CN115896528B - Refractory intermetallic compound reinforced platinum-rhodium-based superalloy, and preparation method and application thereof - Google Patents
Refractory intermetallic compound reinforced platinum-rhodium-based superalloy, and preparation method and application thereof Download PDFInfo
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- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 75
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims description 24
- 239000000956 alloy Substances 0.000 claims abstract description 183
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 182
- 239000010948 rhodium Substances 0.000 claims abstract description 28
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 64
- 238000005245 sintering Methods 0.000 claims description 47
- 239000000843 powder Substances 0.000 claims description 42
- 238000000137 annealing Methods 0.000 claims description 39
- 238000005097 cold rolling Methods 0.000 claims description 34
- 238000000498 ball milling Methods 0.000 claims description 30
- 238000010273 cold forging Methods 0.000 claims description 27
- 239000011812 mixed powder Substances 0.000 claims description 25
- 238000012545 processing Methods 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 17
- 238000000748 compression moulding Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229910052703 rhodium Inorganic materials 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000004663 powder metallurgy Methods 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 38
- 238000007254 oxidation reaction Methods 0.000 abstract description 38
- 229910018967 Pt—Rh Inorganic materials 0.000 abstract description 18
- 230000003014 reinforcing effect Effects 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 61
- 230000000052 comparative effect Effects 0.000 description 49
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- 229910001257 Nb alloy Inorganic materials 0.000 description 30
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- 238000005728 strengthening Methods 0.000 description 14
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- 229910000629 Rh alloy Inorganic materials 0.000 description 10
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
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- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 2
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a refractory intermetallic compound reinforced platinum-rhodium-based superalloy, which comprises the following components in percentage by mass: rh 0-10wt%, re 3 Nb 0.05-1.0 wt% and Pt for the rest. The invention adopts a certain amount of novel refractory X-phase intermetallic compound (Re) 3 Nb is used as a reinforcing phase, and Re is used as a reinforcing phase 3 The Nb is uniformly dispersed in the Pt-Rh alloy, so that the Pt-Rh-based alloy with the X phase enhanced and low Rh content has excellent high-temperature mechanical property and oxidation resistance, the consumption of noble metal Rh and the alloy cost are greatly reduced, and the Pt element and the Rh element with higher melting points are utilized to improve the oxidation resistance, the corrosion resistance and the chemical stability of the prepared refractory intermetallic compound enhanced platinum-rhodium-based superalloy.
Description
Technical Field
The invention relates to the technical field of platinum-rhodium alloy materials, in particular to a refractory intermetallic compound reinforced platinum-rhodium-based superalloy, a preparation method and application thereof.
Background
The platinum-rhodium alloy has high melting point, excellent high-temperature oxidation resistance, corrosion resistance and high-temperature mechanical properties, is widely applied in industry as a functional and structural material, and becomes an indispensable high-temperature material in many severe environments, such as glass fiber industrial bushing plates, space engine spray pipes, vessel materials for experimental analysis and crystal growth, and the like. With the development of modern industry, increasingly stringent requirements are put on the physicochemical and mechanical properties of platinum-rhodium alloys, for example, glass fiber industry bushing plates need to work stably for a long time at high temperatures of 1200-1500 ℃ and molten glass, while the technical requirements of jet pipes of second-generation aerospace engines are higher: the oxidizing property of the engine propellant is much stronger than that of the atmosphere, the working temperature is required to reach 1500-1600 ℃, and the service life is required to reach more than 10 hours. The method is a main technical direction for innovatively developing novel platinum-rhodium-based alloy, and the temperature resistance of the platinum-rhodium alloy is continuously improved, and the alloy cost is reduced.
At present, the intermetallic compound strengthening of platinum and platinum-rhodium alloy in the prior art mainly adopts a method that a Pt matrix reacts with rare earth, aluminum and transition group metal in situ to form a compound, but the following problems exist in the prior art: (1) Amount of the compoundThe control difficulty of the size and the distribution is high, namely, the control difficulty of the process of forming intermetallic compounds through in-situ reaction is high, the number, the size and the distribution state of the formed compounds are closely related to smelting, processing and heat treatment processes, and the influence factors are complex, so that the variation range of the strengthening effect of the intermetallic compounds is large, and the alloy performance is unstable; (2) For the enhancement of Pt-RE intermetallic compound, pt and RE element form Pt in situ in the smelting and cooling process 5 RE and Pt 3 The RE intermetallic compound has stronger strengthening effect on the mechanical properties of the alloy at room temperature and below 1400 ℃, but the strengthening effect is drastically reduced when the using temperature exceeds 1400 ℃ because the melting point of the formed Pt-RE compound is lower (at most 1640 ℃); in addition, RE element is easy to gather at the grain boundary, so that more Pt-RE compounds appear at the grain boundary, the alloy performance is embrittled, and the processing performance is reduced; (3) For the enhancement of Pt-transition group intermetallic compound, during the smelting process, pt and high-melting-point transition group metal form intermetallic compound Pt with a higher melting point (about 2000 ℃) which is coherent with a Pt matrix in situ 3 The reinforcing effect on the platinum-based alloy is more obvious in the X phase (x= Zr, hf, nb, ta). However, because the solid solubility of the elements in Pt is large, more than 10 weight percent of alloy elements must be added to form a precipitation strengthening phase, while Zr, hf, nb, ta and the like are easily oxidized elements, and a large amount of solid-dissolved Zr, hf, nb, ta elements are easily oxidized in a high-temperature oxidation environment, so that the inherent strong oxidation resistance of platinum and platinum-rhodium alloy is greatly damaged; (4) For the enhancement of Pt-Al intermetallic compound, adding Al element into Pt can also form Pt which is coherent with the matrix in situ 3 And Al precipitation strengthening phase. Al in solid solution state in high temperature oxidation environment diffuses to alloy surface and forms compact alpha-Al 2 O 3 The oxidation resistance of the oxidation-resistant coating is obviously better than that of a platinum-based alloy reinforced by transition group intermetallic compound, and the Pt can be formed by adding more than 10 weight percent of Al element 3 Al phase, so that the melting point of the alloy is reduced to about 1500 ℃, and the use temperature of the material cannot exceed 1300 ℃. In summary, the intermetallic compound strengthening of platinum and platinum-rhodium alloys in the prior artThe intermetallic compound in the reinforced phase is unevenly dispersed in the alloy, and the high-temperature mechanical property and the high-temperature oxidation resistance are poor.
Disclosure of Invention
The invention aims to provide a refractory intermetallic compound reinforced platinum-rhodium-based superalloy, a preparation method and application thereof, and the refractory intermetallic compound reinforced platinum-rhodium-based superalloy (Pt-Rh alloy for short) provided by the invention has excellent high-temperature mechanical property and high-temperature oxidation resistance, and a reinforced phase Re 3 Nb is uniformly dispersed in the Pt-Rh alloy.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a refractory intermetallic compound reinforced platinum-rhodium-based superalloy, which comprises the following components in percentage by mass: rh 0-10wt%, re 3 Nb 0.05-1.0 wt% and Pt for the rest.
