CN117305803A - Preparation method of high-purity molybdenum-rhenium alloy - Google Patents
Preparation method of high-purity molybdenum-rhenium alloy Download PDFInfo
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- CN117305803A CN117305803A CN202311239444.6A CN202311239444A CN117305803A CN 117305803 A CN117305803 A CN 117305803A CN 202311239444 A CN202311239444 A CN 202311239444A CN 117305803 A CN117305803 A CN 117305803A
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- molybdenum
- rhenium
- purity
- rhenium alloy
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- YUSUJSHEOICGOO-UHFFFAOYSA-N molybdenum rhenium Chemical compound [Mo].[Mo].[Re].[Re].[Re] YUSUJSHEOICGOO-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910000691 Re alloy Inorganic materials 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 28
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 25
- 239000011733 molybdenum Substances 0.000 claims abstract description 25
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000003754 machining Methods 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000011978 dissolution method Methods 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- WSWMGHRLUYADNA-UHFFFAOYSA-N 7-nitro-1,2,3,4-tetrahydroquinoline Chemical group C1CCNC2=CC([N+](=O)[O-])=CC=C21 WSWMGHRLUYADNA-UHFFFAOYSA-N 0.000 claims description 9
- 229910021637 Rhenium(VI) chloride Inorganic materials 0.000 claims description 9
- DBGPLCIFYUHWKA-UHFFFAOYSA-H hexachloromolybdenum Chemical compound Cl[Mo](Cl)(Cl)(Cl)(Cl)Cl DBGPLCIFYUHWKA-UHFFFAOYSA-H 0.000 claims description 9
- GSGIQJBJGSKCDZ-UHFFFAOYSA-H hexachlororhenium Chemical compound Cl[Re](Cl)(Cl)(Cl)(Cl)Cl GSGIQJBJGSKCDZ-UHFFFAOYSA-H 0.000 claims description 9
- YUCDNKHFHNORTO-UHFFFAOYSA-H rhenium hexafluoride Chemical group F[Re](F)(F)(F)(F)F YUCDNKHFHNORTO-UHFFFAOYSA-H 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 17
- 239000010959 steel Substances 0.000 description 17
- 239000000956 alloy Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000010587 phase diagram Methods 0.000 description 4
- 238000009853 pyrometallurgy Methods 0.000 description 4
- 238000012958 reprocessing Methods 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910001325 element alloy Inorganic materials 0.000 description 3
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 238000013094 purity test Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910015275 MoF 6 Inorganic materials 0.000 description 1
- 229910019595 ReF 6 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4412—Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45512—Premixing before introduction in the reaction chamber
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a preparation method of a high-purity molybdenum-rhenium alloy, which comprises the following steps: s1, carrying out primary premixing on metal precursors of molybdenum and rhenium to form a mixture; s2, introducing the mixture into a secondary mixing process, uniformly mixing again in the secondary mixing process, and preheating the mixture; s3, introducing the preheated mixture and hydrogen into a reactor with a matrix material for reaction, and depositing a reaction product on the matrix; and S4, taking out the product obtained in the step S3, and removing the matrix by adopting an acid dissolution method or a machining method to obtain the high-purity molybdenum-rhenium alloy product. The invention firstly utilizes the chemical vapor deposition method to react the two metal precursors under specific conditions to prepare the high-purity molybdenum-rhenium alloy, and not only can prepare the high-purity molybdenum-rhenium alloy, but also can recycle the byproducts of the chemical vapor deposition reaction and the raw materials which do not participate in the reaction, thereby improving the utilization rate of the raw materials, reducing the production cost and being beneficial to industrial production.
Description
Technical Field
The invention relates to the special technical field of refractory metal preparation, in particular to a preparation method of a high-purity molybdenum-rhenium alloy.
