CN117884617A - Preparation method of high-plasticity recrystallized molybdenum and molybdenum alloy - Google Patents
Preparation method of high-plasticity recrystallized molybdenum and molybdenum alloy Download PDFInfo
- Publication number
- CN117884617A CN117884617A CN202311819818.1A CN202311819818A CN117884617A CN 117884617 A CN117884617 A CN 117884617A CN 202311819818 A CN202311819818 A CN 202311819818A CN 117884617 A CN117884617 A CN 117884617A
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- powder
- recrystallized
- percent
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910001182 Mo alloy Inorganic materials 0.000 title claims abstract description 71
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 65
- 239000011733 molybdenum Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 13
- 239000010419 fine particle Substances 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 34
- 238000005245 sintering Methods 0.000 claims description 25
- 238000012545 processing Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 238000009694 cold isostatic pressing Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000005096 rolling process Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910000691 Re alloy Inorganic materials 0.000 claims description 9
- YUSUJSHEOICGOO-UHFFFAOYSA-N molybdenum rhenium Chemical compound [Mo].[Mo].[Re].[Re].[Re] YUSUJSHEOICGOO-UHFFFAOYSA-N 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005242 forging Methods 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- -1 vacuum Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 abstract description 7
- 239000003870 refractory metal Substances 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000002245 particle Substances 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
The invention belongs to the technical field of refractory metal preparation, and particularly relates to a preparation method of high-plasticity recrystallized molybdenum and molybdenum alloy. The invention adopts low-oxygen medium-fine particle molybdenum powder or alloy powder, effectively reduces the brittleness of the grain boundary caused by oxygen, and is favorable for the tiny and uniform of recrystallized grains; and (3) utilizing a continuous thermal deformation reducing process, regulating the dynamic recrystallization degree through the thermal deformation amount, and obtaining a specific recrystallization microstructure after annealing. In addition, the grain size of the recrystallized molybdenum and molybdenum alloy prepared by the invention is less than or equal to 30 mu m, and the texture proportion of <110>// RD is more than or equal to 50%; the total elongation at break is more than or equal to 60 percent, more preferably more than or equal to 100 percent; the strength is not lower than 450MPa, more preferably not lower than 650MPa, and the refractory metal is expected to be applied in more severe environments such as ultrahigh temperature, high vacuum and the like.
Description
Technical Field
The invention belongs to the technical field of refractory metal preparation, and particularly relates to a preparation method of high-plasticity recrystallized molybdenum and molybdenum alloy.
Background
Molybdenum and molybdenum alloy materials are widely used in the key fields of aerospace (turbines), radar communication (traveling wave tubes), equipment manufacturing (furnace heating), nuclear industry (fuel cladding) and the like due to their excellent mechanical properties, high-temperature creep resistance, strong corrosion resistance and excellent electrical and thermal conductivity. However, room temperature brittleness due to molybdenum intrinsic brittleness (due to the special electron configuration of the transition metal) and complete recrystallization (i.e., grain boundary oxygen-enriched induced intergranular brittle fracture) greatly hinders its wide application as a structural material under extreme conditions.
Extensive research has shown that pure molybdenum is susceptible to complete recrystallization (or significant grain growth) under thermal or mechanical stimulation, which greatly reduces the deformability of the pure molybdenum, resulting in low strength and poor plasticity. In recent years, alloying has been applied to improve room temperature and high temperature properties of molybdenum materials, including solid solution softening (decreasing the strength of the partesvalley of screw dislocation motion by adding elements having a large number of d-shell electrons, such as rhenium), solid solution strengthening (increasing the resistance to dislocation motion by lattice distortion) and second phase strengthening (pinning dislocations and inhibiting recrystallization). Plastic deformation at high temperature is a diffusion-controlled process, not a slip-controlled process. This depends to a large extent on the lattice bonding of the matrix itself. Thus, once the operating temperature exceeds 1500 ℃, the alloying strategy of molybdenum-based metallic materials may become less effective in delaying recrystallization and maintaining mechanical properties. Therefore, how to design high performance molybdenum and molybdenum alloy materials by tuning the inherent thermo-mechanical treatment of molybdenum. It is required to alleviate inter-grain fracture often observed in grain boundary engineering on the one hand, and to improve dislocation storage capacity inside grains on the other hand. However, there are still great challenges in preparing molybdenum and molybdenum alloy materials with room temperature superplastic deformability.