The invention also provides a preparation method of the refractory intermetallic compound reinforced platinum-rhodium-based superalloy, which comprises the following steps:
(1) The mass ratio of the substances is 3:1 and Nb are mixed and then are sequentially smelted and naturally cooled to obtain Re 3 Casting Nb ingot;
(2) Obtaining Re from the step (1) 3 Crushing and ball milling Nb cast ingots sequentially to obtain Re 3 Nb powder;
(3) Obtaining Re from the step (2) 3 Mixing Nb powder with sponge Pt and Rh powder, and performing second ball milling to obtain mixed powder;
(4) Sequentially drying and compression molding the mixed powder obtained in the step (3) to obtain an alloy ingot blank;
(5) Performing vacuum sintering on the alloy ingot blank obtained in the step (4) to obtain a sintered alloy ingot blank;
(6) Carrying out cold forging or cold rolling on the sintered alloy ingot blank obtained in the step (5) to obtain refractory intermetallic compound reinforced platinum-rhodium-based superalloy;
and (3) when the accumulated deformation of the cold forging process or the cold rolling process in the step (6) is independently 45-75%, performing intermediate annealing on the alloy after the cold forging process or the cold rolling process.
Preferably, before smelting in the step (1), vacuumizing is carried out firstly until the vacuum degree of equipment for smelting is less than or equal to 10 -2 Pa, and then filling argon of 0.11-0.13 MPa.
Preferably, re in the step (2) 3 The grain diameter of Nb powder is less than or equal to 10 mu m.
Preferably, the second ball milling in the step (3) is carried out for 9-22 hours, the ball-to-material ratio of the second ball milling is (3.5-1.5): 1, and the rotating speed of the second ball milling is 40-100 rpm.
Preferably, the pressure of the compression molding in the step (4) is 40-60 MPa, and the time of the compression molding is 4-15 min.
Preferably, the vacuum degree of the vacuum sintering in the step (5) is less than or equal to 5 multiplied by 10 -3 Pa, the temperature of the vacuum sintering is 1200-1550 ℃, and the time of the vacuum sintering is 1.5-5 h.
Preferably, when the sintered alloy ingot blank in the step (6) is a cylindrical ingot blank, performing cold forging processing on the sintered alloy ingot blank;
and (3) when the sintered alloy ingot blank in the step (6) is square, performing cold rolling processing on the sintered alloy ingot blank.
Preferably, the temperature of the intermediate annealing in the step (6) is 750-1100 ℃, and the time of the intermediate annealing is 8-18 min.
The invention also provides application of the refractory intermetallic compound reinforced platinum-rhodium-based superalloy or the refractory intermetallic compound reinforced platinum-rhodium-based superalloy prepared by the preparation method in glass fiber bushing, crystal growth crucible and aerospace engine nozzle materials.
The invention provides a refractory intermetallic compound reinforced platinum-rhodium-based superalloy (Pt-Rh alloy for short), which comprises the following components in mass content: rh 0-10wt%, re 3 Nb 0.05-1.0 wt% and Pt for the rest. The invention adopts a certain amount of novel refractory X-phase intermetallic compound with high melting point (the melting point is up to 2640℃)Re 3 Nb is used as a reinforcing phase, and Re is used as a reinforcing phase 3 The Nb is uniformly dispersed in the Pt-Rh alloy, so that the Pt-Rh-based alloy with the X phase enhanced and low Rh content has excellent high-temperature mechanical property and oxidation resistance, the consumption of noble metal Rh and the alloy cost are greatly reduced, and the Pt element and the Rh element with higher melting point are utilized to improve the oxidation resistance, the corrosion resistance and the chemical stability of the prepared refractory intermetallic compound enhanced platinum-rhodium-based superalloy. The results of the examples show that Pt-10Rh-1.0Re as described in example 4 of the present invention 3 The 10h endurance strength of Nb alloy at 1500 ℃ and 1600 ℃ can reach 11.3MPa and 8.0MPa respectively, and Pt-10Rh-0.5Re is described in example 3 3 Nb alloy with oxidation weight loss as low as 3.0X10 at 1500 DEG C -2 mg/cm 2 ·h。
Drawings
FIG. 1 is a schematic view of Re in a refractory intermetallic compound-enhanced platinum-rhodium-based superalloy prepared in example 4 of the invention 3 Scanning electron microscope photograph of the distribution state of Nb in the alloy.
Detailed Description
The invention provides a refractory intermetallic compound reinforced platinum-rhodium-based superalloy, which comprises the following components in percentage by mass: rh 0-12 wt%, re 3 0.03 to 1.2wt% of Nb and the balance of Pt.
The refractory intermetallic compound reinforced platinum-rhodium-based superalloy provided by the invention comprises 0-12 wt% of Rh, preferably 0-10 wt%. In the invention, rh mainly plays a solid solution strengthening role, among a plurality of solid solution strengthening elements, rh is the most stable high-temperature solid solution strengthening element of the Pt alloy and can keep the strong oxidation resistance of the Pt alloy.
The refractory intermetallic compound enhanced platinum-rhodium base provided by the invention comprises the following components in percentage by massSuperalloy comprises Re 3 Nb 0.03-1.2 wt%, preferably 0.05-1.0 wt%. The present invention is achieved by employing an amount of an intermetallic compound Re 3 Nb is used as a reinforcing phase, and Re is used as a reinforcing phase 3 The Nb is uniformly dispersed in the Pt-Rh alloy, so that the refractory intermetallic compound reinforced platinum-rhodium-based superalloy has excellent high-temperature mechanical property and high-temperature oxidation resistance.
The refractory intermetallic compound enhanced platinum rhodium-based superalloy provided by the invention comprises the balance of Pt. According to the invention, the refractory intermetallic compound reinforced platinum-rhodium-based superalloy with excellent oxidation resistance and corrosion resistance is obtained by adopting the Pt element with a higher melting point as an alloy matrix.
The invention also provides a preparation method of the refractory intermetallic compound reinforced platinum-rhodium-based superalloy, which comprises the following steps:
(1) The mass ratio of the substances is 3:1 and Nb are mixed and then are sequentially smelted and naturally cooled to obtain Re 3 Casting Nb ingot;
(2) Obtaining Re from the step (1) 3 Crushing and ball milling Nb cast ingots sequentially to obtain Re 3 Nb powder;
(3) Obtaining Re from the step (2) 3 Mixing Nb powder with sponge Pt and Rh powder, and performing second ball milling to obtain mixed powder;
(4) Sequentially drying and compression molding the mixed powder obtained in the step (3) to obtain an alloy ingot blank;
(5) Performing vacuum sintering on the alloy ingot blank obtained in the step (4) to obtain a sintered alloy ingot blank;
(6) Carrying out cold forging or cold rolling on the sintered alloy ingot blank obtained in the step (5) to obtain refractory intermetallic compound reinforced platinum-rhodium-based superalloy;
and (3) when the accumulated deformation of the cold forging process or the cold rolling process in the step (6) is independently 45-75%, performing intermediate annealing on the alloy after the cold forging process or the cold rolling process.
