdenum powder and tungsten powder according to the weight ratio of the raw materials, then filling the mixture into a die, welding and packaging the mixture, and degassing the mixture at the temperature of 300 ℃ until the vacuum degree in the sheath is less than or equal to 1E-3Pa to obtain a molybdenum-tungsten sheath;
wherein the ball milling and mixing comprises premixing ball milling and final mixing ball milling which are sequentially carried out; the premixed ball milling comprises the following steps: mixing tungsten powder and 30wt% of molybdenum powder, and performing ball milling for 10 hours to obtain a premix; the final mixing ball milling comprises the following steps: dividing the rest molybdenum powder into 7 times, mixing with the obtained premix, and ball-milling for 30h;
the density of the die filling is more than or equal to 65 percent;
(2) Carrying out hot isostatic pressing on the molybdenum-tungsten sheath obtained in the step (1) for 4h at the temperature of 1000 ℃ and under the pressure of 200MPa, then cooling and depressurizing, and then carrying out heat treatment for 2h at the temperature of 1400 ℃ to obtain a molybdenum-tungsten alloy blank;
(3) And (3) sequentially cutting and machining the molybdenum-tungsten alloy blank obtained in the step (2) to obtain the high-density molybdenum-tungsten alloy material.
Example 3
The embodiment provides a high-density molybdenum-tungsten alloy material, which is prepared from the following raw materials in parts by weight: 78% molybdenum powder and 22% tungsten powder;
the density of the high-density molybdenum-tungsten alloy material is 11.38g/cm 3 。
The preparation method of the high-density molybdenum-tungsten alloy material comprises the following steps:
(1) Ball-milling and mixing molybdenum powder and tungsten powder according to the weight ratio of the raw materials, then filling the mixture into a die, welding and packaging the mixture, and degassing the mixture at the temperature of 700 ℃ until the vacuum degree in the sheath is less than or equal to 1E-3Pa to obtain a molybdenum-tungsten sheath;
the ball milling and mixing comprises premixing ball milling and final mixing ball milling which are sequentially carried out; the pre-mixing ball milling comprises the following steps: mixing tungsten powder and 60wt% molybdenum powder, and ball-milling for 30h to obtain a premix; the final mixing ball milling comprises the following steps: dividing the rest molybdenum powder into 4 times, mixing with the obtained premix, and ball-milling for 20h;
the density of the die is more than or equal to 65%;
(2) Carrying out hot isostatic pressing on the molybdenum-tungsten sheath obtained in the step (1) at 1400 ℃ and 180MPa for 4h, then cooling and depressurizing, and then carrying out heat treatment at 1200 ℃ for 6h to obtain a molybdenum-tungsten alloy blank;
(3) And (3) sequentially cutting and machining the molybdenum-tungsten alloy blank obtained in the step (2) to obtain the high-density molybdenum-tungsten alloy material.
Example 4
The embodiment provides a high-density molybdenum-tungsten alloy material, which is prepared from the following raw materials in parts by weight: 35% of molybdenum powder and 65% of tungsten powder;
the density of the high-density molybdenum-tungsten alloy material is 14.71g/cm 3 。
The preparation method of the high-density molybdenum-tungsten alloy material comprises the following steps:
(1) Ball-milling and mixing molybdenum powder and tungsten powder according to the weight ratio of the raw materials, then filling the mixture into a die, welding and packaging the mixture, and degassing the mixture at the temperature of 600 ℃ until the vacuum degree in the sheath is less than or equal to 1E-3Pa to obtain a molybdenum-tungsten sheath;
wherein the ball milling and mixing comprises premixing ball milling and final mixing ball milling which are sequentially carried out; the pre-mixing ball milling comprises the following steps: mixing tungsten powder and 50wt% molybdenum powder, and ball-milling for 26h to obtain a premix; the final mixing ball milling comprises the following steps: the rest molybdenum powder is divided into 5 times to be mixed with the obtained premix for ball milling for 19 hours;
the density of the die filling is more than or equal to 65 percent;
(2) Hot isostatic pressing the molybdenum-tungsten sheath obtained in the step (1) at 1350 ℃ and 190MPa for 6h, cooling and depressurizing, and then heat treating at 1260 ℃ for 5h to obtain a molybdenum-tungsten alloy blank;
(3) And (3) sequentially cutting and machining the molybdenum-tungsten alloy blank obtained in the step (2) to obtain the high-density molybdenum-tungsten alloy material.
