CN116287833A - Preparation method of in-situ authigenic two-dimensional carbide dispersion strengthening and toughening molybdenum alloy - Google Patents

Preparation method of in-situ authigenic two-dimensional carbide dispersion strengthening and toughening molybdenum alloy Download PDF

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CN116287833A
CN116287833A CN202310238874.XA CN202310238874A CN116287833A CN 116287833 A CN116287833 A CN 116287833A CN 202310238874 A CN202310238874 A CN 202310238874A CN 116287833 A CN116287833 A CN 116287833A
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molybdenum alloy
molybdenum
dimensional
carbide dispersion
dispersion strengthening
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杨璐
魏世忠
郑鑫园
王晓东
邓锐
梁栋
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Henan University of Science and Technology
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    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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    • 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
    • B22F3/02—Compacting only
    • B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
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    • 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
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0005—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with at least one oxide and at least one of carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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

Abstract

The invention relates to a preparation method of in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy, moO 2 And two dimensionsAnd (3) mixing and sieving the MAX ceramic material, then carrying out high-temperature hydrogen reduction to prepare molybdenum alloy precursor powder, then selecting a cold isostatic press to compact, carrying out pressureless sintering and high-temperature calcination, carrying out thermoplastic processing, and finally carrying out annealing treatment to obtain the high-strength and high-toughness molybdenum alloy. According to the invention, the two-dimensional MAX ceramic material is used as a doping phase, the two-dimensional carbide generated in situ by MAX at high temperature has large specific surface area and high surface energy, and can promote densification of the material, so that mechanical properties such as strength and toughness of the molybdenum alloy are improved, movement and deformation of a grain boundary at high temperature are effectively prevented, microstructure of the material at high temperature is more stable, high-temperature strength of the molybdenum alloy at 1200 ℃ is more than 300MPa, and recrystallization temperature is up to 1500 ℃, so that performance of the molybdenum alloy at high-temperature scene is improved, and application range of the molybdenum alloy is enlarged.

Description

Preparation method of in-situ authigenic two-dimensional carbide dispersion strengthening and toughening molybdenum alloy
Technical Field
The invention belongs to the technical field of powder metallurgy, and particularly relates to a preparation method of in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy.
Background
Molybdenum metal is one of the most widely used refractory metal materials in industry. Since molybdenum has a high melting point (2620.+ -. 20 ℃ C.), a high density (10.2 g/cm) 3 ) High elastic modulus (280-390 GPa), low linear thermal expansion coefficient (5.8X10) -6 ～6.2×10 -6 K), high wear resistance, good electric conduction and heat conduction performance, good acid and alkali resistance, liquid metal corrosion resistance and the like, and molybdenum and the alloy thereof have wide application prospects in various industrial fields of iron and steel, metallurgy, machinery, chemical industry, nuclear energy, electronics, aerospace and the like as high-temperature-resistant structural materials and functional materials. Molybdenum metals and alloys thereof, while possessing many performance advantages, still have insufficient room temperature and high temperature strength to meet the rapidly evolving needs of technology for high temperature resistant structural materials. In particular, the low room temperature ductility of molybdenum metal results in poor processability, which severely limits its industrial application.
Oxide (La) 2 O 3 、Ce 2 O 3 、Y 2 O 3 、ZrO 2 、Al 2 O 3 ) And carbide (TiC, zrC, hfC, taC) are commonA reinforcing phase for reinforcing the molybdenum alloy. For example, adding the oxide Al to a molybdenum matrix 2 O 3 Can obviously improve the hardness and the wear resistance of the molybdenum alloy, and La is added into the molybdenum matrix 2 O 3 Can prepare high-strength and high-toughness molybdenum alloy with yield strength reaching 813MPa, and can also obtain higher fracture toughness (121.5 MPa.m 2 ) And the elongation (37.5%), the addition of rare earth oxide can also raise the recrystallization temperature of molybdenum alloy, make molybdenum alloy have better high-temperature creep resistance; if carbide TiC particles are further added to the TZM alloy, it was found that the addition of 5vol.% TiC particles increased the vickers hardness of the alloy by 50%, while the flexural strength was increased by 46%, but the ductility of the alloy was reduced. The performance of the molybdenum alloy is improved by adding the oxide, the size of the oxide particles is in the nanometer level, the particles are dispersed and uniformly distributed in the molybdenum crystal grains, the process is complex, the equipment requirement is high, and the large-scale application is not easy to realize. The carbide is required to have high melting point, high hardness and high chemical stability when being added to improve the high-temperature mechanical property, and the properties of the carbide are closely related to component control, deformation process, heat treatment process and the like, so that the carbide is required to be high and difficult to control.
