CN117187655A - Molybdenum-rhenium-ruthenium alloy and preparation method thereof - Google Patents
Molybdenum-rhenium-ruthenium alloy and preparation method thereof Download PDFInfo
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- CN117187655A CN117187655A CN202311161379.XA CN202311161379A CN117187655A CN 117187655 A CN117187655 A CN 117187655A CN 202311161379 A CN202311161379 A CN 202311161379A CN 117187655 A CN117187655 A CN 117187655A
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- 229910000929 Ru alloy Inorganic materials 0.000 title claims abstract description 110
- USRNGRFVRRDMRF-UHFFFAOYSA-N molybdenum rhenium ruthenium Chemical compound [Re].[Mo][Ru] USRNGRFVRRDMRF-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 238000010894 electron beam technology Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- OUFGXIPMNQFUES-UHFFFAOYSA-N molybdenum ruthenium Chemical compound [Mo].[Ru] OUFGXIPMNQFUES-UHFFFAOYSA-N 0.000 claims description 17
- 239000011812 mixed powder Substances 0.000 claims description 12
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910000691 Re alloy Inorganic materials 0.000 abstract description 18
- YUSUJSHEOICGOO-UHFFFAOYSA-N molybdenum rhenium Chemical compound [Mo].[Mo].[Re].[Re].[Re] YUSUJSHEOICGOO-UHFFFAOYSA-N 0.000 abstract description 18
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 15
- 238000003723 Smelting Methods 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000005242 forging Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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Abstract
The invention discloses a molybdenum-rhenium-ruthenium alloy, which comprises the following components in percentage by mass: 12% -15% of Re, 0.3% -0.6% of Ru and the balance of Mo and other impurity elements; the preparation method of the molybdenum-rhenium-ruthenium alloy comprises the following steps: 1. dissolving hydrated ruthenium trichloride with absolute ethyl alcohol, mixing molybdenum powder for hydrogen reduction, and adding an ammonium perrhenate aqueous solution for uniform mixing; 2. obtaining molybdenum-rhenium-ruthenium alloy powder through two-stage calcination reduction; 3. performing cold isostatic pressing and vacuum sintering to obtain a molybdenum-rhenium-ruthenium alloy sintered blank; 4. the molybdenum-rhenium-ruthenium alloy is obtained through twice vacuum electron beam smelting and once vacuum consumable electrode arc smelting. According to the invention, ruthenium is added into the molybdenum-rhenium alloy, so that the high-temperature corrosion resistance, strength and plasticity of the molybdenum-rhenium alloy are improved, and the growth of grains is inhibited in the smelting process; the smelting mode of the invention obtains the molybdenum-rhenium-ruthenium alloy with finer grain structure, more uniform components and lower impurity content, and avoids defects and cracks in subsequent processing.
Description
Technical Field
The invention belongs to the technical field of metal material processing, and particularly relates to a molybdenum-rhenium-ruthenium alloy and a preparation method thereof.
Background
The molybdenum-rhenium alloy obviously improves the intrinsic brittleness and irradiation brittleness of molybdenum due to the rhenium effect, improves the alloy processing and welding performance, and is a very promising advanced reactor candidate cladding, heat pipe and structural material. Due to the high melting point of the molybdenum-rhenium alloy, the blank is usually prepared by a powder metallurgy method, but the blank prepared by the powder metallurgy method is high in oxygen content, and the impurity elements can be obviously removed by adopting electron beam melting, so that the method has a good purification effect. However, the molybdenum-rhenium alloy subjected to electron beam melting, particularly the molybdenum-rhenium alloy with the rhenium content of about 12% -15%, is extremely easy to have defects in the hot pressing process due to coarse grains and fragile grain boundaries.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a molybdenum-rhenium-ruthenium alloy aiming at the defects of the prior art. According to the molybdenum-rhenium-ruthenium alloy, the ruthenium element is added into the molybdenum-rhenium alloy, so that the high-temperature corrosion resistance, strength and plasticity of the molybdenum-rhenium alloy are improved, the grain boundary is strengthened, and the growth of grains is effectively inhibited in the smelting process of preparing the molybdenum-rhenium-ruthenium alloy, so that the molybdenum-rhenium-ruthenium alloy has better performance than the traditional molybdenum-rhenium alloy.