Example 5
The embodiment provides a high-density molybdenum-tungsten alloy material, which is prepared from the following raw materials in parts by weight: 30% of molybdenum powder and 70% of tungsten powder;
the density of the high-density molybdenum-tungsten alloy material is 15.23g/cm 3 。
The preparation method of the high-density molybdenum-tungsten alloy material in the embodiment is different from that in the embodiment 1 only in that: in this example, the ball-milling mixing in step (1) was changed to one-step ball-milling mixing for 24h.
Example 6
The embodiment provides a high-density molybdenum-tungsten alloy material, which is prepared from the following raw materials in parts by weight: 30% of molybdenum powder and 70% of tungsten powder;
the density of the high-density molybdenum-tungsten alloy material is 15.23g/cm 3 。
The preparation method of the high-density molybdenum-tungsten alloy material in the embodiment is different from that in the embodiment 1 only in that: this example changed the temperature of hot isostatic pressing described in step (2) to 900 ℃.
Example 7
The embodiment provides a high-density molybdenum-tungsten alloy material, which is prepared from the following raw materials in parts by weight: 30% of molybdenum powder and 70% of tungsten powder;
the density of the high-density molybdenum-tungsten alloy material is 15.23g/cm 3 。
The preparation method of the high-density molybdenum-tungsten alloy material in the embodiment is different from that in the embodiment 1 only in that: this example changed the temperature of hot isostatic pressing described in step (2) to 1500 ℃.
Example 8
The embodiment provides a high-density molybdenum-tungsten alloy material, which is prepared from the following raw materials in parts by weight: 30% of molybdenum powder and 70% of tungsten powder;
the density of the high-density molybdenum-tungsten alloy material is 15.23g/cm 3 。
The preparation method of the high-density molybdenum-tungsten alloy material in the embodiment is different from that in the embodiment 1 only in that: this example changed the temperature of the heat treatment described in step (2) to 1150 ℃.
Example 9
The embodiment provides a high-density molybdenum-tungsten alloy material, which is prepared from the following raw materials in parts by weight: 30% of molybdenum powder and 70% of tungsten powder;
the density of the high-density molybdenum-tungsten alloy material is 15.23g/cm 3 。
The preparation method of the high-density molybdenum-tungsten alloy material in the embodiment is different from that in the embodiment 1 only in that: this example changed the temperature of the heat treatment described in step (2) to 1450 ℃.
Example 10
The embodiment provides a high-density molybdenum-tungsten alloy material, which is prepared from the following raw materials in parts by weight: 30% of molybdenum powder and 70% of tungsten powder;
the density of the high-density molybdenum-tungsten alloy material is 15.23g/cm 3 。
The preparation method of the high-density molybdenum-tungsten alloy material in the embodiment is different from that in the embodiment 1 only in that: in the present example, the time for the heat treatment in step (2) was changed to 1.5 hours.
Example 11
The embodiment provides a high-density molybdenum-tungsten alloy material, which is prepared from the following raw materials in parts by weight: 30% of molybdenum powder and 70% of tungsten powder;
the density of the high-density molybdenum-tungsten alloy material is 15.23g/cm 3 。
The preparation method of the high-density molybdenum-tungsten alloy material in the embodiment is different from that in the embodiment 1 only in that: this example changed the heat treatment time of step (2) to 6.5 hours.
Comparative example 1
The comparative example provides a high-density molybdenum-tungsten alloy material which is prepared from the following raw materials in parts by weight: 90% of molybdenum powder and 10% of tungsten powder;
the density of the high-density molybdenum-tungsten alloy material is 10.7g/cm 3 。
The preparation method of the high-density molybdenum-tungsten alloy material of the comparative example is the same as that of the example 1.
The high-density molybdenum-tungsten alloy materials provided in examples 1 to 11 and comparative example 1 were tested for relative density, purity, and microscopic grain size, and the test results are shown in table 1.
TABLE 1
In conclusion, the tungsten content of the high-density molybdenum-tungsten alloy material provided by the invention can reach 70% at most. The microscopic crystal grains are fine and uniform, the use requirements in the fields of industrial high-temperature furnaces, electronic light sources and LCD display coating films are completely met, and the method is simple, low in cost and convenient for batch production.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The high-density molybdenum-tungsten alloy material is characterized by being prepared from the following raw materials in parts by weight: 30-80% of molybdenum powder and 20-70% of tungsten powder;
the density of the high-density molybdenum-tungsten alloy material is 11.26-15.23 g/cm 3 。
2. The high-density molybdenum-tungsten alloy material according to claim 1, wherein the molybdenum powder has an average particle size of 1 to 3 μm;
preferably, the Mo content in the molybdenum powder is more than or equal to 99.96 percent;
preferably, the average particle size of the tungsten powder is 1 to 3 μm;
preferably, the W content in the tungsten powder is more than or equal to 99.96 percent.