Molybdenum and molybdenum alloy materials prepared by a combination of processes including powder metallurgy, continuous thermal deformation and high temperature annealing have stable fine grains and a high proportion of <110>// RD texture after ultra-high temperature annealing (1000-2200 ℃) and exhibit high plastic deformation capability at room temperature. The combination of the low-cost and high-efficiency preparation process is beneficial to design and development of high-strength refractory metal products which are suitable for harsher environments such as ultra-high temperature, high vacuum and the like.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation method of high-plasticity recrystallized molybdenum and molybdenum alloy. The method specifically comprises the following steps:
a preparation method of high-plasticity recrystallized molybdenum and molybdenum alloy comprises the following steps:
(1) Uniformly mixing the powder: mixing pure molybdenum powder or alloy powder purified by high-temperature hydrogen according to a certain proportion to obtain pure molybdenum or molybdenum alloy powder;
(2) Cold isostatic pressing: cold isostatic pressing is carried out on molybdenum powder and molybdenum alloy powder to prepare molybdenum or molybdenum alloy rod pressed billets;
(3) Hydrogen-vacuum composite sintering: pre-sintering the molybdenum or molybdenum alloy rod pressed compact at 1100-1400 ℃ with hydrogen and sintering in vacuum at 1600-2300 ℃ to obtain sintered molybdenum or molybdenum alloy rod pressed compact;
(4) Continuous heat deformation reducing processing: heating the molybdenum or molybdenum alloy rod blank obtained in the step (3) to 1000-1800 ℃, and performing multi-pass continuous thermal deformation processing (such as Y rolling, finish forging, finish rolling and the like), wherein the intermediate annealing temperature is 900-1500 ℃;
(5) Alkali washing and grinding: performing surface alkaline washing and hot water washing on the molybdenum or molybdenum alloy rod blank obtained in the step (4), and performing polishing treatment;
(6) High-temperature annealing treatment: carrying out high-temperature annealing treatment on the molybdenum or molybdenum alloy rod blank obtained in the step (5), and cooling along with a furnace;
preferably, the high-purity low-oxygen medium-fine particle molybdenum powder purified by high-temperature hydrogen in the step (1): mo content not less than 99.9 wt%, fisher size of 1-5 microns, and C/O not more than 50/500ppm; in the pure molybdenum powder or molybdenum alloy powder, 47.5 to 100 percent of Mo, 0 to 52.5 percent of Re, 0 to 2 percent of Ti, 0 to 1 percent of Zr, 0 to 1 percent of Hf, 0 to 0.5 percent of C and 0 to 5 percent of RE are calculated according to mass percent; preferably, RE is one or more of La, Y and Ce;
more preferably, the molybdenum alloy powder is TZM alloy powder, wherein the mass percentage of Ti is 0.40-0.55%, the mass percentage of Zr is 0.06-0.12%, the mass percentage of C is 0.01-0.04%, and the balance is Mo;
more preferably, the molybdenum alloy powder is molybdenum-rhenium alloy powder, and comprises, by mass, 47.5-98% of Mo and 2-52.5% of Re;
and respectively weighing molybdenum powder, rhenium source, titanium source, zirconium source, hafnium source, carbon powder and rare earth element-containing powder according to the mass percentages, and carrying out high-efficiency mixing treatment at the rotating speed of 30-90 r/min for 2-8 h to obtain high-uniformity pure molybdenum powder or molybdenum alloy powder.
Preferably, the cold isostatic pressing in the step (2) adopts a soft rubber mold, the outside of the soft rubber film is fixed and limited by a rigid sleeve, the pressure is 150-250 MPa, and the pressure maintaining time is 5-30 min.
Preferably, the hydrogen pre-sintering and vacuum sintering in the step (3) are performed in the same furnace directly by converting the atmosphere. The presintering time of the hydrogen is 0.5 to 4 hours, and the dew point of the high-purity hydrogen is less than or equal to minus 40 ℃; the vacuum degree of the vacuum sintering is better than 10 -2 Pa, sintering time is 4-10 h.
Preferably, in the step (4), the molybdenum or molybdenum alloy sintered rod blank is subjected to multi-pass continuous thermal deformation processing (such as Y rolling, finish forging, finish rolling and the like) with the deformation rate of 0.1 to 10 seconds -1 The total deformation is not less than 70% and the relative density is not less than 99.5%.
Preferably, in the step (5), the molybdenum or molybdenum alloy rod blank is washed with hot water after being subjected to alkali washing on the surface of molten sodium hydroxide.