In order to solve the technical problems, the invention adopts the following technical scheme: the molybdenum-rhenium-ruthenium alloy is characterized by comprising the following components in percentage by mass: 12% -15% of Re, 0.3% -0.6% of Ru0.3% and the balance of Mo and other impurity elements, wherein the total amount of other impurity elements is not more than 0.1%.
The molybdenum-rhenium-ruthenium alloy is added with ruthenium element, and because the metal ruthenium is noble metal element, belongs to VIII B group element, has an electronic layer structure similar to Pt, has stable chemical property, reduces the directionality of electronic bonds when molybdenum is alloyed with VIII B element, reduces interatomic stress, reduces low-temperature brittleness of metal molybdenum, improves high-temperature corrosion resistance, strength and plasticity of the molybdenum-rhenium alloy and strengthens grain boundary, and effectively inhibits growth of grains in the smelting process of preparing the molybdenum-rhenium-ruthenium alloy, thereby obtaining better performance compared with the traditional molybdenum-rhenium alloy.
The molybdenum-rhenium-ruthenium alloy is characterized by comprising the following components in percentage by mass: re 14%, ru 0.6%, and the balance Mo and other impurity elements, wherein the total amount of other impurity elements is not more than 0.1%.
In addition, the invention also discloses a method for preparing the molybdenum-rhenium-ruthenium alloy, which is characterized by comprising the following steps:
dissolving hydrated ruthenium trichloride with absolute ethyl alcohol, mixing molybdenum powder for hydrogen reduction to obtain molybdenum ruthenium alloy powder, and then adding an aqueous solution of ammonium perrhenate and uniformly mixing to obtain mixed powder;
step two, placing the mixed powder obtained in the step two into a high-temperature alloy material boat, and then performing two-stage calcination reduction under the hydrogen atmosphere to obtain molybdenum-rhenium-ruthenium alloy powder;
step three, sequentially carrying out cold isostatic pressing and vacuum sintering on the molybdenum-rhenium-ruthenium alloy powder obtained in the step two to obtain a molybdenum-rhenium-ruthenium alloy sintered blank;
and fourthly, sequentially carrying out vacuum electron beam melting and primary vacuum consumable electrode arc melting on the molybdenum-rhenium-ruthenium alloy sintered blank obtained in the third step to obtain the molybdenum-rhenium-ruthenium alloy.
In the first step of the invention, the process of preparing the molybdenum-ruthenium alloy powder by dissolving hydrated ruthenium trichloride by absolute ethyl alcohol and then mixing molybdenum powder for hydrogen reduction is disclosed in the invention patent application No. 202110233893.4, namely a microalloyed molybdenum-ruthenium alloy preparation method
According to the invention, molybdenum-ruthenium alloy powder with uniformly distributed ruthenium elements is uniformly mixed with an aqueous solution of ammonium perrhenate, and then two-stage calcination reduction is carried out, wherein ammonium perrhenate is sequentially decomposed and reduced and converted into simple substance rhenium powder with finer granularity, and uniformly adhered to the molybdenum powder, and then isostatic pressing and sintering are carried out to obtain molybdenum-rhenium-ruthenium alloy blanks with uniform components.
The preparation method is characterized in that the mass content of rhenium element in the ammonium perrhenate in the step one is 69.4%. The invention precisely ensures the addition amount of ruthenium element through the limit.
The preparation method is characterized in that the uniformly mixing process in the first step is as follows: the molybdenum ruthenium alloy powder and the aqueous solution of ammonium perrhenate are stirred and dried, and then are transferred to a three-dimensional mixer for mixing for 4 hours. By adopting the process of uniform mixing, the invention ensures that the ammonium perrhenate solution is uniformly coated on the surface of the molybdenum-ruthenium alloy powder after evaporation and precipitation, and is beneficial to improving the component uniformity of the molybdenum-rhenium-ruthenium alloy.
The preparation method is characterized in that the high-temperature alloy material boat in the second step is a molybdenum material boat.