In the present invention, the purity of Re is preferably not less than 99.99%. In the present invention, the purity of Nb is preferably not less than 99.95%.
The mode of mixing Re and Nb is not particularly limited, and the components can be uniformly mixed.
In the present invention, the apparatus used for smelting is preferably a non-consumable vacuum arc furnace.
In the invention, before the smelting starts, the vacuum is firstly pumped until the vacuum degree of the smelting equipment is less than or equal to 10 -2 Pa, and then, argon gas of 0.11 to 0.13MPa, more preferably argon gas of 0.12 MPa. The invention controls the pressure of argon in smelting equipment within the range, and prevents the oxidation of alloy elements in the smelting process.
Obtaining Re 3 After Nb ingot casting, the invention leads the Re to 3 Crushing and ball milling Nb cast ingots sequentially to obtain Re 3 Nb powder.
In the present invention, the crushing means is preferably an impact method. In the present invention, the apparatus for the first ball milling is preferably a high-energy vibration ball mill. In the present invention, the time of the first ball milling is preferably 30 to 50 seconds.
After the first ball milling is completed, the product of the first ball milling is preferably sieved.
In the present invention, the Re 3 The particle size of the Nb powder is preferably 10 μm or less. The invention uses Re 3 The grain diameter of Nb is controlled within the range, so that the strength enhancement effect of the refractory intermetallic compound enhanced platinum rhodium-based superalloy prepared later is optimal, and Re is avoided 3 The grain size of Nb powder is overlarge, the strengthening effect of mechanical properties of the subsequently prepared superalloy is reduced, and cracks easily generated at a coarse compound/matrix interface of the prepared refractory intermetallic compound reinforced platinum-rhodium-based superalloy are avoided.
The Re is prepared by the arc melting-crushing-high-energy vibration ball milling-sieving method 3 Nb superfine powder has the advantages of short flow and controllable powder granularity, and is favorable for preparing fine X-phase intermetallic compound (Re) when the refractory intermetallic compound enhanced platinum-rhodium-based superalloy is prepared by a powder metallurgy method 3 Nb) is dispersed and distributed in the alloy matrixAnd the enhancement effect produced by the method is improved.
Obtaining Re 3 After Nb powder, the invention leads the Re to 3 And mixing the Nb powder with the sponge Pt and Rh powder, and performing second ball milling to obtain mixed powder.
In the present invention, the particle diameter of the sponge Pt is preferably 10 μm or less. In the present invention, the particle diameter of Rh powder is preferably 10 μm or less. The invention selects the grain diameter and Re 3 The sponge Pt and Rh powder with the same particle size of Nb ensures that the tissue structure of the refractory intermetallic compound reinforced platinum-rhodium-based superalloy prepared later is more uniform, the strengthening effect is better, and the defect that the grains of the refractory intermetallic compound reinforced platinum-rhodium-based superalloy are coarser when the particle sizes of the sponge Pt and Rh powder are too coarse is avoided, so that the strength of the superalloy is reduced.
In the present invention, the purity of Pt is preferably not less than 99.95%. In the present invention, the purity of Rh is preferably not less than 99.95%.
The invention relates to the Re 3 The mixing mode of the Nb powder and the sponge Pt and Rh powder is not particularly limited, and the uniform mixing of the components can be realized.
In the present invention, the second ball milling apparatus is preferably a planetary ball mill. In the present invention, the time of the second ball milling is preferably 9 to 22 hours, more preferably 10 to 20 hours. In the present invention, the ball-to-material ratio of the second ball mill is preferably (3.5 to 1.5): 1, more preferably (3 to 1.8): 1. In the present invention, the rotation speed of the second ball mill is preferably 40 to 100rpm, more preferably 50 to 90rpm. The invention controls the time, the ball-material ratio and the rotating speed of the second ball milling in the above range, so that each component is uniformly distributed, and the invention is favorable for the uniform dispersion distribution of the reinforcing phase in the Pt-Rh alloy.
After the mixed powder is obtained, the mixed powder is dried and compression molded in sequence to obtain an alloy ingot blank.
The drying mode and time are not particularly limited, and drying techniques well known to those skilled in the art may be adopted. According to the invention, the water vapor in the mixed powder is removed by drying, so that adverse effects of the water vapor on the performance of the mixed powder after subsequent compression molding and vacuum sintering are avoided.
In the present invention, the pressure of the compression molding is preferably 40 to 60MPa, more preferably 45 to 55MPa. The invention controls the compression molding pressure in the above range to obtain the complete alloy ingot blank with higher density and no crack, avoids the over-low pressure, has lower density and is easy to crack, and simultaneously avoids the over-high pressure, so that the alloy ingot blank has higher hysteresis elasticity and possibly causes expansion cracking of the alloy ingot blank.
In the present invention, the time for the compression molding is preferably 4 to 15 minutes, more preferably 5 to 10 minutes. In the invention, under a certain pressure, the density of the ingot blank is increased along with the extension of the pressure maintaining time, but the increasing amplitude is gradually reduced, and the invention controls the compression molding time within the range, so that the density of the prepared alloy ingot blank is higher, the too short compression molding time is avoided, the density of the alloy ingot blank does not reach the maximum value, and the process time is saved.
After the alloy ingot blank is obtained, the alloy ingot blank is subjected to vacuum sintering, and the sintered alloy ingot blank is obtained.
In the present invention, the vacuum sintering equipment is preferably a vacuum tungsten wire furnace. In the present invention, the vacuum degree of the vacuum sintering is preferably 5×10 or less -3 Pa, more preferably ∈4.5X10 -3 Pa. The invention controls the vacuum degree of vacuum sintering within the above range to prevent the alloy ingot blank from oxidizing in the vacuum sintering process, thereby being beneficial to obtaining the sintered alloy ingot blank with low gas impurity content and avoiding the alloy ingot blank from oxidizing to a certain extent after sintering due to too low vacuum degree.
In the present invention, the temperature rising rate of the vacuum sintering is preferably 2 to 7 ℃/min, more preferably 3 to 5 ℃/min. The invention controls the temperature rising rate of the vacuum sintering in the range, so that the alloy ingot blank is not cracked and deformed in the vacuum sintering process, the alloy ingot blank is prevented from cracking possibly caused by the too high temperature rising rate, more energy and time are prevented from being consumed due to the too low temperature rising rate, and the service life of equipment is prevented from being damaged.
In the present invention, the temperature of the vacuum sintering is preferably 1200 to 1550 ℃, more preferably 1300 to 1450 ℃. The invention controls the temperature of vacuum sintering in the above range, and can obtain alloy ingot blanks with finer alloy grain structures and higher density, thereby improving the strength and plasticity of the alloy ingot blanks, avoiding the overhigh sintering temperature, coarse grains, reducing the strength of the alloy ingot blanks, and simultaneously avoiding the overlow sintering temperature, lower density of the alloy ingot blanks and even being difficult to process.
In the present invention, the time for the vacuum sintering is preferably 1.5 to 5 hours, more preferably 2 to 4 hours. In the invention, under the condition that the sintering temperature is determined, the density and grain size of the alloy are increased along with the extension of the sintering time, but the increasing amplitude is gradually reduced, and the invention controls the vacuum sintering time in the range, thereby being beneficial to obtaining the alloy ingot blank with high density and high strength, avoiding the too short vacuum sintering time and being incapable of obtaining the ingot blank with high density, avoiding the alloy grain from being increased due to the too long vacuum sintering time and reducing the strength of the alloy.
The method comprises the steps of obtaining a sintered alloy ingot blank, and carrying out cold forging processing or cold rolling processing on the sintered alloy ingot blank to obtain refractory intermetallic compound reinforced platinum-rhodium-based superalloy;
and when the accumulated deformation of the cold forging process or the cold rolling process is independently 45-75%, performing intermediate annealing on the alloy after the cold forging process or the cold rolling process.
In the present invention, when the sintered alloy ingot is a cylindrical ingot, the sintered alloy ingot is preferably subjected to cold forging.
In the present invention, the cold forging process is preferably performed at room temperature.
In the present invention, the pass deformation amount in the cold forging process is preferably 8 to 18%, more preferably 10 to 15%. The method controls the pass deformation of cold forging in the range, can avoid material cracking caused by overlarge pass deformation, ensures the stability of the mechanical property of the finally prepared refractory intermetallic compound reinforced platinum-rhodium-based superalloy, avoids the cracking of the refractory intermetallic compound reinforced platinum-rhodium-based superalloy caused by overlarge pass deformation, and avoids the reduction of the processing or production efficiency of the refractory intermetallic compound reinforced platinum-rhodium-based superalloy caused by overlarge pass deformation.
In the present invention, the intermediate annealing is performed when the cumulative deformation amount in the cold forging is preferably 45 to 75%, more preferably 50 to 70%. The invention selects to perform intermediate annealing within the range of the accumulated deformation amount so as to eliminate the stress after the cold forging reaches the accumulated processing amount, and soften the alloy ingot blank for further processing.
In the present invention, the temperature of the intermediate annealing is preferably 750 to 1100 ℃, more preferably 850 to 1050 ℃. In the present invention, the time of the intermediate annealing is preferably 8 to 18 minutes, more preferably 10 to 15 minutes. The invention controls the temperature and time of the intermediate annealing in the above range to effectively eliminate the residual stress generated by the cold forging process, which is beneficial to further processing, finally prepares the refractory intermetallic compound reinforced platinum-rhodium-based superalloy with excellent mechanical properties, avoids the excessive temperature of the intermediate annealing or the overlong time of the intermediate annealing, causes the grain structure of the alloy to become coarse, reduces the mechanical properties of the alloy, and simultaneously avoids the excessively low temperature of the intermediate annealing or the excessively short time of the intermediate annealing, which can not achieve the effect of eliminating the stress of the cold forging process, and further processing becomes difficult.
In the present invention, when the sintered alloy ingot is a square ingot, the sintered alloy ingot is preferably subjected to cold rolling.
In the present invention, the cold rolling process is preferably performed at room temperature.
In the present invention, the pass deformation amount in the cold rolling is preferably 8 to 18%, more preferably 10 to 15%. The method controls the pass deformation of cold rolling in the range, can avoid material cracking caused by overlarge pass deformation, ensures the stability of the mechanical property of the finally prepared refractory intermetallic compound reinforced platinum-rhodium-based superalloy, avoids the cracking of the refractory intermetallic compound reinforced platinum-rhodium-based superalloy caused by overlarge pass deformation, and avoids the reduction of the processing or production efficiency of the refractory intermetallic compound reinforced platinum-rhodium-based superalloy caused by overlarge pass deformation.
In the present invention, the intermediate annealing is performed when the cumulative deformation amount in the cold rolling is preferably 45 to 75%, more preferably 50 to 70%. The invention selects to perform intermediate annealing within the range of the accumulated deformation amount so as to eliminate the stress of the alloy ingot blank after reaching the accumulated processing amount, and soften the alloy ingot blank for further processing.
In the present invention, the temperature of the intermediate annealing is preferably 750 to 1100 ℃, more preferably 850 to 1050 ℃. In the present invention, the time of the intermediate annealing is preferably 8 to 18 minutes, more preferably 10 to 15 minutes. The invention controls the temperature and time of the intermediate annealing in the above range to effectively eliminate the residual stress generated by cold rolling, which is beneficial to further processing, finally prepares the refractory intermetallic compound reinforced platinum-rhodium-based superalloy with excellent mechanical properties, avoids the overhigh temperature of the intermediate annealing or overlong time of the intermediate annealing, causes the grain structure of the alloy to become coarse, reduces the mechanical properties of the alloy, and simultaneously avoids the overlong temperature of the intermediate annealing or the overlong time of the intermediate annealing, thereby not achieving the effect of eliminating the stress of the cold rolling and further processing to become difficult.
The preparation method provided by the invention firstly utilizes an arc melting-crushing-high-energy vibration ball milling-sieving method to prepare Re 3 Nb ultrafine powder, and control Re 3 The grain diameter of Nb powder is preferably less than or equal to 10 mu m, which is favorable for the uniform dispersion distribution of the Nb powder serving as a reinforcing phase in Pt-Rh alloy and avoids Re 3 The grain size of Nb powder is overlarge, the strengthening effect of mechanical property of the high-temperature alloy prepared later is reduced, and cracks are prevented from being easily generated on a coarse compound/matrix interface by the prepared refractory intermetallic compound strengthened platinum-rhodium-based high-temperature alloy, so that the strength strengthening effect of the refractory intermetallic compound strengthened platinum-rhodium-based high-temperature alloy prepared later is optimal, and the novel refractory intermetallic compound χ phase is Re 3 Nb is used as a reinforcing phase, so that the Pt-Rh alloy with low Rh content has excellent high-temperature mechanical property and oxidation resistance, the consumption of noble metal Rh and alloy cost are greatly reduced, sponge Pt and Rh powder are added, and mixed and then subjected to second ball milling, so thatThe method comprises the steps of obtaining uniformly distributed components, obtaining mixed powder, further facilitating the uniform dispersion distribution of a reinforcing phase in Pt-Rh alloy, sequentially drying and compression molding to remove water vapor in the mixed powder, obtaining a high-density, crack-free and complete alloy ingot, performing vacuum sintering to obtain a sintered alloy ingot, preventing the alloy ingot from being oxidized in the vacuum sintering process, facilitating the obtaining of a sintered alloy ingot with finer alloy grain structure and higher density, further improving the strength and plasticity of the alloy ingot, performing cold forging or cold rolling on the sintered alloy ingot, improving the stability of the finally prepared refractory intermetallic compound for enhancing the mechanical property of the platinum-rhodium-based superalloy, avoiding cracking, and performing intermediate annealing to effectively eliminate residual stress generated by cold forging or cold rolling when the accumulated deformation of the cold forging or cold rolling is independently 45-75%, facilitating the further processing, further improving the mechanical property of the platinum-rhodium-based superalloy reinforced by the intermetallic compound, and finally preparing the platinum-rhodium-based superalloy which has uniform component distribution, obvious enhancement effect and excellent oxidation resistance.
The invention also provides application of the refractory intermetallic compound reinforced platinum-rhodium-based superalloy or the refractory intermetallic compound reinforced platinum-rhodium-based superalloy prepared by the preparation method in glass fiber bushing, crystal growth crucible and aerospace engine nozzle materials.
In the invention, the refractory intermetallic compound reinforced platinum-rhodium-based superalloy can be used for preparing glass fiber bushing plates, crystal growth crucibles and aerospace engine nozzles which work in a high Wen Jijiang oxidation corrosion environment at 1500-1600 ℃.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Refractory intermetallic compound reinforced Pt-Rh base superalloy, named Pt-0.5Re 3 Nb alloy consists of the following components in percentage by mass: re (Re) 3 Nb:0.5wt% and the balance Pt.
Preparation example 1
Refractory intermetallic reinforced platinum rhodium-based superalloys, pt-0.5Re 3 The preparation method of the Nb alloy comprises the following steps:
(1) The mass ratio of the substances is 3:1 and Nb are mixed and placed in a water-cooled copper crucible, and are smelted by adopting a non-consumable vacuum arc furnace, and the arc furnace is firstly pumped to 5 multiplied by 10 -3 Vacuum degree of Pa, charging argon of 0.12MPa, sequentially smelting and naturally cooling to obtain Re 3 Casting Nb ingot;
(2) Obtaining Re from the step (1) 3 Placing the Nb cast ingot into a steel mould, crushing the Nb cast ingot by adopting an impact method, then placing the Nb cast ingot into a high-energy vibration ball mill for first ball milling, and finally sieving to obtain Re with the particle size less than or equal to 10 mu m 3 Nb powder;
(3) Re obtained in the step (2) is obtained 3 Nb powder and sponge Pt having particle size of 10 μm or less were prepared as described in example 1 for Pt-0.5Re 3 Mixing the Nb alloy with the mass content to obtain a mixture, loading 200g of the mixture into a planetary ball mill, and performing second ball milling for 10 hours at the rotating speed of a tank body of 50rpm to obtain mixed powder with uniform components;
(4) Drying the mixed powder obtained in the step (3), and then putting the mixed powder into a square die to be molded for 5min under the pressure of 45MPa, so as to obtain a square pressed alloy ingot blank;
(5) Placing the square pressed alloy ingot blank obtained in the step (4) into a vacuum tungsten wire furnace for vacuum sintering to obtain a sintered alloy ingot blank, namely a square ingot blank; the vacuum degree of the vacuum sintering is 4 multiplied by 10 -3 Pa, wherein the temperature of the vacuum sintering is 1300 ℃, and the time of the vacuum sintering is 2h;
(6) Cold rolling the sintered alloy ingot blank obtained in the step (5) to obtain Pt-0.5Re 3 Nb alloy plates;
the pass deformation amount of the cold rolling process is 15%, when the accumulated deformation amount of the cold rolling process reaches 70%, the intermediate annealing is performed, the temperature of the intermediate annealing is 850 ℃, and the time of the intermediate annealing is 10min.
Example 2
Refractory intermetallic compound reinforced Pt-Rh-based superalloy, noted Pt-7Rh-0.5Re 3 Nb alloy consists of the following components in percentage by mass: rh:7wt%, re 3 Nb:0.5wt% and the balance Pt.
Preparation example 2
Refractory intermetallic reinforced platinum rhodium-based superalloy, pt-7Rh-0.5Re 3 The preparation method of the Nb alloy comprises the following steps:
(1) The mass ratio of the substances is 3:1 and Nb are mixed and placed in a water-cooled copper crucible, and are smelted by adopting a non-consumable vacuum arc furnace, and the arc furnace is firstly pumped to 5 multiplied by 10 -3 Vacuum degree of Pa, charging argon of 0.12MPa, sequentially smelting and naturally cooling to obtain Re 3 Casting Nb ingot;
(2) Obtaining Re from the step (1) 3 Placing the Nb cast ingot into a steel mould, crushing the Nb cast ingot by adopting an impact method, then placing the Nb cast ingot into a high-energy vibration ball mill for first ball milling, and finally sieving the Nb cast ingot to obtain Re with the particle size less than or equal to 10 mu m 3 Nb powder;
(3) Re obtained in the step (2) is obtained 3 Nb powder and sponge Pt with particle size less than or equal to 10 μm, sponge Rh powder were prepared as described in example 2 for Pt-7Rh-0.5Re 3 Mixing the Nb alloy with the mass content to obtain a mixture, loading 200g of the mixture into a planetary ball mill, and performing second ball milling for 17 hours at the rotating speed of a tank body of 50rpm to obtain mixed powder with uniform components;
(4) Drying the mixed powder obtained in the step (3), and then putting the mixed powder into a square die to be molded for 6min under the pressure of 50MPa, so as to obtain a square pressed alloy ingot blank;
(5) Placing the square pressed alloy ingot blank obtained in the step (4) into a vacuum tungsten filament furnace for vacuum sintering to obtain sintered alloyThe ingot blank is square ingot blank; the vacuum degree of the vacuum sintering is 3 multiplied by 10 -3 Pa, wherein the temperature of the vacuum sintering is 1350 ℃, and the time of the vacuum sintering is 3 hours;
(6) Cold rolling the sintered alloy ingot blank obtained in the step (5) to obtain refractory intermetallic compound reinforced platinum-rhodium-based superalloy, namely Pt-7Rh-0.5Re 3 Nb alloy plates;
the pass deformation amount of the cold rolling process is 135%, and when the accumulated deformation amount of the cold rolling process reaches 60%, the intermediate annealing is performed, the temperature of the intermediate annealing is 950 ℃, and the time of the intermediate annealing is 12min.
Example 3
Refractory intermetallic compound reinforced Pt-Rh-based superalloy, noted Pt-10Rh-0.5Re 3 Nb alloy consists of the following components in percentage by mass: rh:10wt%, re 3 Nb:0.5wt% and the balance Pt.
Preparation example 3
Refractory intermetallic reinforced platinum rhodium-based superalloy, pt-10Rh-0.5Re 3 The preparation method of the Nb alloy comprises the following steps:
(1) The mass ratio of the substances is 3:1 and Nb are mixed and placed in a water-cooled copper crucible, and are smelted by adopting a non-consumable vacuum arc furnace, and the arc furnace is firstly pumped to 5 multiplied by 10 -3 Vacuum degree of Pa, charging 0.11MPa argon, sequentially smelting and naturally cooling to obtain Re 3 Casting Nb ingot;
(2) Obtaining Re from the step (1) 3 Placing the Nb cast ingot into a steel mould, crushing the Nb cast ingot by adopting an impact method, then placing the Nb cast ingot into a high-energy vibration ball mill for first ball milling, and finally sieving the Nb cast ingot to obtain Re with the particle size less than or equal to 10 mu m 3 Nb powder;
(3) Re obtained in the step (2) is obtained 3 Nb powder and sponge Pt with particle size less than or equal to 10 μm, sponge Rh powder were prepared according to the method described in example 3 for Pt-10Rh-0.5Re 3 Mixing the Nb alloy with the mass content to obtain a mixture, loading 180g of the mixture into a planetary ball mill, and performing second ball milling for 18 hours at the rotating speed of a tank body of 80rpm to obtain mixed powder with uniform components;
(4) Drying the mixed powder obtained in the step (3), and then putting the mixed powder into a square die to be molded for 8min under the pressure of 55MPa, so as to obtain a square pressed alloy ingot blank;
(5) Placing the square pressed alloy ingot blank obtained in the step (4) into a vacuum tungsten wire furnace for vacuum sintering to obtain a sintered alloy ingot blank, namely a square ingot blank; the vacuum degree of the vacuum sintering is 3 multiplied by 10 -3 Pa, wherein the temperature of the vacuum sintering is 1400 ℃, and the time of the vacuum sintering is 3 hours;
(6) Cold rolling the sintered alloy ingot blank obtained in the step (5) to obtain refractory intermetallic compound reinforced platinum-rhodium-based superalloy, namely Pt-10Rh-0.5Re 3 Nb alloy plates;
the pass deformation amount of the cold rolling process is 11%, when the accumulated deformation amount of the cold rolling process reaches 55%, the intermediate annealing is performed, the temperature of the intermediate annealing is 1000 ℃, and the time of the intermediate annealing is 15min.
Example 4
Refractory intermetallic compound reinforced Pt-Rh-based superalloy, designated Pt-10Rh-1.0Re 3 Nb alloy consists of the following components in percentage by mass: rh:10wt%, re 3 Nb:1.0wt% and the balance Pt.
Preparation example 4
Refractory intermetallic reinforced platinum rhodium-based superalloy, pt-10Rh-1.0Re 3 The preparation method of the Nb alloy comprises the following steps:
(1) The mass ratio of the substances is 3:1 and Nb are mixed and placed in a water-cooled copper crucible, and are smelted by adopting a non-consumable vacuum arc furnace, and the arc furnace is firstly pumped to 5 multiplied by 10 -3 Vacuum degree of Pa, charging 0.11MPa argon, sequentially smelting and naturally cooling to obtain Re 3 Casting Nb ingot;
(2) Obtaining Re from the step (1) 3 Placing the Nb cast ingot into a steel mould, crushing the Nb cast ingot by adopting an impact method, then placing the Nb cast ingot into a high-energy vibration ball mill for first ball milling, and finally sieving the Nb cast ingot to obtain Re with the particle size less than or equal to 10 mu m 3 Nb powder;
(3) Re obtained in the step (2) is obtained 3 Nb powder and sponge Pt with particle size less than or equal to 10 μm, sponge Rh powder were prepared according to the method described in example 4 for Pt-10Rh-1.0Re 3 Mixing the Nb alloy with the mass content to obtain a mixture, loading 150g of the mixture into a planetary ball mill, and performing second ball milling for 20 hours at the rotating speed of a tank body of 90rpm to obtain mixed powder with uniform components;
(4) Drying the mixed powder obtained in the step (3), and then putting the mixed powder into a circular mold to be molded for 10min under the pressure of 55MPa, so as to obtain a cylindrical pressed alloy ingot blank;
(5) Placing the cylindrical pressed alloy ingot blank obtained in the step (4) into a vacuum tungsten wire furnace for vacuum sintering to obtain a sintered alloy ingot blank, namely a cylindrical rod blank; the vacuum degree of the vacuum sintering is 3 multiplied by 10 -3 Pa, wherein the temperature of the vacuum sintering is 1450 ℃, and the time of the vacuum sintering is 4 hours;
(6) Cold forging the sintered alloy ingot blank obtained in the step (5) to obtain refractory intermetallic compound reinforced Pt-Rh-based superalloy (Pt-10 Rh-1.0 Re) 3 Nb alloy bar material;
the pass deformation amount of the cold rolling process is 10%, when the accumulated deformation amount of the cold forging process reaches 50%, the intermediate annealing is performed, the temperature of the intermediate annealing is 1050 ℃, and the time of the intermediate annealing is 15min.
Re in refractory intermetallic compound-enhanced platinum-rhodium-based superalloy prepared in example 4 was observed by scanning electron microscopy 3 The distribution of Nb in the alloy is shown in FIG. 1, and it is understood from FIG. 1 that the refractory intermetallic compound-reinforced platinum-rhodium-based superalloy prepared in example 4 has a reinforcing phase Re 3 Nb is uniformly dispersed in the alloy.
Comparative example 1
The preparation and performance test method of comparative alloy 1 (noted as Pt-0.5Gd alloy) is as follows:
the mass ratio of Pt is as follows: gd=99.5: 0.5 preparing alloy, putting raw materials Pt and Gd into a high-frequency induction furnace for smelting, and adopting a cold processing method to process an alloy ingot into a wire with the diameter of 0.3 mm. Creep experiments were carried out in a MoSi tube furnace with an automatic timing and control system, with a furnace soak zone of 30mm, where the temperature does not vary by more than 5 ℃.
Comparative example 2
The comparative alloy 2 (designated Pt-7Rh alloy) was prepared and tested for performance as follows:
pt with a purity of 99.95% and Rh with a purity of 99.95% were selected as raw materials according to the mass ratio of Pt: rh=93: and 7, preparing an alloy, smelting Pt and Rh alloy elements in the atmosphere, and processing a sample into a wire with the diameter of 0.3mm and annealing. High temperature mechanical property tests at 1200 ℃ and 1400 ℃ were performed in the atmosphere.
Comparative example 3
The preparation and performance test method of comparative alloy 3 (noted as Pt-7Rh-0.35LaCe alloy) is as follows:
the mass ratio of Pt is as follows: rh: (la+ce) =92.65: 7.00:0.35 alloy is prepared, alloy elements Pt, rh, la and Ce (purity is more than 99.9%) are mixed and pressed into blocks, the blocks are put into a corundum crucible, and are melted by a power frequency furnace under the condition of vacuum argon filling, and the molten liquid is injected into a cold copper mold. The ingot is processed into wire or sheet by conventional methods. The endurance strength and creep rupture time at 10MPa stress were then determined at 1200 and 1400℃for 10 hours, 100 hours and 1000 hours.
Comparative example 4
The comparative alloy 4 (designated Pt-10Rh alloy) was prepared and tested for performance as follows:
comparative alloy 4 was prepared as in comparative example 2;
unlike comparative example 2, the alloy raw materials Pt and Rh were in mass ratio of Pt: rh=90: 10.
comparative example 5
The comparative alloy 5 (designated as Pt-30Rh alloy) was prepared and tested for performance as follows:
comparative alloy 5 was prepared as in comparative example 2;
unlike comparative example 2, the alloy raw materials Pt and Rh were in mass ratio of Pt: rh=70: 30.
comparative example 6
The comparative metal 6 (noted Pt) was prepared and tested for performance as follows:
a Pt flake sample with the thickness of 0.03mm for oxidation experiments is prepared by adopting a smelting rolling method, the flake sample is wound on the surface of a quartz cylinder and is hung in a tubular high-temperature furnace, and the oxidation experiments are carried out in dry flowing air. And measuring the weight change of the material by using an automatic continuous recording analyzer to obtain the final weight before and after the experiment, and calculating the oxidation weight loss of the material in unit area and unit time.
Comparative example 7
The comparative alloy 7 (noted Pt-0.5Y alloy) was prepared and tested for performance as follows:
the mass ratio of Pt is as follows: y=99.5: 0.5 preparing alloy, putting raw materials Pt and Y into a high-frequency induction furnace for smelting, and processing an alloy ingot into wires with the diameter of 0.3mm by adopting a cold processing method. The oxidation experiment is carried out in a MoSi tubular heating furnace with an automatic timing and control system, the oxidation temperature is 1400-1500 ℃, and the oxidation time is 4 hours. The weight change before and after the experiment is obtained, and the oxidation weight loss of the material in unit area and unit time is calculated.
Comparative example 8
The comparative alloy 8 (designated as Pt-24Nb-3Ru alloy) was prepared and tested for performance as follows:
the purity of the alloy element is more than or equal to 99.9 percent, and the mass ratio of the alloy element is Pt: nb: ru=73: 24:3 preparing alloy, smelting the alloy by adopting an arc furnace to obtain raw materials Pt, nb and Ru, and carrying out heat treatment for 6 hours at 1350 ℃ on the cast ingot in an argon atmosphere. The oxidized sample surface was polished and the oxidation experiment was performed on a TG-DTA92 thermogravimetric analyzer. The experimental temperatures are 900, 1100, 1300 and 1400 ℃ respectively, and the experimental time is 10000s.
Comparative example 9
The comparative alloy 9 (designated as Pt-24Ta-4Re alloy) was prepared and tested for performance as follows:
comparative alloy 9 was prepared as in comparative example 8;
unlike comparative example 8, the alloy raw material mass ratio was Pt: ta: re=72: 24: pt, ta and Re of 4.
The alloys of examples 1 to 4 and the comparative alloys prepared in comparative examples 1 to 5 were examined for their high temperature mechanical properties (i.e., 10h endurance, 10MPa creep life and 5MPa creep life) by a high temperature creep test method, and the alloys of examples 1 to 4 and the comparative alloys prepared in part by a constant temperature oxidation test method were examined for their high temperature oxidation resistance (i.e., oxidation weight loss), with specific results shown in tables 1 and 2.
TABLE 1 high temperature mechanical Properties of the alloys in examples 1 to 4 and the comparative alloys in comparative examples 1 to 5
In table 1 "—" represents undetected or unreported in the literature.
Table 2 high temperature oxidation resistance of the alloys of examples 1-4 with the comparative metals and a portion of the comparative alloys
In table 2 "—" represents undetected or unreported in the literature.
As can be seen from tables 1 and 2, (1) Pt-0.5Re as described in example 1 at 1400 ℃ 3 The 10h endurance strength and 10MPa creep life of Nb alloy are 7.7MPa and 0.82h respectively, and the strength and life of rare earth Gd-reinforced comparative alloy 1, namely Pt-0.5Gd alloy, are 6.5MPa and 0.63h respectively, pt-0.5Re prepared in example 1 3 The 10h endurance strength and 10MPa creep life of the Nb alloy are respectively 1.18 times and 1.30 times that of the comparative alloy 1 prepared in comparative example 1; pt-0.5Re at 1400 DEG C 3 Oxidation weight loss of Nb alloy is 7.5X10 -3 mg/cm 2 H, slightly higher than the comparative metal 6, i.e. 5.2X10 of pure Pt -3 mg/cm 2 H, but significantly lower than the 2X 10 of the comparative alloy 7, pt-0.5Y alloy -2 mg/cm 2 ·h。
(2) At 1400℃the Pt-7Rh-0.5Re described in example 2 3 The 10h endurance strength and 10MPa creep life of the Nb alloy were 8.6MPa and 2.3h, respectively, and the strength and life of the rare earth-reinforced comparative alloy 3, pt-7Rh-0.35LaCe, described in example 2, was 6.6MPa and 1.7h, respectively 3 The 10h endurance strength and the 10MPa creep life of the Nb alloy are respectively 1.30 times and 1.35 times that of the comparative alloy 3; pt-7Rh-0.5Re at 1400 DEG C 3 Oxidation weight loss of Nb alloy is 7.1X10 -3 mg/cm 2 H, slightly higher than the comparative metal 6, i.e. 5.2X10 of pure Pt -3 mg/cm 2 H, but significantly lower than the 2X 10 of the comparative alloy 7, pt-0.5Y alloy -2 mg/cm 2 ·h。
(3) Pt-10Rh-0.5Re as described in example 3 3 The 10h endurance strength of the Nb alloy at 1500 ℃ and 1600 ℃ is 8.6MPa and 6.2MPa respectively, which are 2.15 times and 2.58 times that of the solid solution reinforced comparative alloy 4, namely Pt-10Rh, respectively, and the endurance strength and creep life of the alloy described in the example 3 are both higher than those of the comparative alloy 5, namely Pt-30Rh, at the corresponding temperature; pt-10Rh-0.5Re as described in example 3 3 Nb alloy has an oxidation weight loss of 3.0X10 at 1500 DEG C -2 mg/cm 2 H, slightly higher than the 2X 10 of the comparative alloy 4, i.e. Pt-10Rh alloy -2 mg/cm 2 ·h。
(4) Pt-10Rh-1.0Re as described in example 4 3 The 10h endurance strength of the Nb alloy at 1500 ℃ and 1600 ℃ is 11.3MPa and 8.0MPa respectively, which are 2.83 times and 3.33 times that of the comparative alloy 4, namely Pt-10Rh alloy, respectively, and the endurance strength and creep life of the alloy described in the example 4 are both higher than those of the comparative alloy 5, namely Pt-30Rh alloy at the corresponding temperature; pt-10Rh-1.0Re as described in example 4 3 Nb alloy has oxidation weight loss of 4.5X10 at 1500 DEG C -2 mg/cm 2 H, slightly higher than the 2X 10 of the comparative alloy 4, i.e. Pt-10Rh alloy -2 mg/cm 2 ·h。
Taken together, it can be seen that Pt-10Rh-1.0Re as described in example 4 of the present invention 3 The 10h endurance strength of Nb alloy at 1500 ℃ and 1600 ℃ can reach 11.3MPa and 8.0MPa respectively, and Pt-10Rh-0.5Re is described in example 3 3 Nb alloy 1500 DEG CAs low as 3.0X10 oxidation weight -2 mg/cm 2 H. The invention provides a preparation method of refractory intermetallic compound reinforced platinum-rhodium-based superalloy, which comprises the steps of firstly preparing a χ phase, namely refractory intermetallic compound Re 3 Nb superfine powder is favorable for the dispersion and distribution of fine X phases in alloy matrix, and refractory intermetallic compound Re with melting point up to 2640℃ is used 3 Nb (0.05-1.0 wt%) is used as reinforcing phase, pt-Rh alloy with low Rh content (Rh=0-10 wt%) is used as matrix, and the Re is prepared by adopting powder metallurgy method 3 The Nb has very remarkable enhancement effect relative to Pt-Rh alloy, and the prepared refractory intermetallic compound enhanced platinum-rhodium-based superalloy has excellent high-temperature mechanical property, maintains the inherent excellent oxidation resistance of the platinum-rhodium alloy, and greatly reduces the consumption of noble metal Rh and the alloy cost.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A refractory intermetallic compound-reinforced platinum-rhodium-based superalloy comprising the following components in mass content: rh 0-12 wt%, re 3 0.03-1.2wt% of Nb and the balance of Pt;
the refractory intermetallic compound reinforced platinum-rhodium-based superalloy is prepared by an arc melting-crushing-high-energy vibration ball milling-sieving method 3 The Nb superfine powder is prepared into refractory intermetallic compound reinforced platinum-rhodium-based superalloy by adopting a powder metallurgy method.
2. A method of preparing a refractory intermetallic-enhanced platinum-rhodium-based superalloy as claimed in claim 1 comprising the steps of:
(1) Re and Nb with the mass ratio of 3:1 are mixed and then are sequentially smelted and naturally cooled to obtain Re 3 Casting Nb ingot;
(2) Obtaining Re from the step (1) 3 Nb cast ingot is broken in sequenceCrushing and first ball milling to obtain Re 3 Nb powder;
(3) Obtaining Re from the step (2) 3 Mixing Nb powder with sponge Pt and Rh powder, and performing second ball milling to obtain mixed powder;
(4) Sequentially drying and compression molding the mixed powder obtained in the step (3) to obtain an alloy ingot blank;
(5) Performing vacuum sintering on the alloy ingot blank obtained in the step (4) to obtain a sintered alloy ingot blank;
(6) Carrying out cold forging or cold rolling on the sintered alloy ingot blank obtained in the step (5) to obtain refractory intermetallic compound reinforced platinum-rhodium-based superalloy;
and (3) when the accumulated deformation of the cold forging or cold rolling in the step (6) is independently 45-75%, performing intermediate annealing on the alloy after the cold forging or cold rolling.
3. The method according to claim 2, wherein the vacuum is first applied to the apparatus for melting to a vacuum degree of 10 or less before the melting in the step (1) is started -2 Pa, and then filling argon of 0.11-0.13 MPa.
4. The method according to claim 2, wherein Re in the step (2) 3 The grain diameter of Nb powder is less than or equal to 10 mu m.
5. The preparation method according to claim 2, wherein the second ball milling time in the step (3) is 9-22 h, the ball-to-material ratio of the second ball milling is (3.5-1.5): 1, and the rotation speed of the second ball milling is 40-100 rpm.
6. The preparation method according to claim 2, wherein the pressure of the compression molding in the step (4) is 40-60 mpa, and the time of the compression molding is 4-15 min.
7. According to claim 2 The preparation method is characterized in that the vacuum degree of the vacuum sintering in the step (5)≤5×10 -3 Pa, the temperature of the vacuum sintering is 1200-1550 ℃, and the time of the vacuum sintering is 1.5-5 h.
8. The production method according to claim 2, wherein when the sintered alloy ingot in the step (6) is a cylindrical rod ingot, the sintered alloy ingot is subjected to cold forging processing;
and (3) when the sintered alloy ingot blank in the step (6) is square, performing cold rolling processing on the sintered alloy ingot blank.
9. The method according to claim 2, wherein the intermediate annealing in the step (6) is performed at a temperature of 750-1100 ℃ for 8-18 min.
10. The refractory intermetallic compound-reinforced platinum-rhodium-based superalloy of claim 1 or the refractory intermetallic compound-reinforced platinum-rhodium-based superalloy prepared by the preparation method of any one of claims 2 to 9, and the refractory intermetallic compound-reinforced platinum-rhodium-based superalloy is used in glass fiber bushing, crystal growth crucible and jet tube materials of aerospace engines.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016047951A (en) * | 2014-08-27 | 2016-04-07 | 石福金属興業株式会社 | Platinum-rhodium alloy and manufacturing method therefor |
| CN108149055A (en) * | 2017-11-16 | 2018-06-12 | 重庆材料研究院有限公司 | It is a kind of for dispersion strengthening type material of platinum rhodium base vessel and its preparation method and application |
| CN110438364A (en) * | 2019-09-02 | 2019-11-12 | 贵研铂业股份有限公司 | Palladium vanadium precision high-resistance alloy and preparation method thereof |
| CN110983095A (en) * | 2019-12-25 | 2020-04-10 | 无锡英特派金属制品有限公司 | Method for compounding dispersion-strengthened platinum rhodium and common platinum rhodium |
| CN111519058A (en) * | 2020-04-29 | 2020-08-11 | 重庆国际复合材料股份有限公司 | Preparation method of in-situ synthesized nano-oxide particle dispersion strengthened platinum-based alloy material |
| CN114107723A (en) * | 2021-11-26 | 2022-03-01 | 昆明富尔诺林科技发展有限公司 | Crucible for drawing glass fiber, Pt-based high-temperature alloy and preparation method thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016047951A (en) * | 2014-08-27 | 2016-04-07 | 石福金属興業株式会社 | Platinum-rhodium alloy and manufacturing method therefor |
| CN108149055A (en) * | 2017-11-16 | 2018-06-12 | 重庆材料研究院有限公司 | It is a kind of for dispersion strengthening type material of platinum rhodium base vessel and its preparation method and application |
| CN110438364A (en) * | 2019-09-02 | 2019-11-12 | 贵研铂业股份有限公司 | Palladium vanadium precision high-resistance alloy and preparation method thereof |
| CN110983095A (en) * | 2019-12-25 | 2020-04-10 | 无锡英特派金属制品有限公司 | Method for compounding dispersion-strengthened platinum rhodium and common platinum rhodium |
| CN111519058A (en) * | 2020-04-29 | 2020-08-11 | 重庆国际复合材料股份有限公司 | Preparation method of in-situ synthesized nano-oxide particle dispersion strengthened platinum-based alloy material |
| CN114107723A (en) * | 2021-11-26 | 2022-03-01 | 昆明富尔诺林科技发展有限公司 | Crucible for drawing glass fiber, Pt-based high-temperature alloy and preparation method thereof |
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