3. A method for preparing the high-density molybdenum-tungsten alloy material as claimed in claim 1 or 2, wherein the method comprises the following steps:
(1) Ball-milling and mixing molybdenum powder and tungsten powder according to the weight ratio of the raw materials, and then sequentially carrying out die filling and degassing to obtain a molybdenum-tungsten sheath;
(2) Sequentially carrying out hot isostatic pressing and heat treatment on the molybdenum-tungsten sheath obtained in the step (1) to obtain a molybdenum-tungsten alloy blank;
(3) And (3) carrying out post-treatment on the molybdenum-tungsten alloy blank obtained in the step (2) to obtain the high-density molybdenum-tungsten alloy material.
4. The preparation method according to claim 3, wherein the ball milling and mixing in step (1) comprises a pre-mixing ball milling and a final mixing ball milling which are sequentially carried out;
preferably, the pre-mix ball mill is: mixing tungsten powder and part of molybdenum powder, and performing ball milling to obtain a premix;
preferably, the part of the molybdenum powder accounts for 30-70 wt% of the total mass of the molybdenum powder;
preferably, the time of the premixed ball milling is 10 to 30 hours;
preferably, the final ball mill is: mixing the rest molybdenum powder with the obtained premix for ball milling for at least two times;
preferably, the time of the final mixing ball milling is 10 to 30 hours.
5. The preparation method according to claim 3 or 4, wherein the compactness of the mold in the step (1) is more than or equal to 65 percent;
preferably, the step (1) is performed with soldering and packaging after the mold filling.
6. The method according to any one of claims 3 to 5, wherein the degassing in step (1) is carried out at a temperature of 300 to 700 ℃;
preferably, the end point of the degassing in the step (1) is that the vacuum degree in the sheath is less than or equal to 1E-3Pa.
7. The method of any one of claims 3-6, wherein the hot isostatic pressing in step (2) is performed at a temperature of 1000-1400 ℃;
preferably, the hot isostatic pressing pressure in the step (2) is 180-200 MPa;
preferably, the hot isostatic pressing time in the step (2) is 4-6 h;
preferably, the hot isostatic pressing in step (2) further comprises a cooling and depressurizing process.
8. The method according to any one of claims 3 to 7, wherein the temperature of the heat treatment in the step (2) is 1200 to 1400 ℃;
preferably, the time of the heat treatment in the step (2) is 2 to 6 hours.
9. The method according to any one of claims 3 to 8, wherein the post-treatment of step (3) comprises cutting and machining performed sequentially.
10. The method according to any one of claims 3 to 9, characterized by comprising the steps of:
(1) Ball-milling and mixing molybdenum powder and tungsten powder according to the weight ratio of the raw materials, then filling the mixture into a die, welding and packaging the mixture, and degassing the mixture at the temperature of 300-700 ℃ until the vacuum degree in the sheath is less than or equal to 1E-3Pa to obtain a molybdenum-tungsten sheath;
wherein the ball milling and mixing comprises premixing ball milling and final mixing ball milling which are sequentially carried out; the pre-mixing ball milling comprises the following steps: mixing tungsten powder and part of molybdenum powder, and performing ball milling for 10-30 h to obtain a premix; the weight of the part of molybdenum powder is 30-70 wt% of the total weight of the molybdenum powder; the final mixing ball milling comprises the following steps: the rest molybdenum powder is divided into at least two times to be mixed with the obtained premix and ball-milled for 10 to 30 hours;
the density of the die filling is more than or equal to 65 percent;
(2) Carrying out hot isostatic pressing on the molybdenum-tungsten sheath obtained in the step (1) at the temperature of 1000-1400 ℃ and under the pressure of 180-200 MPa for 4-6 h, then cooling and depressurizing, and then carrying out heat treatment at the temperature of 1200-1400 ℃ for 2-6 h to obtain a molybdenum-tungsten alloy blank;
(3) And (3) sequentially cutting and machining the molybdenum-tungsten alloy blank obtained in the step (2) to obtain the high-density molybdenum-tungsten alloy material.
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