The design principle of the novel high-performance molybdenum material comprises the following steps: 1) Improving low-temperature brittleness and reducing DBTT of alloy; 2) The recrystallization temperature is improved, and the mechanical property and the structural stability at high temperature are improved; 3) Improving the radiation embrittlement resistance. Conventional ex situ synthesized composite materials are often accompanied by the following disadvantages: residual porosity, large grain size, non-uniform distribution of reinforcing phase, poor wettability, weak bonding interface of reinforcing phase with matrix, etc.
M n+1 AX n The phase (where M is an early transition metal, a is a group a element, X is C or N) is a layered hexagonal solid, and the unique crystal structure of the MAX phase imparts its unique chemical bond characteristics: m and X are combined by strong covalent bonds and ionic bonds; the combination of M and A with weaker covalent or metallic bonds makes MAX compatible and easy to follow the basal plane [0001 ]]Slippage occurs. This unique bonding configuration combines the advantages of ceramic and metallic materials, such as high modulus, low specific gravity, good electrical and thermal conductivity, processability, resistance toThermal shock resistance, high damage tolerance, thermal stability, creep resistance and oxidation resistance. The existing strengthening technology of molybdenum alloy can not simultaneously have high strength, high toughness and high temperature stability at room temperature and high temperature, and restricts the application in high temperature scenes such as nuclear reactors, so that the comprehensive mechanical property and high temperature stability of the molybdenum alloy are required to be further improved in order to meet the use requirement.
Disclosure of Invention
The invention aims to provide a preparation method of an in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy, which is used for improving the room temperature and high temperature strength of the molybdenum alloy, increasing the elongation rate of the molybdenum alloy, refining the particle size of powder, further improving the density of the powder and synchronously improving the toughness and strength of the molybdenum alloy.
The invention is realized by the following technical scheme, and the preparation method of the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy provided by the invention comprises the following steps:
(1): weighing a certain amount of MoO according to the requirement of the final product 2 And two-dimensional MAX ceramic material, adopting a double-power mixer to dry mix for 10-30 h, and sieving for standby;
(2): carrying out high-temperature reduction on the powder prepared in the step (1) in a reducing gas hydrogen atmosphere, wherein the reduction temperature is 700-1000 ℃ and the hydrogen flow is 10-20 m 3 And/h, reducing for 8-25 h, wherein the powder laying height is less than or equal to 2/3, so as to prepare molybdenum alloy precursor powder;
(3): selecting a proper rubber mold according to the required size of a final product, weighing a certain amount of prepared molybdenum alloy precursor powder, loading the molybdenum alloy precursor powder into the rubber mold, and selecting a cold isostatic press for compacting;
(4): carrying out pressureless sintering on the pressed compact obtained in the step (3) under reducing gas, and cooling along with a furnace to obtain a molybdenum alloy sintered blank;
(5): heating the molybdenum alloy sintered blank prepared in the step (4) to 1100-1600 ℃ under a protective atmosphere hydrogen atmosphere (aiming at preventing molybdenum from oxidizing), preserving heat for 30-60 min, and then carrying out thermoplastic processing;
(6): and (3) annealing the molybdenum alloy blank prepared in the step (5) in a protective atmosphere hydrogen atmosphere (aiming at preventing molybdenum from oxidizing), and finally obtaining the high-strength and high-toughness molybdenum alloy, namely the in-situ authigenic two-dimensional carbide dispersion strengthening and toughening molybdenum alloy.
Preferably, the molybdenum dioxide used in the step (1) has a particle size of 8-20 mu m and the impurity potassium content is 5-10 ppm; the two-dimensional MAX ceramic material is lamellar Ti 3 AlC 2 The number of layers is 3-10, the purity is not less than 98%, and the grain diameter is 2-8 μm.
Further, the particle size of the molybdenum alloy precursor powder obtained in the step (2) is 1-2 mu m.
Preferably, the pressure of the cold isostatic pressing compact in the step (3) is 150-230 MPa, and the pressure maintaining time is 10-30 min.
Preferably, the pressureless sintering temperature in the step (4) is 1700-2100 ℃, the heat preservation time is 6-10 h, and the hydrogen flow is 8-15 m 3 And (h) cooling along with the furnace to obtain the molybdenum alloy sintered blank.
Further, in the step (5), the thermoplastic processing is one or a combination of a plurality of rotary forging, rolling, extruding or drawing; the total times of thermoplastic processing is 3-10 times, the deformation of each pass is 15-25%, and the total deformation is more than or equal to 50%.