Background
Pure molybdenum as a body centered cubic metal exhibits brittleness at room temperature and poor workability, which restricts the deep workability and service life of metallic molybdenum to some extent. The addition of rhenium in molybdenum can obviously improve the low-temperature brittleness of molybdenum, further improve the processing performance, increase the strength and keep good plasticity, and the addition of rhenium also changes the mechanical deformation behavior of molybdenum from single sliding to combination of twin sliding in the hot working and cold working processes, inhibits the embrittlement of carbon and oxygen, improves the welding performance of materials, can lead the forged and rolled products to have lower ductile-brittle transition temperature, and can lead the embrittlement degree of the materials to be reduced after recrystallization annealing. This improvement in molybdenum performance by the addition of rhenium is known as the "rhenium effect".
In addition, the molybdenum-rhenium alloy has good compatibility with nuclear fuel and alkali metal coolant, and Re element is a better spectral shift absorber material, so that the critical accident risk of the reactor can be effectively reduced. The molybdenum-rhenium alloy is an optimal reactor core structural material in a space nuclear power supply, the types of rays in a reactor are many, but for metal materials, the influence of the performance is mainly neutron irradiation, the influence of alpha rays, beta rays and gamma rays is smaller, the radiation resistance of the molybdenum-rhenium alloy is mainly dependent on the purity of the alloy material, the higher the purity of the material is, the less precipitation is generated after irradiation, the less irradiation embrittlement is caused, and the service life of the material is prolonged. The existing preparation process of the molybdenum-rhenium alloy mainly comprises a pyrometallurgy process and a powder metallurgy process, wherein the pyrometallurgy process is mainly a vacuum smelting process, the purity of the molybdenum-rhenium alloy prepared by the method is difficult to reach 99.99%, and the structure of the alloy material is uneven; the powder metallurgy process is simple and high in purity compared with the pyrometallurgy process, but the purity of the molybdenum-rhenium alloy prepared by the process depends on the purities of the molybdenum powder and the rhenium powder, and the highest purity of the molybdenum-rhenium alloy at present reaches 99.99% -99.995% due to the limitation of the process per se, so that 99.999% cannot be broken through for a long time.
On the other hand, the research on the performance of the molybdenum-rhenium two-element alloy is mainly based on the existing material with the purity below 4N level, the absolute molybdenum-rhenium two-element alloy cannot be realized due to the existence of impurity elements, and the research on the mechanical performance, the structure, the service life of the material and other aspects of the molybdenum-rhenium two-element alloy by the existing scientific researchers is seriously influenced. In view of this, a new preparation method of high-purity molybdenum-rhenium alloy needs to be studied to overcome the above-mentioned drawbacks of the prior art, especially the technical problem of low purity.
Disclosure of Invention
In order to overcome the defect of low purity of the molybdenum-rhenium alloy, the invention provides a preparation method of the high-purity molybdenum-rhenium alloy, which aims to solve the technical problems.
In order to achieve the aim of the invention, the specific technical scheme of the preparation method of the high-purity molybdenum-rhenium alloy is as follows:
the preparation method of the high-purity molybdenum-rhenium alloy comprises the following steps:
s1, carrying out primary premixing on metal precursors of molybdenum and rhenium to form a mixture, wherein the mol ratio of the precursors of the molybdenum and the rhenium is controlled to be 20:1-1:20;
s2, carrying out secondary mixing on the mixture, uniformly mixing again in the secondary mixing, and preheating the mixture;
s3, heating the reactor with the matrix material, introducing the preheated mixture and hydrogen into the reactor after heating, and reacting at 300-1200 ℃ to deposit a reaction product on the matrix;
and S4, taking out the product obtained in the step S3, and removing the matrix by adopting an acid dissolution method or a machining method to obtain the high-purity molybdenum-rhenium alloy product with the purity of 99.999 percent or more.
Preferably, the preparation method is carried out under the protection of inert gas atmosphere, in particular to connecting inert gas with a reaction system pipeline, and evacuating and replacing the reaction system by using the inert gas.