Preferably, the annealing temperature in the step (6) is 1000-2200 ℃, the atmosphere can be hydrogen, vacuum, inert gas and the like, and the annealing time is not less than 0.5h.
The microstructure of the recrystallized crystalline molybdenum and molybdenum alloy prepared by the preparation method of the invention is a fine equiaxed crystal structure, the average grain size is less than or equal to 30 mu m, and the texture proportion of <110>// RD is more than or equal to 50%; the total elongation at room temperature is more than or equal to 60%, and more preferably, the total elongation at room temperature is more than or equal to 100%; the strength is more than or equal to 450MPa, more preferably, the strength is more than or equal to 650MPa.
The room temperature superplastic recrystallized molybdenum and molybdenum alloy can be widely used in aerospace, radar communication, equipment manufacturing or nuclear industry.
The invention has the beneficial effects that:
1. in the preparation method, high-purity low-oxygen medium-fine particle molybdenum powder and alloy powder subjected to high-temperature hydrogen or vacuum purification treatment are selected, so that the brittleness of crystal boundaries caused by oxygen can be effectively reduced, and the crystal grain sizes of a sintered state, a deformed state and a recrystallized state are thinned, so that the effect of strengthening and toughening fine crystals is realized.
2. In the preparation method, a continuous thermal deformation processing technology is selected for reducing processing, the degree of dynamic recrystallization can be regulated and controlled by effectively controlling the thermal deformation, a specific microstructure comprising fine grains and a high proportion of specific orientation is obtained after high-temperature annealing, the toughness of recrystallized molybdenum and molybdenum alloy is effectively improved, and the application of refractory metals in more severe environments such as ultrahigh temperature, high vacuum and the like is expected to be realized.
3. In the preparation method, after reducing processing, the bar is subjected to alkali washing and grinding, and the pollution layers such as surface oxidation, nitridation and the like are removed through alkali washing, so that corrosion of pollutants on the surface of the material to a hearth of an annealing furnace can be avoided; the defects of cracks, potential cracks and the like at the two ends of the head and the tail and a small amount of middle parts are removed through polishing, so that the risk of cracking and splitting in the subsequent processing is reduced, and the surface and internal quality of the material are improved.
4. The microstructure of the recrystallized molybdenum and molybdenum alloy prepared by the invention is a fine equiaxed crystal structure, the average grain size is less than or equal to 30 mu m, and the texture proportion of <110>// RD is more than or equal to 50%.
5. The total elongation at break of the recrystallized molybdenum and molybdenum alloy prepared by the method is more than or equal to 60 percent, and more preferably, the total elongation at break is more than or equal to 100 percent; the strength is more than or equal to 450MPa, more preferably, the strength is more than or equal to 650MPa.
Drawings
FIG. 1 is a process flow diagram of the disclosed method;
FIG. 2 is a three-dimensional metallographic microstructure of a recrystallized molybdenum rod of example 1 of the present invention;
FIG. 3 is a texture and grain size distribution of the recrystallized molybdenum rod of example 1;
FIG. 4 is an engineering stress-strain curve of the recrystallized molybdenum rod of example 1 after annealing at 1000 ℃ according to the present invention;
FIG. 5 is an engineering stress-strain curve of a TZM alloy rod in a recrystallized state after annealing at 2200℃according to example 2 of the present invention;
FIG. 6 is an engineering stress-strain curve of a recrystallized molybdenum-rhenium alloy rod of example 3 after 1700 ℃ annealing;
FIG. 7 is an engineering stress-strain curve of a recrystallized molybdenum rod of comparative example 1 after annealing at 1100 ℃.
Detailed Description
The invention will now be described in detail with reference to figures 1-7 and the detailed description. The embodiments shown below do not limit the inventive content described in the claims in any way. The whole contents of the constitution shown in the following examples are not limited to the solution of the invention described in the claims.
