CN118773465A - Molybdenum alloy and preparation method thereof - Google Patents
Molybdenum alloy and preparation method thereof Download PDFInfo
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- 229910001182 Mo alloy Inorganic materials 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000005245 sintering Methods 0.000 claims abstract description 54
- 239000000725 suspension Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000005242 forging Methods 0.000 claims abstract description 33
- 239000011812 mixed powder Substances 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 24
- 239000011733 molybdenum Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 21
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 16
- 238000001953 recrystallisation Methods 0.000 claims abstract description 15
- 239000002159 nanocrystal Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 81
- 238000010438 heat treatment Methods 0.000 claims description 70
- 239000002131 composite material Substances 0.000 claims description 43
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 43
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 28
- 239000011268 mixed slurry Substances 0.000 claims description 23
- -1 titanium hydride Chemical compound 0.000 claims description 20
- 229910000048 titanium hydride Inorganic materials 0.000 claims description 20
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 20
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 claims description 20
- 229910000568 zirconium hydride Inorganic materials 0.000 claims description 20
- 239000005715 Fructose Substances 0.000 claims description 15
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 15
- 229930091371 Fructose Natural products 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 2
- 230000007480 spreading Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000004663 powder metallurgy Methods 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 27
- 229910052760 oxygen Inorganic materials 0.000 description 27
- 239000001301 oxygen Substances 0.000 description 27
- 239000002994 raw material Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 19
- 239000006185 dispersion Substances 0.000 description 10
- 238000004108 freeze drying Methods 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 150000004678 hydrides Chemical class 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000005728 strengthening Methods 0.000 description 5
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- 238000012986 modification Methods 0.000 description 4
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- 238000005054 agglomeration Methods 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
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Abstract
The invention provides a molybdenum alloy and a preparation method thereof, and relates to the technical field of preparation of powder metallurgy nanostructure materials, comprising the following steps: step 1) preparing a suspension, mixing the suspension with molybdenum powder, and drying to obtain mixed powder; step 2) sintering the mixed powder to obtain a sintered blank; wherein the microstructure of the sintered blank comprises a molybdenum matrix and a nano reinforcing phase; step 3) performing multi-pass rotary forging treatment on the sintered blank to obtain a molybdenum alloy bar; step 4) carrying out recrystallization annealing on the molybdenum alloy bar, and cooling to obtain molybdenum alloy; wherein, the molybdenum matrix in the molybdenum alloy forms a heterostructure of mixed coarse crystals and nanocrystalline, and the molybdenum alloy is obtained after cooling treatment. According to the invention, through a multi-pass rotary forging cooperative recrystallization annealing process and combining the pinning effect of the nano-reinforcement relative grain boundary, the molybdenum alloy obtains a heterostructure of mixed coarse grains and nano-crystals, so that the strength and the ductility of the molybdenum alloy are improved.
Description
Technical Field
The invention belongs to the technical field of preparation of powder metallurgy nanostructure materials, and particularly relates to a molybdenum alloy and a preparation method thereof.
Background
Molybdenum is a refractory metal with a melting point of 2610deg.C that is stable in the body-centered cubic structure without undergoing phase changes. Molybdenum and molybdenum alloys are often used as candidate materials for fusion reactor components, missiles, turbines, rocket nozzles, and other critical high temperature applications due to their excellent high temperature strength, thermal stability, creep resistance, and high thermal conductivity.
However, due to the ductile-brittle transition of molybdenum at room temperature, deformation of the body-centered cubic structure of molybdenum is mainly by screw dislocation slip, and it is difficult to activate such deformation below the ductile-brittle transition temperature, resulting in poor ductility of the molybdenum alloy. In addition, some impurity solid-solution elements, particularly oxygen, are easily segregated to grain boundaries, thereby weakening the strength thereof, resulting in brittle fracture.
Disclosure of Invention
Therefore, the invention provides a molybdenum alloy and a preparation method thereof, and mainly aims to provide a high-strength and high-toughness molybdenum alloy and a preparation method thereof.
In order to solve the problems, the invention provides a preparation method of molybdenum alloy, comprising the following steps:
step 1) preparing a suspension, mixing the suspension with molybdenum powder, and drying to obtain mixed powder; the suspension comprises nano titanium hydride powder and nano zirconium hydride powder;
Step 2) sintering the mixed powder to obtain a sintered blank; wherein the microstructure of the sintered blank comprises a molybdenum matrix and a nano reinforcing phase;
Step 3) performing multi-pass rotary forging treatment on the sintered blank to obtain a molybdenum alloy bar;
Step 4) carrying out recrystallization annealing on the molybdenum alloy bar, and cooling to obtain molybdenum alloy; wherein, the molybdenum matrix in the molybdenum alloy forms a heterostructure of mixed coarse crystals and nano crystals.
Further, in the step 1), the preparing of the suspension includes:
dispersing agent is added into the mixture containing nano titanium hydride powder, nano zirconium hydride powder and fructose, and then ultrasonic dispersion is carried out to obtain suspension.
Further, the granularity of the nano titanium hydride powder is 50-100 nm; the granularity of the nano zirconium hydride powder is 50-100 nm.
Further, the dispersing agent is one or more of polyvinylpyrrolidone PVP, polyethylene glycol PEG and sodium dodecyl sulfate.
Further, the porosity of the molybdenum powder is more than 60%, and the average particle size of the molybdenum powder is less than 200nm.
Further, the preparation steps of the molybdenum powder are as follows:
reducing the composite molybdenum oxide powder to obtain molybdenum powder; wherein the composite molybdenum oxide powder comprises molybdenum dioxide and molybdenum;
The average particle size of the composite molybdenum oxide powder is less than 200nm.