Preferably, the inert gas is nitrogen, argon or helium, the purity is 99.0% -99.9999%, when the inert gas is pumped out for replacement, the inert gas is pumped to-0.2-0 MPa, the inert gas is pumped to 0.01-0.30 MPa, and the inert gas is repeatedly carried out for 3-20 times until the replacement of the inert gas is completed.
Preferably, the metal precursor of the molybdenum is molybdenum hexafluoride or molybdenum hexachloride, and the purity is 99.0% -99.9999%; the metal precursor of rhenium is rhenium hexafluoride or rhenium hexachloride, the purity is 99.0% -99.9999%, and the purity of hydrogen is 99.0% -99.9999%.
Preferably, when the primary premixing is carried out, the mixing time is 10-120min, and the volume of the mixture is controlled to be 5-80% of that of the primary mixer; during secondary mixing, the preheating temperature of the mixture is 50-200 ℃.
Preferably, the reactor is preheated before the mixture and the hydrogen are introduced in the step S3, the heating rate is controlled to be 50-500 ℃/h, the temperature is raised to 300-1200 ℃, the mixture and the hydrogen are stably maintained for 0.5-5.0 h, and then the mixture and the hydrogen are introduced into the reactor.
Preferably, in the step S3, the flow rate of the introduced hydrogen is controlled to be 0.5-50g/min, the molar ratio of the introduced mixture to the hydrogen is controlled to be 1:1-1:12, the internal pressure of the reactor is controlled to be 0-0.5 MPa, and the molybdenum-rhenium alloy product with the thickness of 0.05 mu m-200 mm is prepared.
The reaction that occurs in this process is:
MoF 6 (g)+3H 2 (g)→6Mo(s)+6HF(g)20kJ/mol
ReF 6 (g)+3H 2 (g)→6Re(s)+6HF(g)288kJ/mol
preferably, after the reaction in the step S3 is completed, the reactor starts to be cooled, and the tail gas treatment device is started to collect and reprocess the reaction byproducts and unreacted raw materials.
Preferably, the tail gas treatment device comprises a two-stage rectifying tower, and the rectified material returns to the one-stage premixing process in the step S1.
Preferably, in the step S4, the acid dissolution method is to use nitric acid, sulfuric acid or hydrochloric acid, and the acid solution is used for removing the substrate by corrosion; the machining method is to adopt linear cutting, grinding machine machining or milling machine machining to remove the matrix.
The preparation method of the high-purity molybdenum-rhenium alloy has the following beneficial effects:
1. the invention provides a preparation method of a high-purity molybdenum-rhenium alloy, the purity of the prepared molybdenum-rhenium alloy material is up to 99.999 percent or more, and compared with the alloy material prepared by adopting the conventional process of pyrometallurgy and powder metallurgy, the purity of the prepared molybdenum-rhenium alloy material is higher, and the influence of impurity elements on the mechanical properties of the alloy is effectively avoided.
2. The invention firstly provides a high-purity molybdenum-rhenium alloy prepared by respectively mixing molybdenum and rhenium metal precursors by a chemical vapor deposition method and then reacting with hydrogen under specific conditions, which defines the parameter control range of each process for preparing the high-purity molybdenum-rhenium alloy by chemical vapor deposition and provides a material with higher purity and more approximate absolute binary alloy for the research and development of molybdenum-rhenium alloy materials.
3. When the molybdenum-rhenium alloy material is prepared, the metal precursors of molybdenum and rhenium are mixed and preheated in two stages, so that the metal precursors of molybdenum and rhenium are mixed more fully, the process of material mixing and heating during reaction is shortened, the metal precursors of molybdenum and rhenium and hydrogen can be reacted rapidly and uniformly, the generated molybdenum-rhenium is arranged in an atomic stack form, the high-purity molybdenum-rhenium alloy material is obtained, the high-purity molybdenum-rhenium alloy material has a more uniform microstructure, and the uniformity of the microstructure is improved, so that the mechanical property of the material is further promoted greatly.