The invention relates to high-plasticity recrystallized molybdenum and molybdenum alloy, which comprise the following specific components in percentage by mass: 47.5 to 100 percent of Mo, 0 to 52.5 percent of Re, 0 to 2 percent of Ti, 0 to 1 percent of Zr, 0 to 1 percent of Hf, 0 to 0.5 percent of C and 0 to 5 percent of RE; preferably, RE is one or more of La, Y and Ce; the microstructure is a fine equiaxed grain structure, the average grain size is less than or equal to 30 mu m, the <110>// RD texture proportion is more than or equal to 50%, the total elongation at break is more than or equal to 60%, the total elongation at break is more preferably more than or equal to 100%, the strength is more preferably more than or equal to 450MPa, and the strength is more preferably more than or equal to 650MPa. Referring to fig. 1, the method for preparing high-plasticity recrystallized molybdenum and molybdenum alloy comprises the following steps:
(1) Uniformly mixing the powder: weighing purified high-purity low-oxygen molybdenum powder (with the Fisher particle size of 1-5 mu m) with the specification of fine particles, wherein the Mo content is not less than 99.9 weight percent, the C/O is less than or equal to 50/500ppm, the mass percent of the Mo is 47.5-100%, the Re is 0-52.5%, the Ti is 0-2%, the Zr is 0-1%, the Hf is 0-1%, the C is 0-0.5%, the RE is 0-5%, and the RE is one or more of La, Y and Ce; and (3) carrying out mixing treatment at the rotating speed of 30-90 r/min for 2-8 h to obtain pure molybdenum powder or molybdenum alloy powder.
(2) Cold isostatic pressing: the pure molybdenum powder or molybdenum alloy powder is used as a raw material, a cold isostatic pressing is adopted to prepare an exquisite molybdenum or molybdenum alloy rod pressed compact, the pressure is 150-250 MPa, the pressure maintaining time is 5-30 min, and the cold isostatic pressing is fixed and limited by a rigid sleeve outside a soft adhesive film.
(3) Hydrogen-vacuum composite sintering: carrying out 1000-1400 ℃ and 0.5-4 h low-temperature hydrogen presintering on the compact of the refined molybdenum or molybdenum alloy rod obtained by cold isostatic pressing, wherein the dew point of the hydrogen is not higher than-40 ℃, and then converting the atmosphere in the same furnace to be better than 10 percent -2 Vacuum sintering at 1600-2300 deg.c for 4-10 hr to obtain density of 9.7 + -0.4 g/cm 3 Low impurity precision sintering bar blank.
(4) Continuous heat deformation reducing processing: heating the molybdenum or molybdenum alloy sintered rod blank to 1000-1800 ℃, and carrying out multi-pass continuous thermal deformation processing (such as Y rolling, finish forging, finish rolling and the like) according to the diameter specification of the molybdenum or molybdenum alloy rod, wherein the intermediate annealing temperature is 900-1500 ℃, and the deformation rate is 0.1-10 s -1 The total deformation is not less than 7%. Heating before or during the deformation process is performed in a hydrogen furnace, and the relative density is not less than 99.5%.
(5) Alkali washing and grinding: the surface of the molybdenum or molybdenum alloy rod blank is washed by hot water after being subjected to alkaline washing by molten sodium hydroxide at 400 ℃, and defects such as surface pressed matters, residual oxide skin, local microcracks and the like are polished according to requirements.
(6) High-temperature annealing treatment: high-temperature annealing treatment with temperature uniformity within + -20 deg.c and precision controllable temperature of not less than 0.5 hr in the temperature range of 1000-1900 deg.c, atmosphere of hydrogen, vacuum, inert gas, etc and subsequent cooling in furnace.
Example 1
The high-temperature hydrogen purified fine particle molybdenum powder with the Fisher particle size of 1 mu m is taken as a raw material, and the Mo content is 99.99 weight percent,Impurity C/O was 40ppm/450ppm, respectively; uniformly filling the molybdenum powder into a soft rubber sleeve fixed and limited by a rigid sleeve, and performing cold isostatic pressing for 10min under 150MPa pressure to obtain a refined molybdenum rod blank; placing the molybdenum rod-shaped pressed compact in a hydrogen-vacuum dual-purpose high-temperature furnace, and sintering for 4 hours at 1100 ℃ in a high-purity hydrogen atmosphere with the dew point of-40 ℃; then directly converting the atmosphere into 10 in the same furnace -3 Pa vacuum, completing high temperature vacuum sintering at 1600 ℃ for 4 hours to obtain density 9.9g/cm 3 Is used for refining the sintered molybdenum rod blank with low impurity. Heating the refined molybdenum rod blank to 1000 ℃ under the protection of hydrogen atmosphere, and carrying out continuous multi-pass Y-rolling processing with the deformation rate of 10s -1 Intermediate annealing temperature 900 ℃, total deformation 95%; after alkaline washing, hot water cleaning and defect grinding treatment of the surface of molten sodium hydroxide at 400 ℃, placing the rod blank in high-purity hydrogen atmosphere with the dew point of-40 ℃, and annealing at 1000 ℃ and the temperature uniformity of +/-5 ℃ for 0.5h; finally, the molybdenum content of 99.98 percent by weight, the relative density of 99.8 percent and the average grain size of 18 mu m (the three-dimensional metallographic microstructure is shown in figure 2),<110>the ratio of the structure of the molybdenum rod (i.e. the molybdenum rod with the tensile strength of 514MPa and the total elongation at break of 108.7 percent (engineering stress-strain curve is shown in figure 4) is 77.9 percent (the structure and the grain size distribution are shown in figure 3).