Further, the reduction treatment includes: carrying out multi-temperature-stage reduction on the composite molybdenum oxide powder in a hydrogen atmosphere;
wherein the multi-temperature zone reduction comprises: heating the composite molybdenum oxide powder to 350-450 ℃ and preserving heat for 1-2 hours, then heating to 550-650 ℃ and preserving heat for 1-2 hours, and then heating to 750-850 ℃ and preserving heat for 1-2 hours; wherein the thickness of the spreading material of the composite molybdenum oxide powder is less than 10mm.
Further, in the step 1), the mixing process includes:
stirring the suspension, adding the molybdenum powder into the suspension while stirring to obtain mixed slurry, and drying the mixed slurry to obtain mixed powder.
Further, in the step 2), the sintering process includes: carrying out multi-temperature-section vacuum sintering on the mixed powder;
Wherein, the multi-temperature section vacuum sintering includes: and heating the mixed powder to 800-1000 ℃ for sintering for 1-2 hours, then heating to 1000-1200 ℃ for sintering for 1-2 hours, heating to 1400-1600 ℃ for sintering for 1-2 hours, and finally heating to 1800-2000 ℃ for sintering for 4-6 hours.
Further, in the step 3), the total deformation of the multi-pass rotary swaging is 60% -95%; wherein the deformation of each pass of rotary forging is less than 25%;
The temperature of the multi-pass rotary forging treatment is 800-1400 ℃.
Further, in the step 4), the recrystallization annealing includes:
Heating the molybdenum alloy bar to 850-1050 ℃ and preserving heat for 0.1-1 hour; then heating to 1050-1250 ℃, preserving heat for 0.1-1 hour, heating to 1250-1350 ℃, and preserving heat for 0.1-1 hour.
In another aspect, the present invention provides a molybdenum alloy comprising, in mass percent: zr:0.05% -0.15%, ti:0.1% -0.8%, C:0.01% -0.02%, and the balance of Mo;
the molybdenum alloy is obtained by adopting any one of the preparation methods.
Further, the structure of the molybdenum alloy comprises a molybdenum matrix and a nano reinforcing phase; the nanometer reinforced phase comprises one or more of a nanometer ZrC phase, a nanometer TiC phase, a nanometer ZrO 2 phase and a nanometer TiO 2 phase.
Further, the molybdenum substrate is a heterostructure, and the heterostructure comprises coarse crystals and nanocrystalline; in the heterostructure, the volume ratio of the nanocrystalline is 15-35%, and the grain size of the nanocrystalline is 50-500 nm; the volume ratio of the coarse crystals is 65-85%, and the grain size of the coarse crystals is 2-5 mu m.
Further, the yield strength of the molybdenum alloy at room temperature is more than 800MPa, and the elongation is more than 30%.
The molybdenum alloy and the preparation method thereof provided by the invention have the following beneficial effects:
1. According to the invention, nano hydride powder is used as a raw material, an internal oxidation process is carried out in a sintering process to form a nano reinforced phase, and then a multi-pass rotary forging cooperative recrystallization annealing process is combined with the pinning effect of nano reinforced relative grain boundaries, so that a molybdenum alloy obtains a heterogeneous structure with mixed coarse grains and nano grains; the multi-pass rotary forging enables uneven strain distribution to be formed in the matrix of the molybdenum alloy bar, when the annealing temperature is lower than the full recrystallization temperature, the area with high strain distribution is recrystallized, the nano reinforcement has obvious pinning effect relative to the grain boundary, and the growth of crystal grains can be effectively prevented, so that nanocrystalline is obtained, and the matrix which is not recrystallized is still coarse. The nanocrystalline provides high strength for the alloy, the coarse grain provides toughness for the alloy, and the nanocrystalline and the coarse grain cooperate when deformed, so that the strength and the ductility of the molybdenum alloy are greatly improved, and the problem of poor room-temperature ductility of the traditional molybdenum alloy is solved.
2. The invention uses the composite molybdenum oxide powder as a molybdenum source, and obtains the superfine molybdenum powder with low oxygen content, high dispersion and high porosity through multi-temperature section reduction treatment while reducing the production cost, thereby ensuring that nano hydrides are uniformly in the pores of the molybdenum powder and strengthening phases are uniformly distributed in the grains in the sintering process; the multi-temperature-section reduction treatment can induce partial molybdenum powder nucleation at low temperature, so that the reduction time at high temperature is shortened; meanwhile, carbon is introduced through fructose instead of carbon powder and graphite, and the fructose is a soluble substance, so that the carbon can be more uniformly distributed, and the formation of a nano ZrC phase and a nano TiC phase is facilitated.
3. Furthermore, the invention is beneficial to the mixing of fructose, nano hydride powder and molybdenum powder by the mode of the cooperation of dispersing agents and ultrasonic dispersion, regulates and controls the distribution of strengthening phases from the source, and solves the phenomenon of agglomeration of strengthening phases in the traditional molybdenum alloy; meanwhile, the nano ZrO 2 phase and the nano TiO 2 phase are formed, so that oxygen element in the matrix is prevented from being biased at a crystal boundary, and brittleness of the molybdenum alloy is ensured.
4. The mixed slurry is dried in a spray drying mode and a freeze drying mode, so that the advanced oxidation of hydride can be avoided, the internal oxidation process is fully carried out, and the oxygen content of the alloy is further reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. The drawings in the following description are merely exemplary and other implementations drawings may be derived from the drawings provided without inventive effort for a person skilled in the art.
FIG. 1 is a strain electron microscope image of a molybdenum alloy bar prepared in example 1 of the present invention;
FIG. 2 is a drawing of a molybdenum alloy prepared in example 1 of the invention;
FIG. 3 is a microscopic structure electron microscope image of the molybdenum alloy prepared in example 1 of the present invention;
FIG. 4 is a microscopic structure electron microscopic image of the molybdenum alloy prepared in comparative example 1 of the present invention;
FIG. 5 is a microscopic structure electron microscopic image of the molybdenum alloy prepared in comparative example 2 of the present invention;
FIG. 6 is a microscopic structure electron microscopic image of the molybdenum alloy prepared in comparative example 3 of the present invention.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. The drawings in the following description are merely exemplary and other implementations drawings may be derived from the drawings provided without inventive effort for a person skilled in the art.