The preparation method is characterized in that the two-stage calcination reduction system in the second step is as follows: the temperature of the first stage is 300-350 ℃ and the time is 1.5-2 h; the temperature of the second stage is 800-950 ℃ and the time is 2-4 h. The invention is beneficial to enhancing the reduction effect of rhenium element by limiting a two-stage calcination reduction system, and the prepared molybdenum-rhenium-ruthenium alloy powder does not agglomerate.
The preparation method is characterized in that in the fourth step, the molybdenum-rhenium-ruthenium alloy is forged or rolled after being extruded and cogged at high temperature, and a bar or a plate is obtained. The deformation of extrusion and forging or rolling is larger, which is beneficial to improving the mechanical property of bar or plate products.
Compared with the prior art, the invention has the following advantages:
1. according to the molybdenum-rhenium-ruthenium alloy, the ruthenium element is added into the molybdenum-rhenium alloy, so that the high-temperature corrosion resistance, strength and plasticity of the molybdenum-rhenium alloy are improved, the grain boundary is strengthened, and the growth of grains is effectively inhibited in the smelting process of preparing the molybdenum-rhenium-ruthenium alloy, so that the molybdenum-rhenium-ruthenium alloy has better performance than the traditional molybdenum-rhenium alloy.
2. Compared with the method for directly adding rhenium powder, the method provided by the invention has the advantages that the molybdenum-ruthenium alloy powder and the ammonium perrhenate aqueous solution are uniformly mixed and then subjected to two-stage calcination reduction, so that the distribution uniformity of rhenium element in the molybdenum-rhenium-ruthenium alloy blank is improved.
3. The method adopts a mode of once vacuum consumable electrode arc melting after twice vacuum electron beam melting to obtain the molybdenum-rhenium-ruthenium alloy with finer grain structure, more uniform components and lower impurity content, and avoids defects and cracks in the subsequent processing process.
4. The ruthenium element in the molybdenum-rhenium-ruthenium alloy prepared by the method is uniformly distributed, the consumption of noble metal ruthenium is reduced, and the raw material cost of the molybdenum-rhenium-ruthenium alloy is reduced on the premise of obtaining the molybdenum-rhenium-ruthenium alloy with better performance.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a macroscopic metallographic structure diagram of a molybdenum-rhenium-ruthenium alloy ingot prepared in example 1 of the present invention.
FIG. 2a is a longitudinal metallographic view (200X) of a forged bar of molybdenum-rhenium-ruthenium alloy prepared according to example 1 of the present invention.
FIG. 2b is a transverse metallographic view (200X) of a forged bar of molybdenum-rhenium-ruthenium alloy prepared according to example 1 of the present invention.
FIG. 3a is a view (200X) showing the longitudinal metallographic structure of a forged bar of molybdenum-rhenium-ruthenium alloy according to example 1 of the present invention after recrystallization annealing.
FIG. 3b is a transverse metallographic structure (200X) of a forged bar of molybdenum-rhenium-ruthenium alloy prepared in example 1 of the present invention after recrystallization annealing.
Fig. 4 is a macroscopic metallographic structure diagram of the molybdenum-rhenium alloy ingot prepared in comparative example 1 of the present invention.
Detailed Description
Example 1
The molybdenum-rhenium-ruthenium alloy of the embodiment comprises the following components in percentage by mass: re 14%, ru 0.6%, and the balance Mo and other impurity elements, wherein the total amount of other impurity elements is not more than 0.1%.