4. The invention prepares the high-purity molybdenum-rhenium alloy, and simultaneously recovers, processes and recycles byproducts of the chemical vapor deposition reaction and raw materials which do not participate in the reaction, thereby improving the utilization rate of the raw materials, reducing the production cost and being beneficial to industrial production.
5. The invention provides a preparation method of a high-purity molybdenum-rhenium alloy, which is more stable and reliable than the traditional process, and effectively improves the tensile strength and yield strength of the material.
Drawings
FIG. 1 is a schematic flow chart of the preparation process of the invention;
FIG. 2 is a metallographic structure diagram of the molybdenum-rhenium alloy prepared by the invention.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description will refer to the specific implementation, structure, characteristics and effects according to the present invention with reference to the accompanying drawings and preferred embodiments.
Example 1
As shown in fig. 1, which is a schematic flow chart of the preparation process of the present invention, the preparation method of the high-purity molybdenum-rhenium alloy in this embodiment includes the following steps:
s1, connecting molybdenum hexafluoride and rhenium hexafluoride with the purity of 99.9 percent, hydrogen with the purity of 99.9 percent and nitrogen with the purity of 99.9 percent with a reaction system pipeline;
starting a valve of a nitrogen steel cylinder, starting to evacuate the reaction system to 0MPa by using nitrogen, and pressurizing to 0.05MPa, and performing circulation for 5 times;
respectively starting steel cylinders of molybdenum hexafluoride and rhenium hexafluoride, controlling the mole ratio of the molybdenum hexafluoride to the rhenium hexafluoride to be 20:1, fully and uniformly mixing the two metal precursors in a primary mixer for 10min, and controlling the mixing time to be 5% of the volume of the primary mixer;
s2, opening a valve of an outlet pipeline of the primary mixer, enabling the mixture to enter a secondary mixer, opening a heating device of the secondary mixer, and heating the secondary mixer to 50 ℃, wherein the mixture becomes gaseous and is uniformly mixed in the secondary mixer;
s3, starting a heating device of the reactor, and stabilizing the substrate in the reactor for 1.0h after heating to 300 ℃ at a heating rate of 100 ℃/h;
opening a hydrogen steel bottle, and controlling the hydrogen flow to be 0.5g/min;
opening an outlet valve of the secondary mixer, adjusting the flow of the mixture, controlling the molar ratio of the mixture gas outlet to the hydrogen gas outlet to be 1:1, controlling the pressure of a reaction system to be 0.05MPa, and starting the chemical vapor deposition reaction in the process, wherein molybdenum-rhenium alloy is deposited on a substrate to prepare a molybdenum-rhenium alloy product with the thickness of 0.05 mu m;
closing a molybdenum-rhenium metal precursor steel cylinder and a mixer outlet valve, closing a mixing heating device, closing a reactor heating device, and starting cooling the reactor at a cooling rate controlled to be 20 ℃/h;
starting a tail gas treatment device, collecting and reprocessing the reaction byproducts and unreacted raw materials in the test, wherein the tail gas treatment device comprises a two-stage rectifying tower, and the rectified materials are returned to a first-stage mixer in the step S1;
and S4, taking out the product obtained in the step S3 after the temperature is reduced to normal temperature, and removing the matrix by adopting nitric acid to obtain the high-purity molybdenum-rhenium alloy product.