Example 2
Taking high-temperature hydrogen purified molybdenum powder with particle size of 5 μm, wherein the Mo content is 99.99 wt%, the impurity C/O is 45ppm/480ppm, and 0.45 wt% of TiH with particle size of 3 μm is added 2 0.08 wt.% of ZrH of the Fisher size 3 μm particle size 2 0.04 weight percent of carbon powder with the particle size of 1 mu m is subjected to mixing treatment, the rotating speed is 30r/min, and the mixing time is 8 hours; uniformly filling the TZM alloy powder into a soft rubber sleeve fixed and limited by a rigid sleeve, uniformly knocking a pestle during filling, binding by an iron wire, tightly sealing, and carrying out cold isostatic pressing for 5min under the pressure of 250MPa to obtain a refined TZM alloy rod blank; placing the TZM alloy bar-shaped pressed compact in a hydrogen-vacuum dual-purpose high-temperature furnace, and sintering at 1400 ℃ for 0.5h under the high-purity hydrogen atmosphere with the dew point of-40 ℃; then directly converting the atmosphere into 10 in the same furnace -3 Pa vacuum, completing 2300 ℃ high-temperature vacuum sintering for 10 hoursJunction to give a density of 9.5g/cm 3 The low impurity refined sintered TZM alloy rod blank. Heating the refined TZM alloy bar blank to 1800 ℃ under the protection of hydrogen atmosphere, and carrying out continuous multipass precision forging processing with the deformation rate of 1s -1 Intermediate annealing temperature 1500 ℃, total deformation 70%; after alkaline washing, hot water cleaning and defect grinding treatment of the molten sodium hydroxide surface at 420 ℃, placing the rod blank in a vacuum atmosphere, and annealing at 2200 ℃ and the temperature uniformity of +/-20 ℃ for 4 hours; finally, the relative density is 99.8 percent, the average grain size is 23 mu m,<110>the TZM alloy rod with the texture ratio of/(RD) of 56.8%, the tensile strength of 713MPa and the total elongation at break of 100.2% (engineering stress-strain curve is shown in FIG. 5).
Example 3
Taking high-temperature hydrogen purified fine-particle molybdenum powder with the Fisher particle size of 3 mu m as a raw material, wherein the Mo content is 99.99 wt% and the impurity C/O is 43ppm/470ppm respectively, adding 47.5 wt% of the fine-particle rhenium powder with the Fisher particle size of 3 mu m, mixing, and the rotating speed is 60r/min, and the mixing time is 4h; uniformly filling the molybdenum-rhenium alloy powder into a soft rubber sleeve fixed and limited by a rigid sleeve, and performing cold isostatic pressing for 30min under the pressure of 200MPa to obtain a refined molybdenum-rhenium alloy rod blank; placing the molybdenum-rhenium alloy rod-shaped pressed compact in a hydrogen-vacuum dual-purpose high-temperature furnace, and sintering for 2h at 1200 ℃ in a high-purity hydrogen atmosphere with the dew point of-40 ℃; then directly converting the atmosphere into 10 in the same furnace -3 Pa vacuum, completing high temperature vacuum sintering at 2000 ℃ for 6 hours to obtain density 9.7g/cm 3 Is used for refining the sintered molybdenum-rhenium alloy rod blank with low impurity. Heating the refined molybdenum-rhenium alloy rod blank to 1300 ℃ under the protection of hydrogen atmosphere, and carrying out continuous multipass finish rolling processing with the deformation rate of 0.1s -1 Intermediate annealing temperature 1000 ℃, total deformation 87%; after alkaline washing, hot water cleaning and defect grinding treatment of the surface of molten sodium hydroxide at 390 ℃, placing the rod blank in high-purity hydrogen atmosphere with the dew point of-40 ℃, and annealing for 2 hours at 1700 ℃ and the temperature uniformity of +/-10 ℃; finally, the relative density is 99.8 percent, the average grain size is 26.8 mu m,<110>the molybdenum-rhenium alloy rod with the texture proportion of 65.4 percent, the tensile strength of 678MPa and the total elongation at break of 98.3 percent (engineering stress-strain curve is shown in figure 6).