The invention provides a preparation method of molybdenum alloy, which comprises the following steps:
Step 1) preparing a suspension, mixing the suspension with molybdenum powder, and drying to obtain mixed powder; the suspension comprises nano titanium hydride powder and nano zirconium hydride powder;
Step 2) sintering the mixed powder to obtain a sintered blank; wherein the microstructure of the sintered blank comprises a molybdenum matrix and a nano reinforcing phase;
step 3) performing multi-pass rotary forging treatment on the sintered blank to obtain a molybdenum alloy bar;
step 4) carrying out recrystallization annealing on the molybdenum alloy bar, and cooling to obtain molybdenum alloy; wherein, the molybdenum matrix in the molybdenum alloy forms a heterostructure of mixed coarse crystals and nano crystals.
Based on the method, the nano hydride particles are used as additives, and the aim of the invention is to reduce the oxygen content of the alloy while forming a strengthening phase in the internal oxidation process in the sintering process. Firstly, carrying out surface modification on the hydride through dispersion treatment, and improving the wettability and dispersibility of the nano hydride; then reducing the composite molybdenum oxide powder, regulating and controlling the porous structure morphology of the molybdenum powder so as to realize uniform mixing of the hydride and the molybdenum powder, and laying a foundation for realizing uniform distribution of internal oxidation products; and then, a multipass rotary forging and recrystallization annealing process is adopted, and the pinning effect of the nano-reinforced relative grain boundary formed by internal oxidation is utilized, so that a heterostructure of mixed coarse grains and nano-crystals in the molybdenum alloy is realized, the strength and the ductility of the molybdenum alloy are greatly improved, and the problem of poor room-temperature ductility of the traditional molybdenum alloy is solved.
The molybdenum alloy bar is subjected to multi-pass rotary forging treatment, the strain distribution is uneven, recrystallization annealing is carried out, a part of the matrix with high strain energy is recrystallized preferentially, the nano reinforcement has obvious pinning effect on the grain boundary, and the growth of crystal grains can be effectively prevented, so that nanocrystalline is obtained; the matrix in which no recrystallization occurred was coarse-grained. The nanocrystalline and the coarse crystal have distinct flow stress, so that the material cannot be freely plastically deformed, and dislocation is required to be generated at the grain boundary of the coarse crystal to adapt, thereby generating a cooperative strengthening effect. With the increase of the deformation amount of the material, the nanocrystalline and the coarse grain are subjected to plastic deformation at the same time, the coarse grain bears larger plastic strain relative to the nanocrystalline, and a strain gradient is generated at the junction of the coarse grain and the nanocrystalline, so that the material is subjected to back stress work hardening, and the comprehensive performance of the material can be greatly improved.
In some embodiments, in step 1), preparing the suspension comprises:
dispersing agent is added into the mixture containing nano titanium hydride powder, nano zirconium hydride powder and fructose, and then ultrasonic dispersion is carried out to obtain suspension.
In some embodiments, the particle size of the nano titanium hydride powder is 50-100 nm; the granularity of the nanometer zirconium hydride powder is 50-100 nm.
In some embodiments, the dispersant is one or more of polyvinylpyrrolidone PVP, polyethylene glycol PEG, and sodium dodecyl sulfate.
In some embodiments, the molybdenum powder has a porosity of greater than 60% and an average particle size of less than 200nm.
In some embodiments, the molybdenum powder is prepared by the steps of:
reducing the composite molybdenum oxide powder to obtain molybdenum powder; wherein the composite molybdenum oxide powder comprises molybdenum dioxide and molybdenum;
the average particle size of the composite molybdenum oxide powder is less than 200nm.
In some embodiments, the reduction process comprises: carrying out multi-temperature-stage reduction on the composite molybdenum oxide powder in a hydrogen atmosphere;
Wherein the multi-temperature zone reduction comprises: heating the composite molybdenum oxide powder to 450-650 ℃ and preserving heat for 1-2 hours, and then heating to 750-850 ℃ and preserving heat for 3-5 hours; the thickness of the paving material of the composite molybdenum oxide powder is less than 10mm.
In some embodiments, in step 1), the mixing process comprises:
stirring the suspension, adding molybdenum powder into the suspension while stirring to obtain mixed slurry, and drying the mixed slurry to obtain mixed powder.
In some embodiments, in step 2), the sintering process comprises: carrying out multi-temperature-section vacuum sintering on the mixed powder;
wherein, the multi-temperature section vacuum sintering includes: heating the mixed powder to 800-1000 ℃ for sintering for 1-2 hours, then heating to 1000-1200 ℃ for sintering for 1-2 hours, heating to 1400-1600 ℃ for sintering for 1-2 hours, and finally heating to 1800-2000 ℃ for sintering for 4-6 hours.
In some embodiments, in step 3), the total deformation of the multi-pass swaging is 60% -95%; wherein the deformation of each pass of rotary forging is less than 25%; the deformation of each pass of rotary forging is too large, so that cracks can be generated;
The temperature of the multi-pass rotary forging treatment is 800-1400 ℃.
In some embodiments, in step 4), the recrystallization anneal comprises:
heating the molybdenum alloy bar to 850-1050 ℃ and preserving heat for 0.1-1 hour; then heating to 1050-1250 ℃, preserving heat for 0.1-1 hour, heating to 1250-1350 ℃, and preserving heat for 0.1-1 hour.
In another aspect, the present invention provides a molybdenum alloy comprising, in mass percent: zr:0.05% -0.15%, ti:0.1% -0.8%, C:0.01% -0.02%, and the balance of Mo;
The molybdenum alloy is obtained by adopting the preparation method of any one of the above.
In some embodiments, the structure of the molybdenum alloy includes a molybdenum matrix and a nano-reinforcement phase; the nanometer reinforced phase comprises one or more of nanometer ZrC phase, nanometer TiC phase, nanometer ZrO 2 phase and nanometer TiO 2 phase.