Example 2
The preparation method of the high-purity molybdenum-rhenium alloy comprises the following steps:
s1, connecting molybdenum hexafluoride and rhenium hexafluoride with the purity of 99.99%, hydrogen with the purity of 99.99% and helium with the purity of 99.99% with a reaction system pipeline;
starting a helium steel cylinder valve, evacuating the reaction system to-0.10 MPa by helium, pressurizing to 0.15MPa, and circularly performing for 10 times;
respectively starting steel cylinders of molybdenum hexafluoride and rhenium hexafluoride, controlling the mole ratio of the molybdenum hexafluoride to the rhenium hexafluoride to be 1:1, fully and uniformly mixing the two metal precursors in a primary mixer for 60min, and controlling the mixing time to be 50% of the volume of the primary mixer;
s2, opening a valve of an outlet pipeline of the primary mixer, enabling the mixture to enter a secondary mixer, opening a heating device of the secondary mixer, and heating the secondary mixer to 100 ℃;
s3, starting a heating device of the reactor, and heating a substrate in the reactor to 600 ℃ and then stabilizing for 3.0h, wherein the heating rate is 300 ℃/h;
opening a hydrogen steel bottle, and controlling the hydrogen flow to be 20g/min;
opening an outlet valve of the secondary mixer, adjusting the flow of the mixture, controlling the molar ratio of the mixture gas outlet to the hydrogen gas outlet to be 1:3, controlling the pressure of a reaction system to be 0.2MPa, and starting the chemical vapor deposition reaction in the process, wherein molybdenum-rhenium alloy is deposited on a substrate to prepare a molybdenum-rhenium alloy product with the thickness of 10 mm;
closing a molybdenum-rhenium metal precursor steel cylinder and a mixer outlet valve, closing a mixing heating device, closing a reactor heating device, and starting cooling the reactor, wherein the cooling rate is controlled to be 100 ℃/h;
starting a tail gas treatment device, collecting and reprocessing the reaction byproducts and unreacted raw materials in the test, wherein the tail gas treatment device comprises a two-stage rectifying tower, and the rectified materials are returned to a first-stage mixer in the step S1;
and S4, taking out the product obtained in the step S3 after the temperature is reduced to normal temperature, and removing the matrix by sulfuric acid to obtain the high-purity molybdenum-rhenium alloy product.
Example 3
The preparation method of the high-purity molybdenum-rhenium alloy comprises the following steps:
s1, connecting molybdenum hexachloride and rhenium hexachloride with the purity of 99.9999 percent, hydrogen with the purity of 99.9999 percent and argon with the purity of 99.9999 percent with a reaction system pipeline;
opening an argon steel cylinder valve, starting to evacuate the reaction system to-0.15 MPa by using argon, and pressurizing to 0.30MPa, and circularly performing for 20 times;
respectively starting steel cylinders of molybdenum hexachloride and rhenium hexachloride, controlling the mole ratio of the molybdenum hexachloride to the rhenium hexachloride to be 1:20, fully and uniformly mixing the two metal precursors in a primary mixer for 120min, and controlling the mixing time to be 80% of the volume of the primary mixer;
s2, opening a valve of an outlet pipeline of the primary mixer, enabling the mixture to enter a secondary mixer, opening a heating device of the secondary mixer, and heating the secondary mixer to 200 ℃;
s3, starting a heating device of the reactor, and heating a substrate in the reactor to 1200 ℃ and then stabilizing for 4.0 hours, wherein the heating rate is 400 ℃/h;
opening a hydrogen steel bottle, and controlling the hydrogen flow to be 50g/min;
opening an outlet valve of the secondary mixer, adjusting the flow of the mixture, controlling the molar ratio of the mixture gas outlet to the hydrogen gas outlet to be 1:12, controlling the pressure of a reaction system to be 0.5MPa, and starting the chemical vapor deposition reaction in the process, wherein molybdenum-rhenium alloy is deposited on a substrate to prepare a molybdenum-rhenium alloy product with the thickness of 200 mm;
closing a molybdenum-rhenium metal precursor steel cylinder and a mixer outlet valve, closing a mixing heating device, closing a reactor heating device, and starting cooling the reactor, wherein the cooling rate is controlled to be 200 ℃/h;
starting a tail gas treatment device, collecting and reprocessing the reaction byproducts and unreacted raw materials in the test, wherein the tail gas treatment device comprises a two-stage rectifying tower, and the rectified materials are returned to a first-stage mixer in the step S1;
and S4, taking out the product obtained in the step S3 after the temperature is reduced to normal temperature, and removing the matrix by adopting linear cutting to obtain the high-purity molybdenum-rhenium alloy product.
Fig. 2 is a metallographic structure diagram of the molybdenum-rhenium alloy prepared by the invention, and the gold phase diagram of the high-purity molybdenum-rhenium alloy prepared in examples 1-3 is detected, and from the obtained gold phase diagram, we can see that the gold phase diagram shows that the metallographic phase is quite uniform. Because the molybdenum and rhenium metal precursors are mixed and preheated in two stages in the preparation process of the molybdenum-rhenium alloy, the molybdenum and rhenium metal precursors are mixed more fully, the material mixing and heating processes in the reaction process are shortened, the molybdenum and rhenium metal precursors and hydrogen can be reacted rapidly and uniformly, and molybdenum-rhenium is generated and arranged in an atomic stack form, so that the high-purity molybdenum-rhenium alloy material has a more uniform microstructure, and the improvement of the uniformity of the microstructure further promotes the great improvement of the mechanical property of the material.
Comparative example 1
Molybdenum hexafluoride and rhenium hexafluoride with the purity of 99.9 percent, hydrogen with the purity of 99.9 percent and nitrogen with the purity of 99.9 percent are connected with a pipeline of a reaction system;
starting a valve of a nitrogen steel cylinder, starting to evacuate the reaction system to 0MPa by using nitrogen, and pressurizing to 0.05MPa, and performing circulation for 5 times;
starting a heating device of the reactor, heating a substrate in the reactor to 300 ℃ and then stabilizing for 1.0h, wherein the heating rate is 100 ℃/h;
opening a hydrogen steel bottle, and controlling the hydrogen flow to be 20g/min;
respectively starting steel cylinders of molybdenum hexachloride and rhenium hexachloride, adjusting the flow rates of the molybdenum hexachloride and the rhenium hexachloride, controlling the molar ratio of the total gas outlet amount of the molybdenum hexachloride and the rhenium hexachloride to the gas outlet amount of hydrogen to be 1:3, controlling the pressure of a reaction system to be 0.2MPa, and starting the chemical vapor deposition reaction in the process, wherein molybdenum-rhenium alloy is deposited on a substrate to prepare a molybdenum-rhenium alloy product;
closing steel cylinders of molybdenum hexachloride and rhenium hexachloride, closing a hydrogen steel cylinder, closing a reactor heating device, and starting cooling the reactor at a cooling rate of 100 ℃/h;
starting a tail gas treatment device, and collecting and reprocessing the reaction byproducts and unreacted raw materials of the test;
and taking out the molybdenum-rhenium alloy product after the temperature is reduced to normal temperature, and removing the matrix by sulfuric acid to obtain the molybdenum-rhenium alloy.
Comparative example 1 differs from example 1 in that the process preparation step does not involve a primary premixing in S1, a secondary mixing and preheating in S2, and the molybdenum and rhenium metal precursors and hydrogen are directly fed into the reactor for chemical vapor deposition reaction to produce the molybdenum-rhenium alloy article.
Comparative example 2
Comparative example 2 differs from example 1 in that in process preparation step S3, the substrate in the reactor was heated to 290 ℃, and the remaining preparation steps were substantially identical to example 1, resulting in a molybdenum-rhenium alloy article.
The high purity molybdenum-rhenium alloys prepared in examples 1 to 3 were examined as follows:
(1) Glow Discharge Mass Spectrometry (GDMS) test: a glow discharge device of model Thermofisher Element GD is adopted; the high-purity molybdenum-rhenium alloy can be tested for the types and the contents of elements except C, N, H and O;
(2) C, N, H and O detection (IGA): adopting a device with the model of Leco CS-200, leco TC600 and Leco RH 400; can test the content of C, N, H and O elements in the high-purity molybdenum-rhenium alloy
The molybdenum-rhenium alloys prepared in examples 1 to 3 were subjected to purity tests, and the results were substantially identical, as shown in tables 1 and 2:
TABLE 1 GDMS test results
TABLE 2 IGA test results
The test results in tables 1 and 2 show that the purity of the high purity molybdenum-rhenium alloy in examples 1 to 3 is higher than 99.999%, as shown in table 3.
TABLE 3 purity of high purity molybdenum rhenium alloys
| Examples | Example 1 | Example 2 | Example 3 |
| Purity/% | 99.999 | 99.999 | 99.999 |
The molybdenum-rhenium alloy prepared in comparative example 1 is subjected to purity test, the detection result shows that the purity of the molybdenum-rhenium alloy is 99.995%, and the gold phase diagram shows that the metallographic phase of the molybdenum-rhenium alloy is uneven, so that the preparation process of the molybdenum-rhenium alloy of the invention is characterized in that the primary pre-mixing and secondary mixing and preheating processes of the molybdenum and rhenium metal precursors are necessary, the two-stage mixing and preheating of the molybdenum and rhenium metal precursors are carried out, the mixing of the molybdenum and rhenium metal precursors is more sufficient, the material mixing and heating process during the reaction is shortened, the molybdenum and rhenium metal precursors and hydrogen can be rapidly reacted, and the high-purity molybdenum-rhenium alloy material and the alloy material structure are uniform.
The molybdenum-rhenium alloy prepared in the comparative example 2 is subjected to purity test, and the detection result shows that the sum of the contents of other impurity metals, C, N, H and O reaches 0.012%, so that the purity of the obtained molybdenum-rhenium alloy is 99.988%, and as can be seen, when the temperature is lower than 300 ℃ in the preparation process of the molybdenum-rhenium alloy, the temperature is too low, and other impurity metals and nonmetallic elements are doped into the molybdenum-rhenium alloy during vapor deposition reaction, so that the reaction temperature cannot be lower than 300 ℃; and when the reaction temperature is greater than 1200 ℃, the molybdenum-rhenium alloy will not deposit on the reaction substrate, thus defining the reaction temperature of the present invention as 300-1200 ℃.
The molybdenum-rhenium alloys prepared in examples 1-3 and the conventional process molybdenum-rhenium alloys were subjected to tensile strength and yield strength tests, as shown in table 4.
TABLE 4 Table 4
| Molybdenum-rhenium alloy | Irradiation temperature/. Degree.C | Material state | Tensile strength/MPa | Yield strength/MPa |
| Sample piece for traditional technology | 800℃ | Annealed state | 850 | 460 |
| Example 1 | 800℃ | Annealed state | 1000 | 550 |
| Example 2 | 800℃ | Annealed state | 1050 | 580 |
| Example 3 | 800℃ | Annealed state | 1020 | 560 |
As can be seen from Table 4, the molybdenum-rhenium alloys prepared in examples 1 to 3 of the present invention effectively improve the tensile strength and yield strength of the materials compared with the molybdenum-rhenium alloys prepared by the conventional process. The molybdenum-rhenium alloy with the content of 99.999 percent and above is applied to the field of nuclear industry, the volatilization of low-melting-point substances in the material under the high-temperature application condition is effectively reduced by improving the purity of the material, so that the inter-crystal bonding force of the material is greatly improved, the tensile strength and the yield strength of the material are further improved, the radiation resistance of the material is effectively enhanced, the precipitation generated after irradiation is greatly reduced, and the embrittlement of the material after irradiation is effectively improved.
From the detection results, the high-purity molybdenum-rhenium alloy prepared by the preparation method of the high-purity molybdenum-rhenium alloy disclosed by the invention meets the industry standard of YS/T1305-2019 molybdenum-rhenium alloy sheet, and the consistency of quality is ensured.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the high-purity molybdenum-rhenium alloy is characterized by comprising the following steps of:
s1, carrying out primary premixing on metal precursors of molybdenum and rhenium to form a mixture, wherein the mol ratio of the precursors of the molybdenum and the rhenium is controlled to be 20:1-1:20;
s2, carrying out secondary mixing on the mixture, uniformly mixing again in the secondary mixing, and preheating the mixture;
s3, heating the reactor with the matrix material, introducing the preheated mixture and hydrogen into the reactor after heating, and reacting at 300-1200 ℃ to deposit a reaction product on the matrix;
and S4, taking out the product obtained in the step S3, and removing the matrix by adopting an acid dissolution method or a machining method to obtain the high-purity molybdenum-rhenium alloy product with the purity of 99.999 percent or more.
2. The method for preparing the high-purity molybdenum-rhenium alloy according to claim 1, wherein the preparation method is carried out under the protection of inert gas atmosphere, specifically, inert gas is connected with a reaction system pipeline, and the reaction system is subjected to evacuation replacement by the inert gas.
3. The method for preparing a high purity molybdenum-rhenium alloy according to claim 2, wherein the inert gas is nitrogen, argon or helium, the purity is 99.0% -99.9999%, the inert gas is pumped to-0.2-0 MPa and is pumped to 0.01-0.30 MPa when the evacuation replacement is performed, and the steps are repeated for 3-20 times until the replacement of the inert gas is completed.
4. The method for preparing the high-purity molybdenum-rhenium alloy according to claim 1, wherein the metal precursor of molybdenum is molybdenum hexafluoride or molybdenum hexachloride, and the purity is 99.0-99.9999%; the metal precursor of rhenium is rhenium hexafluoride or rhenium hexachloride, the purity is 99.0% -99.9999%, and the purity of hydrogen is 99.0% -99.9999%.
5. The method for preparing the high-purity molybdenum-rhenium alloy according to claim 1, wherein the mixing time is 10-120min when primary premixing is carried out, and the mixing is controlled to be 5% -80% of the volume of a primary mixer; during secondary mixing, the preheating temperature of the mixture is 50-200 ℃.
6. The method for preparing a high-purity molybdenum-rhenium alloy according to claim 1, wherein the reactor is preheated before the mixture and hydrogen are introduced in the step S3, the heating rate is controlled to be 50-500 ℃/h, the temperature is stably maintained for 0.5-5.0 h after the temperature is raised to 300-1200 ℃, and then the mixture and the hydrogen are introduced into the reactor.
7. The method for preparing the high-purity molybdenum-rhenium alloy according to claim 1, wherein in the step S3, the flow rate of the introduced hydrogen is controlled to be 0.5-50g/min, the molar ratio of the introduced mixture to the hydrogen is controlled to be 1:1-1:12, the internal pressure of the reactor is controlled to be 0-0.5 MPa, and the molybdenum-rhenium alloy product with the thickness of 0.05 mu m-200 mm is prepared.
8. The method for preparing a high purity molybdenum-rhenium alloy according to claim 1, wherein after the reaction in step S3 is completed, the reactor is cooled, and a tail gas treatment device is started to collect and reprocess the reaction byproducts and unreacted raw materials.
9. The method for preparing a high purity molybdenum-rhenium alloy according to claim 8, wherein the tail gas treatment device comprises a two-stage rectifying tower, and the rectified material is returned to the one-stage premixing process in step S1.
10. The method for preparing a high purity molybdenum-rhenium alloy according to claim 1, wherein in step S4, the acid dissolution method is to use nitric acid, sulfuric acid or hydrochloric acid, and the acid solution is used to etch away the substrate; the machining method is to adopt linear cutting, grinding machine machining or milling machine machining to remove the matrix.
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