Example 4
Taking high-temperature hydrogen purified fine-grained molybdenum powder with the Fisher size of 4 mu m as a raw material, wherein the Mo content is 99.99 wt%, the impurity C/O is 39ppm/460ppm respectively, and 0.5 wt% of La with the Fisher size of 3 mu m is added 2 O 3 Powder, 0.2 wt% of Y of particle size 2 μm of Fisher particle size 2 O 3 Powder, and 0.1 wt% CeO of Fisher size 2 μm particle size 2 Powder is mixed, the rotating speed is 30r/min, and the mixing time is 6h; uniformly filling the rare earth doped molybdenum alloy powder into a soft rubber sleeve fixed and limited by a rigid sleeve, and performing cold isostatic pressing for 15min under the pressure of 200MPa to obtain a refined rare earth doped molybdenum alloy rod blank; placing the rare earth doped molybdenum alloy bar-shaped pressed compact in a hydrogen-vacuum dual-purpose high-temperature furnace, and sintering for 4 hours at 1300 ℃ in a high-purity hydrogen atmosphere with the dew point of-40 ℃; then directly converting the atmosphere into 10 in the same furnace -3 Pa vacuum, completing high temperature vacuum sintering at 2100 ℃ for 6 hours to obtain density 9.8g/cm 3 Is a low impurity refined sintered rare earth doped molybdenum alloy rod blank. Heating the refined rare earth doped molybdenum alloy bar blank to 1500 ℃ under the protection of hydrogen atmosphere, and carrying out continuous multi-pass Y rolling processing with the deformation rate of 1s -1 Intermediate annealing temperature 1300 ℃, total deformation 84%; after alkaline washing, hot water cleaning and defect grinding treatment of the surface of molten sodium hydroxide at 380 ℃, placing the rod blank in high-purity hydrogen atmosphere with the dew point of-40 ℃, and annealing for 4 hours at 1600 ℃ and the temperature uniformity of +/-10 ℃; finally, the relative density is 99.8 percent, the average grain size is 22.5 mu m,<110>the texture proportion of the V/RD is 59.6 percent, the tensile strength is 636MPa, and the total elongation at break is 85.9 percent.
Comparative example 1
Taking coarse-grain molybdenum powder with the Fisher size of 6 mu m as a raw material, wherein the Mo content is 99.99 weight percent, and the impurity C/O is 100ppm/1000ppm respectively; filling the molybdenum powder into a soft rubber sleeve, and performing cold isostatic pressing for 10min under the pressure of 200MPa to obtain a molybdenum rod blank; the molybdenum rod-shaped pressed compact is placed in a hydrogen high-temperature furnace and sintered for 4 hours at 1900 ℃ in the hydrogen atmosphere to obtain the density of 9.8g/cm 3 A sintered molybdenum rod blank. Heating the molybdenum rod blank to the temperature under the protection of hydrogen atmosphereCarrying out multi-pass rotary forging processing at 1100 ℃, wherein the intermediate annealing temperature is 800 ℃, and the total deformation is 91%; placing the rod blank in a hydrogen atmosphere, and carrying out annealing treatment for 1h at 1100 ℃; the average grain size was finally obtained as 68 μm,
<110>// RD texture ratio 20.5%, tensile strength 519MPa, total elongation at break 12.6% (engineering stress-strain curve is shown in FIG. 7).
Performance test:
the pure molybdenum or molybdenum alloy rods prepared in examples 1 to 4 of the present invention and comparative example 1 were subjected to performance tests, see GB-T228.1-2021 section 1 of tensile test for metallic materials: room temperature test method "tensile test was performed, and the results are shown in table 1.
As can be seen from the results in Table 1, the pure molybdenum or molybdenum alloy rods produced in examples 1 to 4 of the present invention have a higher tensile strength than comparative example 1, wherein example 3 has a tensile strength of 650MPa or more; the total elongation at break is much higher than in the comparative examples, where examples 1 and 2 can be more than or equal to 100%.