Preferably, the annealing temperature in the step (6) is 900-1500 ℃, and the heat preservation time is 30-200 min.
Further, the prepared in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy comprises molybdenum crystal grains and nano TiC uniformly distributed in the molybdenum crystal grains 0.67 Wherein, the average grain diameter of the molybdenum crystal grain is 10-20 mu m, and the nano TiC is uniformly distributed in the molybdenum crystal grain 0.67 The average particle diameter of (2) is 0.5 to 3 mu m.
The invention can also adopt the method to make MoO 2 Replacement to WO 3 Preparing in-situ autogenous two-dimensional carbide dispersion strengthening tungsten alloy; or MoO is to 2 Replacing the copper alloy with CuO to prepare in-situ authigenic two-dimensional carbide dispersion strengthening copper alloy; or MoO is to 2 The nickel alloy is replaced by NiO to prepare in-situ authigenic two-dimensional carbide dispersion strengthening nickel alloy, so that the invention is expanded and applied.
Further, the steps of(1) The two-dimensional MAX ceramic material in the ceramic material can also be Zr 3 AlC 2 、Si 3 AlC 2 、Hf 3 AlC 2 、Zr 2 AlC、Si 2 AlC、Hf 2 AlC 2 、Zr 4 AlC 3 、Si 4 AlC 3 、Hf 4 AlC 3 Any one or more of them, not limited to Ti 3 AlC 2 。
Compared with the prior art, the invention has obvious advantages and beneficial effects, and at least has the following advantages:
(1) According to the invention, MAX phase materials with high melting point, high hardness and high fracture toughness are used as doping phases, and the high-strength and toughness molybdenum alloy is obtained by controlling the mass ratio of molybdenum dioxide to two-dimensional MAX materials, reducing initial powder by hydrogen, cold isostatic pressing, pressureless sintering by introducing hydrogen, thermoplastic treatment and annealing. The enhanced phase MAX material is selectively etched to remove Al under high temperature sintering, and is decomposed into Al and two-dimensional Mxene material (TiC) 0.67 ) Al generates alumina by absorbing impurity oxygen, and alumina particles and carbide generated by in-situ reaction decomposition are dispersed in a molybdenum matrix. Wherein, al decomposed in situ reduces the brittleness of the alloy by absorbing impurity oxygen to generate alumina, while the other Mxene particles generated in situ are finer, have large specific surface area and high surface energy, and can promote the densification of the material, thereby improving the mechanical properties of molybdenum alloy such as yield strength, fracture toughness and the like; and the Mxene particles generated by in-situ reaction have better thermal stability and are mainly distributed on the grain boundary, so that the movement and deformation of the grain boundary at high temperature are effectively prevented, the microstructure of the material at high temperature is more stable, the molybdenum alloy has good high-temperature strength and high recrystallization temperature, the performance of the molybdenum alloy in a high-temperature scene is improved, and the application range of the molybdenum alloy is enlarged.
(2) The appearance and granularity of the molybdenum powder have inheritance on the performance of the molybdenum alloy, and the appearance evolution of the particle aggregate has obvious inheritance phenomenon and is accompanied with a certain degree of variation according to the inheritance concept in biology; for the morphology of single particles, each generation has the intrinsic characteristics of itself, and the variation is dominantStatus, there is basically no genetic phenomenon; the genetic characteristic of the Fisher size is that the raw material particles are coarser, and the corresponding product particles are coarser; the raw material particles are finer, and the corresponding product particles are finer; the inheritance of impurity elements has obvious characteristics, the elements which are easy to volatilize and are easy to pollute are mainly mutated in the reduction process, and other impurity elements which are difficult to volatilize and are not polluted are mainly inherited. The invention is realized by the method that in MoO 2 Fine secondary phase elements are introduced in the particle aggregation, so that the inheritance of the particle aggregation is broken. Controlling MoO 2 The process of reducing Mo is mainly based on internal diffusion, the apparent activation energy of the step is 30.1kJ/mol, and the MoO is small particles 2 The transition of (2) follows a chemical vapor migration model. Due to the introduction of the secondary phase, the Mo powder is over-burned, and the edge is arcing, so that the Mo powder is nearly spheroidized. The invention prepares the fine and uniform molybdenum powder with the Fisher particle size of 1-2 mu m and the apparent density of 0.7-0.9 g/cm 3 。
(3) The invention can further refine grains and improve the compactness and performance of the molybdenum alloy through a thermoplastic deformation process. The microstructure of the in-situ self-generated two-dimensional carbide dispersion strengthening molybdenum alloy prepared by the method comprises molybdenum grains and nano TiC uniformly distributed in the molybdenum grains 0.67 Wherein the average width of the molybdenum crystal grains is 10-20 mu m, and nano TiC which is uniformly distributed in the molybdenum crystal grains 0.67 The average particle diameter of the particles is 0.5-3 mu m.