The preparation method of the molybdenum-rhenium-ruthenium alloy comprises the following steps:
dissolving hydrated ruthenium trichloride with absolute ethyl alcohol, mixing into molybdenum powder, carrying out hydrogen reduction to obtain molybdenum ruthenium alloy powder with the mass content of ruthenium element of 0.7%, dissolving 1.8kg of ammonium perrhenate with the mass content of rhenium element of 69.4% in water, adding 8.75kg of molybdenum ruthenium alloy powder, stirring, drying, transferring into a 20L polytetrafluoroethylene mixing bucket, and installing in a three-dimensional mixer for mixing for 4 hours to obtain mixed powder;
step two, placing the mixed powder obtained in the step two into a molybdenum material boat, and then performing two-stage calcination reduction under a hydrogen atmosphere, wherein the temperature of the first stage is 300 ℃ for 2 hours, the temperature of the second stage is 800 ℃ for 4 hours, so as to obtain molybdenum-rhenium-ruthenium alloy powder;
loading the molybdenum-rhenium-ruthenium alloy powder obtained in the step two into a rubber sleeve with the diameter of 110mm for cold isostatic pressing, wherein the pressing pressure is 190MPa, the pressure is maintained for 60s, and then vacuum sintering is carried out, the sintering temperature is 2200 ℃, and the heat preservation time is 8h, so that a molybdenum-rhenium-ruthenium alloy sintered blank with the diameter of 90mm is obtained;
and step four, sequentially carrying out vacuum electron beam melting and primary vacuum consumable electrode arc melting on the molybdenum-rhenium-ruthenium alloy sintered blank obtained in the step three to obtain a molybdenum-rhenium-ruthenium alloy cast ingot with the diameter of 90mm, and carrying out high-temperature forging after high-temperature extrusion cogging to obtain a molybdenum-rhenium-ruthenium alloy forged bar with the diameter of 30 mm.
Through detection, the mass content of Re in the molybdenum-rhenium-ruthenium alloy cast ingot prepared in the embodiment is 14.4%, and the mass content of Ru is 0.61%.
Fig. 2a is a longitudinal metallographic diagram (200×) of the molybdenum-rhenium-ruthenium alloy forging bar prepared in this example, and fig. 2b is a transverse metallographic diagram (200×) of the molybdenum-rhenium-ruthenium alloy forging bar prepared in this example, and it can be seen from fig. 2a and fig. 2b that the crystal grains in the molybdenum-rhenium-ruthenium alloy forging bar form a fibrous structure due to deformation and elongation, and the crystal grains are uniform and have no defects and cracks.
Fig. 3a is a longitudinal metallographic structure diagram (200×) of the molybdenum-rhenium-ruthenium alloy forging bar prepared in this example after recrystallization annealing (1600 ℃/2 h), and fig. 3b is a transverse metallographic structure diagram (200×) of the molybdenum-rhenium-ruthenium alloy forging bar prepared in this example after recrystallization annealing, and it can be seen from fig. 3a and 3b that the molybdenum-rhenium-ruthenium alloy forging bar has uniform crystal grains after recrystallization annealing, no abnormal growth, bent crystal boundaries, and no formation of linear crystal boundaries of common molybdenum alloy, so that the molybdenum-rhenium alloy forging bar has a better elongation.
Comparative example 1
This comparative example differs from example 1 in that: the alloy does not contain ruthenium element and is Mo14Re alloy.
Fig. 1 is a macroscopic metallographic structure diagram of a molybdenum-rhenium-ruthenium alloy ingot prepared in example 1 of the present invention, fig. 4 is a macroscopic metallographic structure diagram of a molybdenum-rhenium alloy ingot prepared in comparative example 1 of the present invention, and comparing fig. 1 with fig. 4, it can be known that the grains in the molybdenum-rhenium-ruthenium alloy ingot are smaller, which indicates that the present invention effectively inhibits the growth of grains in the electron beam melting process by adding ruthenium element into the molybdenum-rhenium alloy, and the columnar crystals are significantly reduced, so that the structure is refined.
Example 2
The molybdenum-rhenium-ruthenium alloy of the embodiment comprises the following components in percentage by mass: 12% of Re, 0.3% of Ru, the balance of Mo and other impurity elements, and the total amount of other impurity elements is not more than 0.1%.
The preparation method of the molybdenum-rhenium-ruthenium alloy comprises the following steps:
dissolving hydrated ruthenium trichloride with absolute ethyl alcohol, mixing into molybdenum powder, carrying out hydrogen reduction to obtain molybdenum ruthenium alloy powder with the mass content of ruthenium element of 0.4%, dissolving 1.5kg of ammonium perrhenate with the mass content of rhenium element of 69.4% in water, adding 8.75kg of molybdenum ruthenium alloy powder, stirring, drying, transferring into a 20L polytetrafluoroethylene mixing bucket, and installing in a three-dimensional mixer for mixing for 4 hours to obtain mixed powder;
step two, placing the mixed powder obtained in the step two into a molybdenum material preparing boat, and then performing two-stage calcination reduction under a hydrogen atmosphere, wherein the temperature of the first stage is 350 ℃, the time is 1.5h, the temperature of the second stage is 950 ℃, and the time is 2h, so as to obtain molybdenum-rhenium-ruthenium alloy powder;
loading the molybdenum-rhenium-ruthenium alloy powder obtained in the step two into a rubber sleeve with the diameter of 110mm for cold isostatic pressing, wherein the pressing pressure is 190MPa, the pressure is maintained for 60s, and then vacuum sintering is carried out, the sintering temperature is 2200 ℃, and the heat preservation time is 8h, so that a molybdenum-rhenium-ruthenium alloy sintered blank with the diameter of 90mm is obtained;
and step four, sequentially carrying out vacuum electron beam melting and primary vacuum consumable electrode arc melting on the molybdenum-rhenium-ruthenium alloy sintered blank obtained in the step three to obtain a molybdenum-rhenium-ruthenium alloy cast ingot with the diameter of 90mm, and carrying out high-temperature rolling after high-temperature extrusion cogging to obtain a molybdenum-rhenium-ruthenium alloy rolled plate with the thickness of 10 mm.
Through detection, the mass content of Re in the molybdenum-rhenium-ruthenium alloy cast ingot prepared in the embodiment is 12.1%, and the mass content of Ru is 0.28%.
Example 3
The molybdenum-rhenium-ruthenium alloy of the embodiment comprises the following components in percentage by mass: re 14%, ru0.3%, and the balance Mo and other impurity elements, and the total amount of other impurity elements is not more than 0.1%.
The preparation method of the molybdenum-rhenium-ruthenium alloy comprises the following steps:
dissolving hydrated ruthenium trichloride with absolute ethyl alcohol, mixing into molybdenum powder, carrying out hydrogen reduction to obtain molybdenum ruthenium alloy powder with the mass content of ruthenium element of 0.4%, dissolving 1.8kg of ammonium perrhenate with the mass content of rhenium element of 69.4% in water, adding 8.75kg of molybdenum ruthenium alloy powder, stirring, drying, transferring into a 20L polytetrafluoroethylene mixing bucket, and installing in a three-dimensional mixer for mixing for 4 hours to obtain mixed powder;
step two, placing the mixed powder obtained in the step two into a molybdenum material boat, and then performing two-stage calcination reduction under a hydrogen atmosphere, wherein the temperature of the first stage is 300 ℃ for 2 hours, the temperature of the second stage is 900 ℃ for 2 hours, and molybdenum-rhenium-ruthenium alloy powder is obtained;
loading the molybdenum-rhenium-ruthenium alloy powder obtained in the step two into a rubber sleeve with the diameter of 110mm for cold isostatic pressing, wherein the pressing pressure is 190MPa, the pressure is maintained for 60s, and then vacuum sintering is carried out, the sintering temperature is 2200 ℃, and the heat preservation time is 8h, so that a molybdenum-rhenium-ruthenium alloy sintered blank with the diameter of 90mm is obtained;
and step four, sequentially carrying out vacuum electron beam melting and primary vacuum consumable electrode arc melting on the molybdenum-rhenium-ruthenium alloy sintered blank obtained in the step three to obtain a molybdenum-rhenium-ruthenium alloy cast ingot with the diameter of 90mm, and carrying out high-temperature rolling after high-temperature extrusion cogging to obtain a molybdenum-rhenium-ruthenium alloy rolled plate with the thickness of 10 mm.
Through detection, the mass content of Re in the molybdenum-rhenium-ruthenium alloy cast ingot prepared in the embodiment is 14.1%, and the mass content of Ru is 0.31%.
Example 4
The molybdenum-rhenium-ruthenium alloy of the embodiment comprises the following components in percentage by mass: re 13%, ru 0.5%, and the balance Mo and other impurity elements, wherein the total amount of other impurity elements is not more than 0.1%.
The preparation method of the molybdenum-rhenium-ruthenium alloy comprises the following steps:
dissolving hydrated ruthenium trichloride with absolute ethyl alcohol, mixing into molybdenum powder, carrying out hydrogen reduction to obtain molybdenum ruthenium alloy powder with the mass content of ruthenium element of 0.5%, dissolving 1.7kg of ammonium perrhenate with the mass content of rhenium element of 69.4% in water, adding 8.75kg of molybdenum ruthenium alloy powder, stirring, drying, transferring into a 20L polytetrafluoroethylene mixing bucket, and installing in a three-dimensional mixer for mixing for 4 hours to obtain mixed powder;
step two, placing the mixed powder obtained in the step two into a molybdenum material boat, and then performing two-stage calcination reduction under a hydrogen atmosphere, wherein the temperature of the first stage is 300 ℃ for 2 hours, the temperature of the second stage is 900 ℃ for 2 hours, and molybdenum-rhenium-ruthenium alloy powder is obtained;
loading the molybdenum-rhenium-ruthenium alloy powder obtained in the step two into a rubber sleeve with the diameter of 110mm for cold isostatic pressing, wherein the pressing pressure is 190MPa, the pressure is maintained for 60s, and then vacuum sintering is carried out, the sintering temperature is 2200 ℃, and the heat preservation time is 8h, so that a molybdenum-rhenium-ruthenium alloy sintered blank with the diameter of 90mm is obtained;
and step four, sequentially carrying out vacuum electron beam melting and primary vacuum consumable electrode arc melting on the molybdenum-rhenium-ruthenium alloy sintered blank obtained in the step three to obtain a molybdenum-rhenium-ruthenium alloy cast ingot with the diameter of 90mm, and carrying out high-temperature forging after high-temperature extrusion cogging to obtain a molybdenum-rhenium-ruthenium alloy forged bar with the diameter of 30 mm.
Through detection, the mass content of Re in the molybdenum-rhenium-ruthenium alloy cast ingot prepared in the embodiment is 13.4%, and the mass content of Ru is 0.48%.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (8)
1. The molybdenum-rhenium-ruthenium alloy is characterized by comprising the following components in percentage by mass: 12% -15% of Re, 0.3% -0.6% of Ru, the balance of Mo and other impurity elements, and the total amount of other impurity elements is not more than 0.1%.
2. The molybdenum-rhenium-ruthenium alloy according to claim 1, which is characterized by comprising the following components in percentage by mass: re 14%, ru 0.6%, and the balance Mo and other impurity elements, wherein the total amount of other impurity elements is not more than 0.1%.
3. A method of preparing a molybdenum-rhenium-ruthenium alloy according to claim 1 or 2, comprising the steps of:
dissolving hydrated ruthenium trichloride with absolute ethyl alcohol, mixing molybdenum powder for hydrogen reduction to obtain molybdenum ruthenium alloy powder, and then adding an aqueous solution of ammonium perrhenate and uniformly mixing to obtain mixed powder;
step two, placing the mixed powder obtained in the step two into a high-temperature alloy material boat, and then performing two-stage calcination reduction under the hydrogen atmosphere to obtain molybdenum-rhenium-ruthenium alloy powder;
step three, sequentially carrying out cold isostatic pressing and vacuum sintering on the molybdenum-rhenium-ruthenium alloy powder obtained in the step two to obtain a molybdenum-rhenium-ruthenium alloy sintered blank;
and fourthly, sequentially carrying out vacuum electron beam melting and primary vacuum consumable electrode arc melting on the molybdenum-rhenium-ruthenium alloy sintered blank obtained in the third step to obtain the molybdenum-rhenium-ruthenium alloy.
4. A production method according to claim 3, wherein the mass content of rhenium element in the ammonium perrhenate in the step one is 69.4%.
5. The method according to claim 3, wherein the step of uniformly mixing comprises the steps of: the molybdenum ruthenium alloy powder and the aqueous solution of ammonium perrhenate are stirred and dried, and then are transferred to a three-dimensional mixer for mixing for 4 hours.
6. The method according to claim 3, wherein the high-temperature alloy boat in the second step is a molybdenum boat.
7. The method according to claim 3, wherein the two-stage calcination reduction system in the second step is: the temperature of the first stage is 300-350 ℃ and the time is 1.5-2 h; the temperature of the second stage is 800-950 ℃ and the time is 2-4 h.
8. The method according to claim 3, wherein in the fourth step, the molybdenum-rhenium-ruthenium alloy is forged or rolled after being subjected to high-temperature extrusion and cogging, so as to obtain a bar or a plate.
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