Table 1 shows the performance results of the pure molybdenum or molybdenum alloy bars produced in examples 1-4 and comparative example 1 of the present invention.
| Tensile strength/MPa | Total elongation at break/% | |
| Example 1 | 514 | 108.7 |
| Example 2 | 713 | 100.2 |
| Example 3 | 678 | 98.3 |
| Example 4 | 636 | 85.9 |
| Comparative example 1 | 519 | 12.6 |
Claims (10)
1. The preparation method of the high-plasticity recrystallized molybdenum and molybdenum alloy is characterized by comprising the following steps of:
(1) Uniformly mixing the powder: mixing pure molybdenum powder or alloy powder purified by high-temperature hydrogen according to a certain proportion to obtain pure molybdenum or molybdenum alloy powder;
(2) Cold isostatic pressing: cold isostatic pressing is carried out on molybdenum powder or molybdenum alloy powder to obtain molybdenum and molybdenum alloy rod pressed billets;
(3) Hydrogen-vacuum composite sintering: pre-sintering the molybdenum or molybdenum alloy rod pressed compact at 1100-1400 ℃ with hydrogen and sintering in vacuum at 1600-2300 ℃ to obtain sintered molybdenum or molybdenum alloy rod pressed compact;
(4) Continuous heat deformation reducing processing: heating the molybdenum or molybdenum alloy rod blank obtained in the step (3) to 1000-1800 ℃ for continuous thermal deformation processing (such as Y rolling, finish forging, finish rolling and the like), and intermediate annealing temperature is 900-1500 ℃;
(5) Alkali washing and grinding: performing surface alkaline washing and hot water washing on the molybdenum or molybdenum alloy rod blank obtained in the step (4), and performing polishing treatment;
(6) High-temperature annealing treatment: and (3) carrying out high-temperature annealing treatment on the molybdenum or molybdenum alloy rod blank obtained in the step (5), and cooling along with a furnace.
2. The method for preparing high-plasticity recrystallized molybdenum and molybdenum alloy according to claim 1, wherein the purified high-purity low-oxygen medium-fine-particle molybdenum powder in step (1): mo content not less than 99.9 wt%, fisher size of 1-5 microns, and C/O not more than 50/500ppm; in the pure molybdenum powder or molybdenum alloy powder, 47.5 to 100 percent of Mo, 0 to 52.5 percent of Re, 0 to 2 percent of Ti, 0 to 1 percent of Zr, 0 to 1 percent of Hf, 0 to 0.5 percent of C and 0 to 5 percent of RE are calculated according to mass percent; RE is one or more of La, Y and Ce.
3. The method for producing high-plasticity recrystallized molybdenum and molybdenum alloy according to claim 1, wherein the purified high-purity low-oxygen medium-fine-particle molybdenum powder in the step (1) is TZM alloy powder, and the mass percentage of Ti is 0.40-0.55%, zr is 0.06-0.12%, C is 0.01-0.04%, and the balance is Mo.
4. The method for preparing high-plasticity recrystallized molybdenum and molybdenum alloy according to claim 1, wherein the purified high-purity low-oxygen medium-fine particle molybdenum powder in the step (1) is molybdenum-rhenium alloy powder, and the mass percentage of the molybdenum is 47.5-98% and the mass percentage of the Re is 2-52.5%.
5. The method for preparing high-plasticity recrystallized molybdenum and molybdenum alloy according to claim 1, wherein in the step (1), molybdenum powder, rhenium source, titanium source, zirconium source, hafnium source, carbon powder and rare earth element-containing powder are respectively weighed according to the mass percentages and are subjected to high-efficiency mixing treatment, the rotating speed is 30-90 r/min, and the mixing time is 2-8 h, so that high-uniformity pure molybdenum powder or molybdenum alloy powder is obtained.
6. The method for preparing high-plasticity recrystallized molybdenum and molybdenum alloy according to claim 1, wherein the hydrogen pre-sintering and vacuum sintering in the step (3) are performed in the same furnace directly by converting the atmosphere. The presintering time of the hydrogen is 0.5 to 4 hours, and the dew point of the high-purity hydrogen is less than or equal toAt-40 ℃; the vacuum degree of the vacuum sintering is better than 10 -2 Pa, sintering time is 4-10 h.