(4) The molybdenum alloy has excellent comprehensive performance and outstanding high-temperature performance, the preparation method is green and efficient, can be used for large-scale production, can be used for manufacturing large-size products, has great industrial application value, and has very good application prospects in nuclear reactors, aerospace key parts and the like.
Drawings
FIG. 1 is an SEM image of a molybdenum alloy precursor powder prepared according to example 1;
FIG. 2 is a schematic diagram of the in-situ two-dimensional carbide dispersion strengthened molybdenum alloy prepared in example 1;
FIG. 3 is a schematic diagram of an optical lens gold phase of an in situ autogenous two-dimensional carbide dispersion strengthened molybdenum alloy prepared in example 2;
FIG. 4 is a schematic diagram of the in-situ two-dimensional carbide dispersion strengthened molybdenum alloy prepared in example 3;
FIG. 5 is a stress-strain curve of in-situ self-generated two-dimensional carbide dispersion strengthened molybdenum alloy prepared in example 1-example 3 and pure molybdenum;
FIG. 6 is a high temperature stress strain curve of the in situ self-generated two-dimensional carbide dispersion strengthened molybdenum alloy prepared in example 1-example 3 and pure molybdenum at 1200 ℃.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The invention provides a preparation method of in-situ authigenic two-dimensional carbide dispersion strengthening and toughening molybdenum alloy, which mainly comprises the following steps:
(1): weighing a certain amount of MoO according to the requirement of the final product 2 And Ti is 3 AlC 2 Dry-mixing the powder for 10-30 hours by adopting a double-power mixer, and sieving for standby; the grain diameter of the molybdenum dioxide is 8-20 mu m, and the content of impurity potassium is 5-10 ppm; ti (Ti) 3 AlC 2 The layer is lamellar, the number of layers is 3-10, the purity is not less than 98%, and the grain diameter is 2-8 mu m;
(2): carrying out high-temperature reduction on the powder prepared in the step (1) in a reducing gas hydrogen atmosphere, wherein the reduction temperature is 700-1000 ℃ and the hydrogen flow is 10-20 m 3 Preparing molybdenum alloy precursor powder with the particle size of 1-2 mu m, wherein the reduction time is 8-25 h, and the powder laying height is less than or equal to 2/3;
(3): according to the required size of the final product, selecting a proper rubber mold, weighing a certain amount of prepared molybdenum alloy precursor powder, loading the molybdenum alloy precursor powder into the rubber mold, and selecting a cold isostatic press for compacting, wherein the pressure is 150-230 MPa, and the pressure maintaining time is 10-30 min.
(4): pressureless sintering is carried out on the pressed compact obtained in the step (3) under reducing gas hydrogen, the sintering temperature is 1700-2100 ℃, the heat preservation time is 6-10 h, and the hydrogen flow is 8-15 m 3 And (h) cooling along with the furnace to obtain a molybdenum alloy sintered blank; the grain size of molybdenum crystal grains in the molybdenum alloy is about 20-50 mu m;
(5): heating the molybdenum alloy blank prepared in the step (4) to 1100-1500 ℃ in a protective gas hydrogen atmosphere (aiming at preventing molybdenum oxidation), preserving heat for 15-60 min, and then performing thermoplastic processing, wherein the thermoplastic processing is one or a combination of a plurality of rotary forging, rolling, extrusion or drawing, the total times of the thermoplastic deformation processing are 3-10 times, the deformation amount of each pass is 15-25%, and the total deformation amount is more than or equal to 50%.
(6): and (3) annealing the molybdenum alloy blank prepared in the step (5) in a protective gas hydrogen atmosphere, wherein the annealing temperature is 900-1500 ℃, and the heat preservation is carried out for 30-200 min, so that the high-strength and high-toughness molybdenum alloy, namely the in-situ authigenic two-dimensional carbide dispersion strengthening and toughening molybdenum alloy, is finally obtained.
The microstructure of the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy prepared by the method comprises molybdenum crystal grains and nano TiC uniformly distributed in the molybdenum crystal grains 0.67 Wherein the average width of the molybdenum crystal grains is 10-20 mu m, and nano TiC which is uniformly distributed in the molybdenum crystal grains 0.67 The average particle diameter of the particles is 0.5-3 mu m.
As a further preference, moO in step (1) 2 Is based on MoO 2 And Ti is 3 AlC 2 95 to 99.5 percent of the total mass of the mixed powder, ti 3 AlC 2 Is based on MoO 2 And Ti is 3 AlC 2 0.5 to 5 percent of the total mass of the mixed powder.
The invention adopts the method to obtain the in-situ self-generated two-dimensional carbide dispersion strengthening molybdenum alloy, and in other embodiments, the two-dimensional MAX ceramic material Ti 3 AlC 2 Is replaced by 312-phase MAX-phase ceramic (Zr) 3 AlC 2 Or Si (or) 3 AlC 2 Or Hf 3 AlC 2 ) MAX phase ceramic (Zr) of 211 phase 2 AlC or Si 2 AlC or Hf 2 AlC 2 ) And 413 phase MAX phase ceramic (Zr) 4 AlC 3 Or Si (or) 4 AlC 3 Or Hf 4 AlC 3 ) Any one or more of these can also be obtained in situ, self-generated two-dimensional carbide dispersion strengthening molybdenum alloys, but the strengthening phase carbide is changed, and the alternative is easily understood by those skilled in the art, and the invention is not repeated.
At the same time, by changing the raw material MoO 2 The method can also be used for preparing in-situ self-generated two-dimensional carbide dispersion strengthening tungsten alloy, copper alloy or nickel alloy, for example, WO can be selected as a metal matrix material when preparing in-situ self-generated two-dimensional carbide dispersion strengthening tungsten alloy 3 The metal matrix material used for preparing the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening copper alloy can be CuO, and the metal matrix material used for preparing the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening nickel alloy can be NiO, and the preparation method is the same as the preparation method of the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy, and the invention is not repeated.
The following is a detailed description of specific embodiments:
example 1
(1): according to the requirements of the final product, 99 parts of MoO is calculated according to parts by weight 2 And 1 part of Ti 3 AlC 2 Putting the powder into a double-power mixer for dry mixing for 20 hours, and sieving with a 300-mesh sieve for standby;
(2): carrying out high-temperature reduction on the powder obtained in the step (1) in a reducing gas hydrogen atmosphere, wherein the reduction temperature is 800 ℃ and the hydrogen flow is 18m 3 Preparing molybdenum alloy precursor powder with the particle size of 1-2 mu m, wherein the reduction time is 22h and the powder laying height is 2/3;
(3): according to the required size of the final product, selecting a proper rubber mold, weighing a certain amount of prepared molybdenum alloy precursor powder, loading the molybdenum alloy precursor powder into the rubber mold, and selecting a cold isostatic press for compacting, wherein the pressure is 200MPa, and the pressure maintaining time is 15min.
(4): carrying out pressureless sintering on the pressed compact obtained in the step (3) under reducing gas hydrogen, wherein the sintering temperature is 2000 ℃, the heat preservation time is 10 hours, and cooling along with a furnace to obtain a molybdenum alloy sintered compact; the grain size of molybdenum crystal grains in the molybdenum alloy is about 35-50 mu m;
(5): heating the molybdenum alloy blank prepared in the step (4) to 1200 ℃ under the hydrogen atmosphere of a protective atmosphere, preserving heat for 60min, and then performing thermoplastic processing, wherein the thermoplastic processing is rolling, the total times of the thermoplastic deformation processing are 5 times, the deformation amount of each time is 25%, and the total deformation amount is 76.23%.
(6): annealing the molybdenum alloy blank prepared in the step (5) in a protective atmosphere hydrogen atmosphere at the annealing temperature of 1000 ℃ for 160min, and finally obtaining the high-strength and high-toughness molybdenum alloy, namely the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy, wherein the grain diameter of the molybdenum alloy blank is 12-20 mu m, and the secondary phase TiC is uniformly dispersed in molybdenum grains 0.67 The grain diameter of the particles is 0.5-3 mu m, and the density of the molybdenum alloy is 99%.
The room temperature mechanical property of the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy prepared in the embodiment is tested by an American INSTRON-5967 universal testing machine, and the high temperature compressive strength of the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy is tested by an American Gleeble-1500D thermal simulation testing machine, wherein the room temperature tensile strength of the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy obtained in the embodiment is 809MPa, the elongation is 47.8%, the high temperature compressive strength of 1200 ℃ is 320MPa, and compared with pure molybdenum, the room temperature mechanical property of the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy is respectively improved by 72.1%, 91.2% and 113.3%, so that the strength of the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy is not reduced while the plastic toughness of the molybdenum alloy is improved.
FIG. 1 is a morphology diagram of the molybdenum alloy precursor powder prepared in step (2) of this example, which is known to be a nearly spherical powder of 1 to 2. Mu.m.
FIG. 2 is a structural morphology diagram (optical glass phase diagram) of an in-situ self-generated two-dimensional carbide dispersion strengthening molybdenum alloy prepared in the embodiment, wherein the grain diameter of the molybdenum alloy is 12-20 mu m, larger secondary phases are uniformly distributed at grain boundaries, and fine secondary phase particles are uniformly distributed in the grains.
Example 2
(1): according to the requirements of the final product, 98.5 parts of MoO is added according to parts by weight 2 And 1.5 parts of Ti 3 AlC 2 Putting the powder into a double-power mixer for dry mixing for 20 hours, and sieving with a 300-mesh sieve for standby;
(2)：carrying out high-temperature reduction on the powder obtained in the step (1) in a reducing gas hydrogen atmosphere, wherein the reduction temperature is 900 ℃ and the hydrogen flow is 20m 3 Reducing time is 18h, and powder laying height is less than or equal to 2/3, so as to prepare molybdenum alloy precursor powder with particle size of 1-2 mu m;
(3): according to the required size of the final product, selecting a proper rubber mold, weighing a certain amount of prepared molybdenum alloy precursor powder, loading the molybdenum alloy precursor powder into the rubber mold, and selecting a cold isostatic press for compacting, wherein the pressure is 200MPa, and the pressure maintaining time is 15min.
(4): carrying out pressureless sintering on the pressed compact obtained in the step (3) under reducing gas hydrogen, wherein the sintering temperature is 1900 ℃, the heat preservation time is 10 hours, and cooling along with a furnace to obtain a molybdenum alloy sintered compact; the grain size of molybdenum crystal grains in the molybdenum alloy is about 25-35 mu m;
(5): heating the molybdenum alloy blank prepared in the step (4) to 1300 ℃ under a protective atmosphere hydrogen atmosphere (aiming at preventing molybdenum from oxidizing), preserving heat for 60min, and then performing thermoplastic processing, wherein the thermoplastic processing is one or a combination of a plurality of rotary forging, rolling, extruding or drawing, the total number of times of thermoplastic deformation processing is 8, the deformation amount of each time is 20%, and the total deformation amount is 83.22%.
(6): annealing the molybdenum alloy blank prepared in the step (5) in a protective atmosphere of hydrogen, wherein the annealing temperature is 1100 ℃, and preserving heat for 160min to finally obtain the high-strength and high-toughness molybdenum alloy, namely the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy, wherein the grain diameter of the molybdenum alloy blank is 10-15 mu m, and the secondary phase TiC is uniformly dispersed in molybdenum grains 0.67 The grain diameter of the particles is 0.5-3 mu m, and the density of the molybdenum alloy is 99.2%.
The room temperature mechanical property and the high temperature compressive strength of the in-situ self-generated two-dimensional carbide dispersion strengthening molybdenum alloy prepared in the embodiment are tested by adopting the method described in the embodiment 1, the room temperature tensile strength is 1024MPa, the elongation is 48.5%, the high temperature compressive strength at 1200 ℃ is 335MPa, 118%, 94% and 123.3% are respectively improved compared with pure molybdenum metal, and the strength is not reduced while the plastic toughness of the molybdenum alloy is improved.
FIG. 3 is a structural morphology diagram (optical glass phase diagram) of an in-situ self-generated two-dimensional carbide dispersion strengthening molybdenum alloy prepared in the embodiment, wherein the grain diameter of the molybdenum alloy is 10-15 mu m, larger secondary phases are uniformly distributed at grain boundaries, and fine secondary phase particles are uniformly distributed in the grains.
Example 3
(1): according to the requirements of the final product, 98 parts of MoO are calculated according to parts by weight 2 And 2 parts of Ti 3 AlC 2 Putting the powder into a double-power mixer for dry mixing for 20 hours, and sieving with a 300-mesh sieve for standby;
(2): carrying out high-temperature reduction on the powder obtained in the step (1) in a reducing gas hydrogen atmosphere, wherein the reduction temperature is 1000 ℃ and the hydrogen flow is 15m 3 Reducing time is 20h, and powder laying height is less than or equal to 2/3, so as to prepare molybdenum alloy precursor powder with particle size of 1-2 mu m;
(3): according to the required size of the final product, selecting a proper rubber mold, weighing a certain amount of prepared molybdenum alloy precursor powder, loading the molybdenum alloy precursor powder into the rubber mold, and selecting a cold isostatic press for compacting, wherein the pressure is 200MPa, and the pressure maintaining time is 15min.
(4): carrying out pressureless sintering on the pressed compact obtained in the step (3) under reducing gas hydrogen, wherein the sintering temperature is 1800 ℃, the heat preservation time is 10 hours, and cooling along with a furnace to obtain a molybdenum alloy sintered compact; the grain size of molybdenum crystal grains in the molybdenum alloy is about 20-35 mu m;
(5): heating the molybdenum alloy blank prepared in the step (4) to 1400 ℃ under a protective atmosphere hydrogen atmosphere (aiming at preventing molybdenum from oxidizing), preserving heat for 60min, and then performing thermoplastic processing, wherein the thermoplastic processing is one or a combination of a plurality of rotary forging, rolling, extruding or drawing, the total number of times of thermoplastic deformation processing is 10, the deformation amount of each time is 25%, and the total deformation amount is 94.5%.
(6): annealing the molybdenum alloy blank prepared in the step (5) in a protective atmosphere hydrogen atmosphere at 1300 ℃, and preserving heat for 160min to finally obtain the high-strength and high-toughness molybdenum alloy, namely the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy, wherein the grain diameter of the molybdenum alloy blank is 10-12 mu m, and the secondary phase TiC is uniformly dispersed in molybdenum grains 0.67 The grain diameter of the particles is 0.5-3 mu m, and the density of the molybdenum alloy is 99.4%.
The room temperature mechanical property and the high temperature compressive strength of the in-situ self-generated two-dimensional carbide dispersion strengthening molybdenum alloy prepared in the embodiment are tested by adopting the method described in the embodiment 1, the room temperature tensile strength is 1305MPa, the elongation is 47.9%, the high temperature compressive strength at 1200 ℃ is 415MPa, and compared with pure molybdenum, 177.6%, 91.6% and 176.6% of the high temperature compressive strength are respectively improved, so that the strength is not reduced while the toughness of the molybdenum alloy plastic is improved.
FIG. 4 is a structural morphology diagram (optical glass phase diagram) of an in-situ self-generated two-dimensional carbide dispersion strengthening molybdenum alloy prepared in the embodiment, wherein the grain diameter of the molybdenum alloy is 10-12 mu m, larger secondary phases are uniformly distributed at grain boundaries, and fine secondary phase particles are uniformly distributed in the grains.
Comparative example 1
In the step (1), ti is not added 3 AlC 2 The other steps are the same as in example 1, a molybdenum product is obtained, the test is carried out according to the test method of example 1, the grain diameter of the prepared pure molybdenum is 70-100 mu m, the compactness is 96%, the room temperature tensile strength is 470MPa, the elongation is 25%, and the high temperature compressive strength at 1200 ℃ is 150MPa.
FIG. 5 is a plot of stress strain for the in situ autogenous two-dimensional carbide dispersion strengthened molybdenum alloy obtained in each example versus the pure molybdenum obtained in comparative example 1, with the tensile strength slightly different from the molybdenum alloy obtained in the different processes of the examples, but with the overall strength higher than that of the pure molybdenum.
FIG. 6 shows the high temperature stress strain curves of the in situ self-generated two-dimensional carbide dispersion strengthening molybdenum alloy obtained in each example and the pure molybdenum obtained in comparative example 1 at 1200 ℃, and the compressive strength of the molybdenum alloy obtained in different processes of the examples is greatly improved compared with that of the pure molybdenum at 1200 ℃.
Comparative example 2
Molybdenum dioxide and lanthanum oxide are added in the step (1), and other steps are the same as those of the example 1 to obtain a molybdenum product, and the molybdenum alloy prepared by testing according to the testing method of the example 1 has the particle size of 30-50 mu m, the compactness of 97%, the room-temperature tensile strength of 653MPa, the elongation of 20% and the high-temperature compressive strength of 210MPa at 1200 ℃, and has improved strength but poorer plasticity and toughness compared with the pure molybdenum of the comparative example 1.
The foregoing is merely an embodiment of the present invention, and the present invention is not limited in any way, and may have other embodiments according to the above structures and functions, which are not listed. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention without departing from the scope of the technical solution of the present invention will still fall within the scope of the technical solution of the present invention.

Claims (10)

1. The preparation method of the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy is characterized by comprising the following steps of:
(1): weighing a certain amount of MoO according to the requirement of the final product 2 And two-dimensional MAX ceramic material, adopting a double-power mixer to dry mix for 10-30 h, and sieving for standby;
(2): carrying out high-temperature reduction on the powder prepared in the step (1) in a hydrogen atmosphere, wherein the reduction temperature is 700-1000 ℃ and the hydrogen flow is 10-20 m 3 And/h, reducing for 8-25 h, wherein the powder laying height is less than or equal to 2/3, so as to prepare molybdenum alloy precursor powder;
(3): selecting a proper rubber mold according to the required size of a final product, weighing a certain amount of prepared molybdenum alloy precursor powder, loading the molybdenum alloy precursor powder into the rubber mold, and selecting a cold isostatic press for compacting;
(4): carrying out pressureless sintering on the pressed compact obtained in the step (3) in a hydrogen atmosphere, and cooling along with a furnace to obtain a molybdenum alloy sintered blank;
(5): heating the molybdenum alloy sintered blank obtained in the step (4) to 1100-1600 ℃ in a hydrogen atmosphere, preserving heat for 30-60 min, and then carrying out thermoplastic processing;
(6): annealing the molybdenum alloy blank obtained in the step (5) in a hydrogen atmosphere to finally obtain the in-situ authigenic two-dimensional carbide dispersion strengthening and toughening molybdenum alloy.
2. The method for preparing in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy according to claim 1, wherein the molybdenum dioxide used in the step (1) has a particle size of 8-20 μm and the impurity potassium content is 5-10 ppm; the two-dimensional MAX ceramic material is lamellar Ti 3 AlC 2 The number of layers is 3-10, the purity is not less than 98%, and the grain diameter is 2-8 μm.
3. The method for preparing the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy according to claim 1 or 2, wherein the particle size of the molybdenum alloy precursor powder obtained in the step (2) is 1-2 μm.
4. The method for preparing an in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy according to claim 1, wherein the pressure of the cold isostatic pressing compact in the step (3) is 150-230 MPa, and the dwell time is 10-30 min.
5. The method for preparing in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy according to claim 1, wherein the pressureless sintering temperature in the step (4) is 1700-2100 ℃, the heat preservation time is 6-10 h, and the hydrogen flow is 8-15 m 3 And (h) cooling along with the furnace to obtain the molybdenum alloy sintered blank.
6. The method for preparing an in-situ self-generated two-dimensional carbide dispersion strengthening molybdenum alloy according to claim 1, wherein the hot plastic working in the step (5) is one or a combination of a plurality of rotary forging, rolling, extrusion or drawing; the total times of thermoplastic processing is 3-10 times, the deformation of each pass is 15-25%, and the total deformation is more than or equal to 50%.
7. The method for preparing the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy according to claim 1, wherein the annealing temperature in the step (6) is 900-1500 ℃, and the heat preservation time is 30-200 min.
8. The method for preparing an in-situ self-generated two-dimensional carbide dispersion strengthened molybdenum alloy according to claim 1 or 2, wherein the prepared in-situ self-generated two-dimensional carbide dispersion strengthened molybdenum alloy comprises molybdenum grains and nano TiC uniformly distributed in the molybdenum grains 0.67 The average grain diameter of the molybdenum crystal grain is 10-20 mu m, and nano TiC which is uniformly distributed in the molybdenum crystal grain 0.67 The average particle diameter of (2) is 0.5 to 3 mu m.
9. The method for preparing the in-situ self-generated two-dimensional carbide dispersion strengthening and toughening molybdenum alloy according to claim 1, wherein MoO is prepared according to the method 2 Replacement to WO 3 Preparing in-situ autogenous two-dimensional carbide dispersion strengthening tungsten alloy;
or MoO is to 2 Replacing the copper alloy with CuO to prepare in-situ authigenic two-dimensional carbide dispersion strengthening copper alloy;
or MoO is to 2 And replacing NiO to prepare the in-situ authigenic two-dimensional carbide dispersion strengthening nickel alloy.
10. The method for preparing in-situ two-dimensional carbide dispersion strengthening and toughening molybdenum alloy according to claim 1 or 9, wherein the two-dimensional MAX ceramic material in the step (1) is Zr 3 AlC 2 、Si 3 AlC 2 、Hf 3 AlC 2 、Zr 2 AlC、Si 2 AlC、Hf 2 AlC 2 、Zr 4 AlC 3 、Si 4 AlC 3 、Hf 4 AlC 3 Any one or more of the following.
CN202310238874.XA 2023-03-14 2023-03-14 Preparation method of in-situ authigenic two-dimensional carbide dispersion strengthening and toughening molybdenum alloy Pending CN116287833A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117383949A (en) * 2023-11-10 2024-01-12 江苏君耀耐磨耐火材料有限公司 Preparation method of carbon nanofiber toughened refractory material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117383949A (en) * 2023-11-10 2024-01-12 江苏君耀耐磨耐火材料有限公司 Preparation method of carbon nanofiber toughened refractory material
CN117383949B (en) * 2023-11-10 2024-04-02 江苏君耀耐磨耐火材料有限公司 Preparation method of carbon nanofiber toughened refractory material

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