In the sintering treatment process, titanium hydride and zirconium hydride in the raw materials react with O in the matrix (i.e. internal oxidation reaction) to form a nano ZrO 2 phase and a nano TiO 2 phase respectively, or form a ZrC phase and a nano TiC phase respectively with C in fructose; interaction of these nano-reinforcing phases with dislocations can enhance alloy strength; meanwhile, the crack can be passivated to prevent the crack from expanding; in addition, during sintering and hot working, the nano reinforced phase pins the grain boundary, and fine grain size can be obtained (the grain boundary of the molybdenum alloy is easy to generate segregation of oxygen element, the higher the oxygen content is, the more serious the performance of the material is deteriorated, and the finer the grain is, the lower the oxygen content is on the unit grain boundary area, thereby being beneficial to reducing the brittleness of the molybdenum alloy).
In some embodiments, the molybdenum substrate is a heterostructure including coarse crystals and nanocrystals; in the heterostructure, the volume ratio of the nanocrystalline is 15-35%, and the grain size of the nanocrystalline is 50-500 nm; the volume ratio of the coarse crystals is 65-85%, and the grain size of the coarse crystals is 2-5 mu m.
In some embodiments, the molybdenum alloy has a yield strength greater than 800MPa and an elongation (at break) greater than 30% at room temperature.
The present invention will be further described with reference to examples and comparative examples.
Example 1
The embodiment provides a preparation method of molybdenum alloy, comprising the following steps:
Step 1) preparing raw materials, and then placing the raw materials in alcohol under the assistance of dispersing agents PVP and PEG for ultrasonic dispersion to obtain uniformly mixed suspension;
in the raw materials, the mass of the nano zirconium hydride powder is 2 g, the average particle size is 50nm, the mass of the nano titanium hydride powder is 8 g, the average particle size is 50nm, and the mass of the fructose is 0.7 g; wherein, the frequency of ultrasonic dispersion is 25kHZ, and the time is 2 hours;
Taking 1322.6 g of composite molybdenum oxide powder, heating the composite molybdenum oxide powder to 450 ℃ under the hydrogen atmosphere, preserving heat for 2 hours, and then heating to 780 ℃ and preserving heat for 4 hours to obtain molybdenum powder with low oxygen content, high dispersion and high porosity; the porosity of the molybdenum powder is 75%, and the average granularity of the molybdenum powder is 150nm;
wherein, the thickness of the paving material of the composite molybdenum oxide powder is 3mm;
Placing the suspension into a magnetic stirrer for stirring, continuously adding molybdenum powder during stirring to obtain uniformly dispersed mixed slurry, and then freeze-drying the mixed slurry to obtain mixed powder;
step 2) sequentially carrying out vacuum pre-sintering on the mixed powder at 1000 ℃, 1200 ℃ and 1600 ℃ for 1 hour, and then carrying out vacuum sintering at 1850 ℃ for 6 hours to obtain a sintered blank;
Wherein the revolution number of the magnetic stirrer is 120 revolutions per minute, and the stirring time is 120 minutes; the pressure of vacuum sintering is 40MPa;
Step 3) heating the sintered blank to 1300 ℃ in a protective atmosphere, preserving heat for 1 hour, and then performing multi-pass rotary forging to obtain a molybdenum alloy bar; wherein the total deformation of the multi-pass rotary forging is 85%;
And 4) heating the molybdenum alloy bar to 950 ℃, preserving heat for 0.5 hour, then heating to 1250 ℃ along with a furnace, preserving heat for 0.3 hour, and then heating to 1300 ℃ along with the furnace, preserving heat for 1 hour, thus obtaining the molybdenum alloy with nanocrystalline and coarse crystal.
The strain distribution of the bar material of the molybdenum alloy prepared in the embodiment is shown in fig. 1, the tensile curve of the prepared molybdenum alloy is shown in fig. 2, and the microstructure photo is shown in fig. 3; as can be seen from fig. 1, the strain distribution is not uniform; the strain distribution is uneven; as can be seen from fig. 2, the room temperature tensile strength of the molybdenum alloy prepared in this example is 919.02.56 mpa; as can be seen from fig. 3, the molybdenum alloy microstructure prepared in this example is a heterostructure including 2-5 μm coarse grains and 50-500nm nanocrystals, wherein the volume ratio of the nanocrystals is about 35% and the volume ratio of the coarse grains is about 65%. The molybdenum alloy prepared in this example was found to have a room temperature yield strength of 895.51MPa, an elongation of 37.2% and an oxygen content of 200ppm.
Example 2
The embodiment provides a preparation method of molybdenum alloy, comprising the following steps:
Step 1) preparing raw materials, and then placing the raw materials in alcohol under the assistance of dispersing agents PVP and PEG for ultrasonic dispersion to obtain uniformly mixed suspension;
in the raw materials, the mass of the nano zirconium hydride powder is 2 g, the average particle size is 50nm, the mass of the nano titanium hydride powder is 8 g, the average particle size is 50nm, and the mass of the fructose is 0.7 g; wherein, the frequency of ultrasonic dispersion is 25kHZ, and the time is 2 hours;
taking 1322.6 g of composite molybdenum oxide powder, heating the composite molybdenum oxide powder to 450 ℃ under the hydrogen atmosphere, preserving heat for 2 hours, and then heating to 750 ℃ and preserving heat for 3.5 hours to obtain molybdenum powder with low oxygen content, high dispersion and high porosity; the porosity of the molybdenum powder is 70%, and the average granularity of the molybdenum powder is 130nm;
wherein, the thickness of the paving material of the composite molybdenum oxide powder is 3mm;
Placing the suspension into a magnetic stirrer for stirring, continuously adding molybdenum powder during stirring to obtain uniformly dispersed mixed slurry, and then freeze-drying the mixed slurry to obtain mixed powder;
step 2) sequentially carrying out vacuum pre-sintering on the mixed powder at 800 ℃, 1000 ℃ and 1400 ℃ for 1 hour, and then carrying out vacuum sintering at 2000 ℃ for 6 hours to obtain a sintered blank;
Wherein the revolution number of the magnetic stirrer is 120 revolutions per minute, and the stirring time is 120 minutes; the pressure of vacuum sintering is 40MPa;
step 3) heating the sintered blank to 1300 ℃ in a protective atmosphere, preserving heat for 1 hour, and then performing multi-pass rotary forging to obtain a molybdenum alloy bar; wherein the total deformation of the multi-pass rotary forging is 75%;
And 4) heating the molybdenum alloy bar to 850 ℃, preserving heat for 0.5 hour, then heating to 1050 ℃ along with a furnace, preserving heat for 0.3 hour, and then heating to 1250 ℃ along with the furnace, preserving heat for 1 hour, thus obtaining the molybdenum alloy with nanocrystalline and coarse crystal.
The molybdenum alloy prepared in this example had a room temperature tensile strength of 927MPa, a room temperature yield strength of 852.51MPa, an elongation of 31% and an oxygen content of 230ppm.
Example 3
The embodiment provides a preparation method of molybdenum alloy, comprising the following steps:
Step 1) preparing raw materials, and then placing the raw materials in alcohol with the aid of dispersing agent sodium dodecyl sulfate for ultrasonic dispersion to obtain uniformly mixed suspension;
in the raw materials, the mass of the nano zirconium hydride powder is 2 g, the average particle size is 50nm, the mass of the nano titanium hydride powder is 8 g, the average particle size is 50nm, and the mass of the fructose is 0.7 g; wherein, the frequency of ultrasonic dispersion is 25kHZ, and the time is 2 hours;
Taking 1322.6 g of composite molybdenum oxide powder, heating the composite molybdenum oxide powder to 650 ℃ under the hydrogen atmosphere, preserving heat for 1 hour, and then heating to 850 ℃ and preserving heat for 3 hours to obtain molybdenum powder with low oxygen content, high dispersion and high porosity;
wherein, the thickness of the paving material of the composite molybdenum oxide powder is 3mm;
Placing the suspension into a magnetic stirrer for stirring, continuously adding molybdenum powder during stirring to obtain uniformly dispersed mixed slurry, and then freeze-drying the mixed slurry to obtain mixed powder;
Step 2) sequentially carrying out vacuum pre-sintering on the mixed powder at 800 ℃, 1200 ℃ and 1600 ℃ for 1 hour, and then carrying out vacuum sintering at 1800 ℃ for 6 hours to obtain a sintered blank;
Wherein the revolution number of the magnetic stirrer is 120 revolutions per minute, and the stirring time is 120 minutes; the pressure of vacuum sintering is 40MPa;
Step 3) heating the sintered blank to 1400 ℃ in a protective atmosphere, preserving heat for 1 hour, and then performing multi-pass rotary forging to obtain a molybdenum alloy bar; wherein the total deformation of the multi-pass rotary forging is 60%;
And 4) heating the molybdenum alloy bar to 1050 ℃, preserving heat for 0.5 hour, then heating to 1150 ℃ along with a furnace, preserving heat for 0.3 hour, and then heating to 1350 ℃ along with the furnace, preserving heat for 1 hour, thus obtaining the molybdenum alloy with nanocrystalline and coarse crystal.
The molybdenum alloy prepared in this example had a room temperature tensile strength of 887MPa, a room temperature yield strength of 832.2MPa, an elongation of 31.3% and an oxygen content of 235ppm.
Example 4
The embodiment provides a preparation method of molybdenum alloy, comprising the following steps:
Step 1) preparing raw materials, and then placing the raw materials in alcohol under the assistance of dispersing agents PVP and PEG for ultrasonic dispersion to obtain uniformly mixed suspension;
in the raw materials, the mass of the nano zirconium hydride powder is 2 g, the average particle size is 50nm, the mass of the nano titanium hydride powder is 8 g, the average particle size is 50nm, and the mass of the fructose is 0.7 g; wherein, the frequency of ultrasonic dispersion is 25kHZ, and the time is 2 hours;
taking 1322.6 g of composite molybdenum oxide powder, heating the composite molybdenum oxide powder to 650 ℃ under the hydrogen atmosphere, preserving heat for 1 hour, and then heating to 750 ℃ and preserving heat for 3.5 hours to obtain molybdenum powder with low oxygen content, high dispersion and high porosity;
wherein, the thickness of the paving material of the composite molybdenum oxide powder is 3mm;
Placing the suspension into a magnetic stirrer for stirring, continuously adding molybdenum powder during stirring to obtain uniformly dispersed mixed slurry, and then freeze-drying the mixed slurry to obtain mixed powder;
Step 2) sequentially carrying out vacuum pre-sintering on the mixed powder at 900 ℃, 1100 ℃ and 1500 ℃ for 1 hour, and then carrying out vacuum sintering at 1900 ℃ for 6 hours to obtain a sintered blank;
Wherein the revolution number of the magnetic stirrer is 120 revolutions per minute, and the stirring time is 120 minutes; the pressure of vacuum sintering is 40MPa;
Step 3) heating the sintered blank to 1400 ℃ in a protective atmosphere, preserving heat for 1 hour, and then performing multi-pass rotary forging to obtain a molybdenum alloy bar; wherein the total deformation of the multi-pass rotary forging is 95%;
And 4) heating the molybdenum alloy bar to 850 ℃, preserving heat for 0.5 hour, then heating to 1050 ℃ along with a furnace, preserving heat for 0.3 hour, and then heating to 1250 ℃ along with the furnace, preserving heat for 1 hour, thus obtaining the molybdenum alloy with nanocrystalline and coarse crystal.
The molybdenum alloy prepared in this example had a room temperature tensile strength of 907MPa, a room temperature yield strength of 852.6MPa, an elongation of 32.7% and an oxygen content of 235ppm.
Comparative example 1
The comparative example provides a method for preparing molybdenum alloy, comprising the following steps:
Step 1) preparing raw materials, and then placing the raw materials in alcohol under the assistance of dispersing agents PVP and PEG for ultrasonic dispersion to obtain uniformly mixed suspension;
The raw materials comprise zirconium hydride powder, titanium hydride powder and fructose; wherein the mass of the zirconium hydride powder is 2 g, the average particle size is 10 mu m, the mass of the titanium hydride powder is 8 g, the average particle size is 10 mu m, and the mass of the fructose is 0.7 g; wherein, the frequency of ultrasonic dispersion is 25kHZ, and the time is 2 hours;
Taking 1322.6 g of composite molybdenum oxide powder, heating the composite molybdenum oxide powder to 450 ℃ under the hydrogen atmosphere, preserving heat for 2 hours, and then heating to 780 ℃ and preserving heat for 4 hours to obtain molybdenum powder with low oxygen content, high dispersion and high porosity;
wherein, the thickness of the paving material of the composite molybdenum oxide powder is 3mm;
Placing the suspension into a magnetic stirrer for stirring, continuously adding molybdenum powder during stirring to obtain uniformly dispersed mixed slurry, and then freeze-drying the mixed slurry to obtain mixed powder;
step 2) sequentially carrying out vacuum pre-sintering on the mixed powder at 1000 ℃, 1200 ℃ and 1600 ℃ for 1 hour, and then carrying out vacuum sintering at 1850 ℃ for 6 hours to obtain a sintered blank;
Wherein the revolution number of the magnetic stirrer is 120 revolutions per minute, and the stirring time is 120 minutes; the pressure of vacuum sintering is 40MPa;
Step 3) heating the sintered blank to 1300 ℃ in a protective atmosphere, preserving heat for 1 hour, and then performing multi-pass rotary forging to obtain a molybdenum alloy bar; wherein the total deformation of the multi-pass rotary forging is 85%;
And 4) heating the molybdenum alloy bar to 950 ℃, preserving heat for 0.5 hour, then heating to 1300 ℃ along with a furnace, preserving heat for 0.3 hour, and then heating to 1330 ℃ along with the furnace, preserving heat for 1 hour, thus obtaining the molybdenum alloy.
The molybdenum alloy prepared in this comparative example had a room temperature tensile strength of 780.3MPa, a room temperature yield strength of 720.6MPa, an elongation of 13% and an oxygen content of 700ppm. It can be seen that the molybdenum alloy has lower room temperature tensile strength, room temperature yield strength and elongation, and higher oxygen content. As shown in fig. 4, a photograph of the microstructure of the molybdenum alloy prepared in this comparative example shows that the microstructure of the molybdenum alloy is a typical recrystallized structure, resulting in a decrease in ductility of the molybdenum alloy. The method is characterized in that the zirconium hydride and the titanium hydride are large in size, the volume fraction of reinforced phase particles formed by internal oxidation is reduced on the premise of unchanged mass fraction, the deoxidizing effect of the internal oxidation process on a matrix is weakened, and the pinning capability of the reinforced phase particles to grain boundaries is enhanced, so that the molybdenum alloy bar is completely recrystallized in the annealing process, and the performance of the material is deteriorated.
Comparative example 2
The comparative example provides a method for preparing molybdenum alloy, comprising the following steps:
Step 1) preparing raw materials, and then placing the raw materials in alcohol under the assistance of dispersing agents PVP and PEG for ultrasonic dispersion to obtain uniformly mixed suspension;
in the raw materials, the mass of the nano zirconium hydride powder is 2 g, the average particle size is 50nm, the mass of the nano titanium hydride powder is 8 g, the average particle size is 50nm, and the mass of the fructose is 0.7 g; wherein, the frequency of ultrasonic dispersion is 25kHZ, and the time is 2 hours;
Taking 1322.6 g of composite molybdenum oxide powder, heating the composite molybdenum oxide powder to 450 ℃ under the hydrogen atmosphere, preserving heat for 2 hours, and then heating to 780 ℃ and preserving heat for 4 hours to obtain molybdenum powder with low oxygen content, high dispersion and high porosity;
wherein, the thickness of the paving material of the composite molybdenum oxide powder is 3mm;
Placing the suspension into a magnetic stirrer for stirring, continuously adding molybdenum powder during stirring to obtain uniformly dispersed mixed slurry, and then freeze-drying the mixed slurry to obtain mixed powder;
step 2) sequentially carrying out vacuum pre-sintering on the mixed powder at 1000 ℃, 1200 ℃ and 1600 ℃ for 1 hour, and then carrying out vacuum sintering at 1850 ℃ for 6 hours to obtain a sintered blank;
Wherein the revolution number of the magnetic stirrer is 120 revolutions per minute, and the stirring time is 120 minutes; the pressure of vacuum sintering is 40MPa;
Step 3) heating the sintered blank to 1300 ℃ in a protective atmosphere, preserving heat for 1 hour, and then performing multi-pass rotary forging to obtain a molybdenum alloy bar; wherein the total deformation of the multi-pass rotary forging is 85%;
And 4) preserving the temperature of the molybdenum alloy bar for 1 hour at 1100 ℃ to obtain the molybdenum alloy.
The molybdenum alloy prepared in this comparative example had a room temperature tensile strength of 820.6MPa, a room temperature yield strength of 768.5MPa, an elongation of 24.2% and an oxygen content of 206ppm. It can be seen that the molybdenum alloy has low room temperature tensile strength, room temperature yield strength and elongation. The microstructure photograph of the molybdenum alloy prepared in this comparative example is shown in fig. 5, and it can be seen that a mixed heterostructure of coarse crystals and nanocrystals is not formed. The molybdenum alloy bar is subjected to stress relief annealing by adopting a traditional process, and the annealing temperature is in a stress relief annealing stage and does not reach the recrystallization temperature, so that microstructure of a heterostructure of recrystallized nanocrystalline and coarse grain mixed cannot be obtained, and the room-temperature tensile strength, the room-temperature yield strength and the elongation are low.
Comparative example 3
The comparative example provides a method for preparing molybdenum alloy, comprising the following steps:
Step 1) preparing raw materials, and then placing the raw materials in alcohol under the assistance of dispersing agents PVP and PEG for ultrasonic dispersion to obtain uniformly mixed suspension;
in the raw materials, the mass of the nano zirconium hydride powder is 2 g, the average particle size is 50nm, the mass of the nano titanium hydride powder is 8 g, the average particle size is 50nm, and the mass of the fructose is 0.7 g; wherein, the frequency of ultrasonic dispersion is 25kHZ, and the time is 2 hours;
taking 1322.6 g of composite molybdenum oxide powder, sequentially heating the composite molybdenum oxide powder to 450 ℃ under the hydrogen atmosphere, preserving heat for 2 hours, and then heating to 780 ℃ and preserving heat for 4 hours to obtain molybdenum powder with low oxygen content, high dispersion and high porosity;
wherein, the thickness of the paving material of the composite molybdenum oxide powder is 3mm;
Placing the suspension into a magnetic stirrer for stirring, continuously adding molybdenum powder during stirring to obtain uniformly dispersed mixed slurry, and freeze-drying the mixed slurry to obtain mixed powder;
step 2) sequentially carrying out vacuum pre-sintering on the mixed powder at 1000 ℃, 1200 ℃ and 1600 ℃ for 1 hour, and then carrying out vacuum sintering at 1850 ℃ for 6 hours to obtain a sintered blank;
Wherein the revolution number of the magnetic stirrer is 120 revolutions per minute, and the stirring time is 120 minutes; the pressure of vacuum sintering is 40MPa;
Step 3) heating the sintered blank to 1300 ℃ in a protective atmosphere, preserving heat for 1 hour, and then performing multi-pass rotary forging to obtain a molybdenum alloy bar; wherein the total deformation of the multi-pass rotary forging is 55%;
And 4) preserving the temperature of the molybdenum alloy bar for 1 hour at 1100 ℃ to obtain the molybdenum alloy.
The molybdenum alloy prepared in this comparative example had a room temperature tensile strength of 820.3MPa, a room temperature yield strength of 790.51MPa, an elongation of 24.2% and an oxygen content of 200ppm. It can be seen that the molybdenum alloy has low room temperature tensile strength, room temperature yield strength and elongation. The microstructure photograph of the molybdenum alloy prepared in this comparative example is shown in fig. 6, and it can be seen that a hetero structure in which coarse crystals and nanocrystals are mixed is not formed. The method is characterized in that the total deformation of multi-pass rotary forging is low, so that dislocation density in the grains of the molybdenum alloy bar is low, and microstructure of a heterostructure cannot be obtained through recrystallization annealing, so that the room-temperature tensile strength, the room-temperature yield strength and the elongation are low.
Comparative example 4
The comparative example provides a method for preparing molybdenum alloy, comprising the following steps:
Step 1) preparing raw materials, and then placing the raw materials in alcohol under the assistance of dispersing agents PVP and PEG for ultrasonic dispersion to obtain uniformly mixed suspension;
In the raw materials, the mass of the nano zirconium hydride powder is 2 g, the average particle size is 50nm, the mass of the nano titanium hydride powder is 8g, the average particle size is 50nm, the mass of the carbon powder is 0.7 g, and the average particle size is 10 mu m; wherein, the frequency of ultrasonic dispersion is 25kHZ, and the time is 2 hours;
Heating 1322.6 g of composite molybdenum oxide powder to 450 ℃ under the hydrogen atmosphere, preserving heat for 2 hours, and then heating to 780 ℃ and preserving heat for 4 hours to obtain molybdenum powder with low oxygen content, high dispersion and high porosity; wherein, the thickness of the paving material of the composite molybdenum oxide powder is 3mm;
Placing the suspension into a magnetic stirrer for stirring, continuously adding molybdenum powder during stirring to obtain uniformly dispersed mixed slurry, and then freeze-drying the mixed slurry to obtain mixed powder;
step 2) sequentially carrying out vacuum pre-sintering on the mixed powder at 1000 ℃, 1200 ℃ and 1600 ℃ for 1 hour, and then carrying out vacuum sintering at 1850 ℃ for 6 hours to obtain a sintered blank;
Wherein the revolution number of the magnetic stirrer is 120 revolutions per minute, and the stirring time is 120 minutes; the pressure of vacuum sintering is 40MPa;
Step 3) heating the sintered blank to 1300 ℃ in a protective atmosphere, preserving heat for 1 hour, and then performing multi-pass rotary forging to obtain a molybdenum alloy bar; wherein the total deformation of the multi-pass rotary forging is 85%;
And 4) heating the molybdenum alloy bar to 950 ℃, preserving heat for 0.5 hour, then heating to 1250 ℃ along with a furnace, preserving heat for 0.3 hour, and then heating to 1300 ℃ along with the furnace, preserving heat for 1 hour, thus obtaining the molybdenum alloy with nanocrystalline and coarse crystal.
The molybdenum alloy prepared in this comparative example had a room temperature tensile strength of 830.7MPa, a room temperature yield strength of 760.4MPa, an elongation of 18.2% and an oxygen content of 300ppm. It can be seen that the molybdenum alloy has lower room temperature tensile strength, room temperature yield strength and elongation and higher oxygen content. The method is characterized in that carbon powder is selected to introduce carbon, the deoxidizing effect of uneven carbon distribution in a matrix is poor, and the oxygen content in the molybdenum alloy is too high, so that the performance of the alloy is reduced due to embrittlement of grain boundaries.
Those skilled in the art will readily appreciate that the advantageous features of the various aspects described above may be freely combined and stacked without conflict.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention. The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that modifications and variations can be made without departing from the technical principles of the present invention, and these modifications and variations should also be regarded as the scope of the invention.
Claims (15)
1. A method for preparing a molybdenum alloy, comprising the steps of:
step 1) preparing a suspension, mixing the suspension with molybdenum powder, and drying to obtain mixed powder; the suspension comprises nano titanium hydride powder and nano zirconium hydride powder;
Step 2) sintering the mixed powder to obtain a sintered blank; wherein the microstructure of the sintered blank comprises a molybdenum matrix and a nano reinforcing phase;
Step 3) performing multi-pass rotary forging treatment on the sintered blank to obtain a molybdenum alloy bar;
Step 4) carrying out recrystallization annealing on the molybdenum alloy bar, and cooling to obtain molybdenum alloy; wherein, the molybdenum matrix in the molybdenum alloy forms a heterostructure of mixed coarse crystals and nano crystals.
2. The method of producing a molybdenum alloy according to claim 1, wherein in the step 1), the producing a suspension includes:
dispersing agent is added into the mixture containing nano titanium hydride powder, nano zirconium hydride powder and fructose, and then ultrasonic dispersion is carried out to obtain suspension.
3. The method for preparing the molybdenum alloy according to claim 2, wherein the particle size of the nano titanium hydride powder is 50-100 nm; the granularity of the nano zirconium hydride powder is 50-100 nm.
4. The method for preparing the molybdenum alloy according to claim 2, wherein the dispersing agent is one or more of polyvinylpyrrolidone PVP, polyethylene glycol PEG and sodium dodecyl sulfate.
5. The method of claim 1, wherein the porosity of the molybdenum powder is greater than 60% and the average particle size of the molybdenum powder is less than 200nm.
6. The method for preparing the molybdenum alloy according to any one of claims 1 to 5, wherein the preparation steps of the molybdenum powder are as follows:
reducing the composite molybdenum oxide powder to obtain molybdenum powder; wherein the composite molybdenum oxide powder comprises molybdenum dioxide and molybdenum;
The average particle size of the composite molybdenum oxide powder is less than 200nm.
7. The method for producing a molybdenum alloy according to claim 6, wherein the reduction treatment comprises: carrying out multi-temperature-stage reduction on the composite molybdenum oxide powder in a hydrogen atmosphere;
Wherein the multi-temperature zone reduction comprises: heating the composite molybdenum oxide powder to 450-650 ℃ and preserving heat for 1-2 hours, and then heating to 750-850 ℃ and preserving heat for 3-5 hours; wherein the thickness of the spreading material of the composite molybdenum oxide powder is less than 10mm.
8. The method of producing a molybdenum alloy according to claim 1, wherein in said step 1), said mixing treatment comprises:
stirring the suspension, adding the molybdenum powder into the suspension while stirring to obtain mixed slurry, and drying the mixed slurry to obtain mixed powder.
9. The method of producing a molybdenum alloy according to claim 1 or 8, wherein in the step 2), the sintering treatment comprises: carrying out multi-temperature-section vacuum sintering on the mixed powder;
Wherein, the multi-temperature section vacuum sintering includes: and heating the mixed powder to 800-1000 ℃ for sintering for 1-2 hours, then heating to 1000-1200 ℃ for sintering for 1-2 hours, heating to 1400-1600 ℃ for sintering for 1-2 hours, and finally heating to 1800-2000 ℃ for sintering for 4-6 hours.
10. The method for producing a molybdenum alloy according to claim 1, wherein in the step 3), the total deformation amount of the multi-pass swaging is 60% -95%; wherein the deformation of each pass of rotary forging is less than 25%;
The temperature of the multi-pass rotary forging treatment is 800-1400 ℃.
11. The method of producing a molybdenum alloy according to claim 1, wherein in said step 4), said recrystallization annealing comprises:
Heating the molybdenum alloy bar to 850-1050 ℃ and preserving heat for 0.1-1 hour; then heating to 1050-1250 ℃, preserving heat for 0.1-1 hour, heating to 1250-1350 ℃, and preserving heat for 0.1-1 hour.
12. A molybdenum alloy, characterized in that it comprises, in mass percent: zr:0.05% -0.15%, ti:0.1% -0.8%, C:0.01% -0.02%, and the balance of Mo;
the molybdenum alloy is obtained by the preparation method of any one of claims 1-11.
13. The molybdenum alloy of claim 12 wherein the structure of the molybdenum alloy comprises a molybdenum matrix and a nano-reinforcement phase; the nanometer reinforced phase comprises one or more of a nanometer ZrC phase, a nanometer TiC phase, a nanometer ZrO 2 phase and a nanometer TiO 2 phase.
14. The molybdenum alloy of claim 12 wherein the molybdenum substrate is a heterostructure including coarse-grain and nanocrystalline; in the heterostructure, the volume ratio of the nanocrystalline is 15-35%, and the grain size of the nanocrystalline is 50-500 nm; the volume ratio of the coarse crystals is 65-85%, and the grain size of the coarse crystals is 2-5 mu m.
15. The molybdenum alloy according to any one of claims 12-14, wherein the molybdenum alloy has a yield strength of greater than 800MPa and an elongation of greater than 30% at room temperature.
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| CN101934372A (en) * | 2010-07-30 | 2011-01-05 | 西北有色金属研究院 | Method for preparing large powder metallurgy TZM blank with uniform carbon and oxygen distribution |
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| US20100083782A1 (en) * | 2007-04-04 | 2010-04-08 | Cheisa Alfred J | Powder metal forging and method and apparatus of manufacture |
| CN101934372A (en) * | 2010-07-30 | 2011-01-05 | 西北有色金属研究院 | Method for preparing large powder metallurgy TZM blank with uniform carbon and oxygen distribution |
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| 罗明: "粉末冶金钼合金热锻的性能和显微组织研究", 中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑, no. 2, 15 February 2012 (2012-02-15), pages 17 - 18 * |
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