7. The method for producing high-plasticity recrystallized molybdenum and molybdenum alloy according to claim 1, wherein in the step (4), the sintered rod blank of molybdenum or molybdenum alloy is subjected to multi-pass continuous heat deformation (such as Y rolling, finish forging, finish rolling, etc.), the deformation rate is 0.1-10 s -1 The total deformation is not less than 70% and the relative density is not less than 99.5%.
8. The method for preparing high-plasticity recrystallized molybdenum and molybdenum alloy according to claim 1, wherein the annealing temperature in the step (6) is 1000-2200 ℃, the atmosphere can be hydrogen, vacuum, inert gas, etc., and the annealing time is not less than 0.5h.
9. A high plasticity recrystallized molybdenum and molybdenum alloy prepared by the preparation method of any one of claims 1-8, wherein the microstructure of the recrystallized molybdenum and molybdenum alloy is a fine equiaxed crystal structure, the average grain size is less than or equal to 30 μm, and the <110>// RD texture ratio is more than or equal to 50%; the total elongation at break is more than or equal to 60 percent.
10. Use of the room temperature superplastic recrystal molybdenum and molybdenum alloys of claim 9 in aerospace, radar communications, equipment manufacturing or nuclear industries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311819818.1A CN117884617A (en) | 2023-12-27 | 2023-12-27 | Preparation method of high-plasticity recrystallized molybdenum and molybdenum alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311819818.1A CN117884617A (en) | 2023-12-27 | 2023-12-27 | Preparation method of high-plasticity recrystallized molybdenum and molybdenum alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117884617A true CN117884617A (en) | 2024-04-16 |
Family
ID=90643758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311819818.1A Pending CN117884617A (en) | 2023-12-27 | 2023-12-27 | Preparation method of high-plasticity recrystallized molybdenum and molybdenum alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117884617A (en) |
-
2023
- 2023-12-27 CN CN202311819818.1A patent/CN117884617A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108145157B (en) | Preparation method of high-performance molybdenum-rhenium alloy bar | |
| CN108145156B (en) | Preparation method of high-performance TZM molybdenum alloy bar | |
| CN110373561B (en) | Method for preparing high-density fine-grain titanium alloy through powder forging | |
| CN112941351B (en) | Preparation method of powder metallurgy titanium and titanium alloy with ultrahigh fatigue strength | |
| CN109434119B (en) | Preparation method of high-toughness MXene phase doped molybdenum alloy | |
| CN115198162B (en) | Entropy alloy in high-toughness heterogeneous multi-phase core-shell organization structure and preparation method thereof | |
| CN107971499A (en) | The method for preparing spherical titanium aluminium-based alloyed powder end | |
| CN108977693B (en) | A kind of recrystallization high-strength titanium alloy and preparation method thereof | |
| CN114134385A (en) | Refractory medium-entropy alloy and preparation method thereof | |
| CN111763841B (en) | Powder metallurgy titanium or titanium alloy product and short-process preparation method thereof | |
| CN107952966A (en) | The preparation method at spherical titanium aluminium-based alloyed powder end | |
| CN116275050B (en) | Preparation method of high-strength molybdenum | |
| CN113862540A (en) | MAX phase added molybdenum alloy and preparation method thereof | |
| CN112143925A (en) | Preparation method of high-strength high-plasticity titanium-magnesium composite material | |
| CN115404385B (en) | Refractory high-entropy alloy with excellent room-temperature tensile ductility and preparation method thereof | |
| CN117884617A (en) | Preparation method of high-plasticity recrystallized molybdenum and molybdenum alloy | |
| CN114086086B (en) | Nano-phase carbon-nitrogen composite particle reinforced invar alloy wire and preparation method thereof | |
| CN109913731A (en) | A kind of high tough Ti-Al series intermetallic compound and preparation method thereof | |
| CN113385671B (en) | High-toughness low-modulus titanium/beta-titanium alloy multilayer composite material and preparation method thereof | |
| CN113025844B (en) | High-temperature titanium alloy and preparation method thereof | |
| CN111411249B (en) | Preparation method of VNbMoTaW high-entropy alloy | |
| CN114836665A (en) | Ta-W-Hf-Re-C alloy and preparation method of bar thereof | |
| CN114990403B (en) | Tungsten-tantalum-niobium alloy material and preparation method thereof | |
| CN115198163B (en) | Preparation method of multi-nano-phase reinforced ODS alloy with tensile plasticity | |
| CN114589305B (en) | Method for manufacturing molybdenum alloy for fast neutron reactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |