CN116590634A - Method for improving high-temperature oxidation resistance of refractory high-entropy alloy, high-performance refractory high-entropy alloy, and preparation and application thereof - Google Patents
Method for improving high-temperature oxidation resistance of refractory high-entropy alloy, high-performance refractory high-entropy alloy, and preparation and application thereof Download PDFInfo
- Publication number
- CN116590634A CN116590634A CN202310472602.6A CN202310472602A CN116590634A CN 116590634 A CN116590634 A CN 116590634A CN 202310472602 A CN202310472602 A CN 202310472602A CN 116590634 A CN116590634 A CN 116590634A
- Authority
- CN
- China
- Prior art keywords
- entropy alloy
- alloy
- refractory
- refractory high
- tinbmoalsi
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 90
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 88
- 230000003647 oxidation Effects 0.000 title claims abstract description 44
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- 230000008021 deposition Effects 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010894 electron beam technology Methods 0.000 claims abstract description 22
- 238000011065 in-situ storage Methods 0.000 claims abstract description 13
- 238000000151 deposition Methods 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000006104 solid solution Substances 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 27
- 238000004381 surface treatment Methods 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 6
- 239000002335 surface treatment layer Substances 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 description 8
- 230000004584 weight gain Effects 0.000 description 7
- 235000019786 weight gain Nutrition 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910008423 Si—B Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
- C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
A method for improving high-temperature oxidation resistance of refractory high-entropy alloy, high-performance refractory high-entropy alloy, and preparation and application thereof. The application belongs to the field of high-temperature alloy materials. The application aims to solve the technical problem that the prior refractory high-entropy alloy has poor inherent oxidation resistance under the high-temperature condition. The method comprises the steps of carrying out surface remelting and surface in-situ deposition of a pure aluminum layer on an as-cast refractory high-entropy alloy through electron beam surface treatment, combining the alloy surface treatment layer with a matrix in a metallurgical mode, and obtaining a high-quality surface treatment layer and a combined interface through regulating and controlling technological parameters such as electron beam current density, wire feeding speed and the like, thereby improving the high-temperature environmental stability of the refractory high-entropy alloy.
Description
Technical Field
The application belongs to the field of high-temperature alloy materials, and particularly relates to a method for improving high-temperature oxidation resistance of refractory high-entropy alloy, high-performance refractory high-entropy alloy, and preparation and application thereof.
Background
With the development of weaponry and aerospace technology, the use temperature and performance requirements of high-temperature structures such as hot end components of turbine guides of aeroengines and the like on high-temperature resistant materials are also increasing. The service temperature of the traditional superalloy can not meet the service requirement of the new generation of hot end components, and development/search of a high-temperature structural material with higher temperature bearing capacity and good comprehensive performance is needed.
At present, though the refractory high-entropy alloy has extremely high-temperature performance, the refractory high-entropy alloy shows poor high-temperature oxidation resistance under high-temperature conditions due to the high content of refractory elements, which restricts the practical application of the refractory high-entropy alloy. The way to improve the high-temperature oxidation resistance of refractory high-entropy alloy at present is to add alloying elements or oxidation coating. However, in consideration of the high-temperature mechanical strength-plasticity synergy, alloying of Al, cr, si is more limited to trace/small amounts, which results in difficulty in formation of Al 2 O 3 、Cr 2 O 3 And SiO 2 Such single and continuous selective oxidation layers; although the use of oxidation resistant coatings, such as Mo-Si-B coatings, may improve the oxidation resistance of the alloy to some extent, heterogeneous bonding between the coating and the base alloy may lead to failure of the coating if operated under high load for a prolonged period of time, which would cause catastrophic oxidation of the base alloy once the coating failed. Therefore, there is still a need to develop a method for effectively improving the inherent oxidation resistance of the matrix alloy, and deeply optimizing the comprehensive properties of refractory high-entropy alloy to promote the refractory high-entropy alloy to be in a high-temperature environmentThe following application has evolved.
Disclosure of Invention
The application aims to solve the technical problem that the inherent oxidation resistance of the existing refractory high-entropy alloy is poor at high temperature, and provides a method for improving the high-temperature oxidation resistance of the refractory high-entropy alloy, a high-performance refractory high-entropy alloy, and preparation and application thereof.
The aim of the application is achieved by the following technical scheme:
one of the purposes of the application is to provide a method for improving the high-temperature oxidation resistance of refractory high-entropy alloy, which comprises the steps of carrying out electron beam surface remelting and electron beam fuse surface in-situ deposition of a pure aluminum layer on the refractory high-entropy alloy under vacuum condition, and carrying out stress relief annealing after cooling.
Further defined, the electron beam surface remelting parameters: beam Density I b 20-30mA, scanning speed (electron beam running speed) V print The scanning distance is 1.5-2.0mm, the scanning times are 1 time, and the scanning path is unidirectional.
Further defined, the e-beam fuse surface in situ deposition of pure aluminum layer parameters: beam Density I b At a scanning speed (electron beam running speed) of 30-40mA print 500-700mm/min, scanning interval of 2.0-3.0mm, wire feeding speed V feed The scanning path is unidirectional and stays between tracks for 15-25s at 1.5-2.0 m/min.
Further defined, the annealing temperature is 350-450 ℃ and the time is 2-4 hours.
Further defined, the refractory high-entropy alloy includes, but is not limited to, a TiNbMoAlSi alloy.
The second object of the application is to provide a preparation method of the high-performance refractory high-entropy alloy, which comprises the following steps:
s1: according to TiNbMo 0.5 Al 0.225 Si x Weighing materials in atomic ratio with x less than or equal to 0.6, preparing alloy ingots by adopting non-consumable vacuum arc melting, obtaining a straight surface by linear cutting, and obtaining a pretreatment sample by grinding, polishing and cleaning;
s2: fixing the substrate and the sample on a workbench, sealing, vacuumizing, and then treating the surface of the sample according to the method to obtain the high-performance TiNbMoAlSi refractory high-entropy alloy.
Further defined, evacuating to 7X 10 in S2 -2 Pa。
The third object of the present application is to provide a high-performance TiNbMoAlSi refractory high-entropy alloy prepared by the above method, in which a pure aluminum layer is metallurgically bonded to a substrate.
Further defined, the alloy structure comprises a BCC solid solution, beta- (Nb, ti) 5 Si 3 、γ-(Nb,Ti) 5 Si 3 、Al 5 Mo and Al 3 Ti。
The application aims at providing an application of the high-performance TiNbMoAlSi refractory high-entropy alloy prepared by the method in hot end components in the aerospace field.
Compared with the prior art, the application has the remarkable effects that:
the application utilizes the electron beam surface treatment technology to combine the alloy surface treatment layer and the matrix in a metallurgical mode, and obtains a high-quality surface treatment layer and a combination interface by regulating and controlling technological parameters such as electron beam current density, wire feeding speed and the like, thereby improving the high-temperature environmental stability of refractory high-entropy alloy. Meanwhile, because the refractory high-entropy alloy has limited plasticity, the application adopts a stress relief annealing procedure, thereby effectively inhibiting the generation of cracks and ensuring the acquisition of high-quality surface treatment alloy. The method has the specific advantages that:
(1) The preparation process of the alloy master ingot is simple, namely, ingots with different components are obtained by a non-consumable arc melting technology.
(2) The application can realize the rapid remelting and rapid deposition of the refractory high-entropy alloy surface, and can obtain a surface treatment layer structure with good forming and compact structure by adjusting the process parameters, thereby effectively inhibiting the generation of microcracks in the rapid solidification process.
(3) The application obviously improves the oxidation resistance of refractory high-entropy alloy on the premise of considering mechanical properties. Compared with the sample treated by the surface remelting and surface deposition pure aluminum layer technology, compared with the sample in an as-cast state, the oxidation weight gain is reduced by 15.64 percent and 20.19 percent after the sample is oxidized for 36 hours at 1000 ℃ in a circulating way.
(4) The preparation method provided by the application has popularization, can be applied to the surface rapid treatment of other high-temperature alloys and the in-situ large-size surface fuse deposition of complex components, and has strong practicability.
Drawings
FIG. 1 is a diagram showing the macroscopic morphology of a TiNbMoAlSi alloy according to an embodiment of the present application after surface remelting and surface deposition;
FIG. 2 is a surface macroscopic view of samples subjected to cyclic high-temperature oxidation before remelting treatment, after remelting treatment and after in-situ deposition of a pure aluminum layer on the surfaces of TiNbMoAlSi alloy according to the embodiment of the application;
FIG. 3 is an XRD pattern of the TiNbMoAlSi alloy according to the embodiment of the application after remelting treatment of the surface and after in-situ deposition of a pure aluminum layer on the surface;
FIG. 4 is a graph showing oxidation kinetics after cyclic high-temperature oxidation of a sample after remelting treatment of the surface of a TiNbMoAlSi alloy and after in-situ deposition of a pure aluminum layer on the surface of the alloy in the embodiment of the application;
FIG. 5 is a microstructure of the TiNbMoAlSi alloy according to the present example after surface remelting treatment;
FIG. 6 is a view showing an oxidized cross-sectional structure of a sample of TiNbMoAlSi alloy before and after the surface remelting treatment in the present example, wherein (a) before the remelting treatment, (b) after the remelting treatment;
FIG. 7 is a microstructure of the TiNbMoAlSi alloy according to the present example after deposition of a pure aluminum layer on the surface;
fig. 8 is an oxidized cross-sectional structure diagram of samples before and after depositing a pure aluminum layer on the surface of the TiNbMoAlSi alloy in this example after cyclic high-temperature oxidation, where (a) is before surface deposition and (b) is after surface deposition.
Detailed Description
The present application will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range. In the description and claims of the application, the range limitations may be combined and/or interchanged, if not otherwise specified, including all the sub-ranges subsumed therein.
The indefinite articles "a" and "an" preceding an element or component of the application are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
Examples:
the preparation method of the high-performance TiNbMoAlSi refractory high-entropy alloy comprises the following steps:
(1) According to TiNbMo 0.5 Al 0.225 Si 0.25 The method comprises the steps of (1) weighing raw materials according to atomic weight ratio, placing the raw materials in a vacuum arc furnace, vacuumizing, filling inert gas, smelting by using a non-consumable vacuum arc smelting technology under the condition of the inert gas to obtain a TiNbMoAlSi refractory high-entropy alloy cast ingot, then obtaining a flat cast ingot surface through linear cutting, polishing the sample surface, carrying out ultrasonic cleaning, and carrying out heat preservation in a drying box at 60 ℃ for 1h to carry out drying treatment so as to remove residual moisture on the surface of the sample.
(2) And (3) carrying out sand paper polishing on a cast iron substrate with the dimensions of 150mm multiplied by 100mm multiplied by 20mm until the surface is smooth and clean, wiping the surface of the substrate by using acetone to remove greasy dirt and impurities on the surface, and then placing the substrate in a drying oven at 60 ℃ for heat preservation for 1h for drying treatment so as to remove residual moisture on the surface.
(3) Clamping the cast iron substrate processed in the step (2) on a moving system in a vacuum chamber of electron beam equipment, and fixing the TiNbMoAlSi refractory high-entropy alloy sample in the step (1) on the substrate.
(4) Closing the cabin door, running the equipment, and waiting for the vacuum degree of the vacuum chamber of the equipment to reach the use requirement (7 multiplied by 10) -2 Pa), scanning the surface of the TiNbMoAlSi refractory high-entropy alloy sample by the electron beam according to preset technological parameters and scanning paths, so that the surface of the sample is melted and solidified to form a remelting layer with fine and uniform structure, wherein the specific remelting technological parameters and scanning paths are as follows: beam Density I b 25mA, scanning speed (electron beam running speed) V print The scanning distance is 1.8mm, the scanning times are 1, and the scanning path is unidirectional, wherein the scanning time is 600 mm/min. The object diagram after surface remelting is shown in figure 1, and the object diagram is compact in surface, free of cracks and good in formability.
(5) The electron beam carries out fuse deposition on the surface of the TiNbMoAlSi refractory high-entropy alloy sample according to preset technological parameters and scanning paths, so that pure aluminum wires are melted and uniformly deposited on the surface of the sample to form metallurgical bonding, and the method has the advantages ofThe deposition process parameters and scan path of the body are as follows: beam Density I b At 35mA, a scanning speed (electron beam running speed) V print 600mm/min, a scan pitch of 2.5mm, a wire feed speed V feed The scanning path is unidirectional at 1.8m/min, and the inter-track residence time is 20s. The physical diagram of the surface in-situ deposited pure aluminum layer is shown in figure 1, and the surface is compact, has no cracks and good formability.
(6) And after the sample is cooled to room temperature, taking out, carrying out the whole process in a vacuum environment, carrying out wire cutting after taking out to obtain the sample conforming to the size of the quartz tube, placing the cut sample in a quartz tube for tube sealing treatment, placing the tube sealing in a heat treatment furnace, and preserving the heat for 3 hours at the constant temperature of 400 ℃ to finish stress-relief annealing to obtain the high-performance TiNbMoAlSi refractory high-entropy alloy.
Detection test
Samples before and after the surface remelting treatment and before and after the surface in-situ deposition of the pure aluminum layer are cut to 6mm multiplied by 3mm by the warp, sandpaper is polished to 1500#, the surface is smooth and flat, the samples are placed in an independent corundum crucible (in order to eliminate the influence of the weight change of the crucible on the experiment in the oxidation experiment process, the crucible is calcined for 6 hours at 1200 ℃) after being cleaned and dried by ultrasound, the samples are placed in a high-temperature muffle furnace for 1000 ℃ circulation high-temperature oxidation, the heating rate is 10 ℃/min, the power supply is cut off after the heat preservation is carried out at 1000 ℃ for 6 hours, the furnace door is opened, and the samples are taken out. Repeating the above operation after the furnace is completely cooled. After each run, all samples were weighed using an electronic scale and the data recorded. And after the cyclic high-temperature oxidation test is finished, observing the section condition of the oxidized oxide layer by using a scanning electron microscope, and comparing the high-temperature oxidation resistance difference of the sample which is not subjected to surface remelting treatment and is subjected to surface remelting treatment.
FIG. 2 is a macroscopic view of a sample oxidized at 1000℃ for 6 hours before, after, and in situ deposition of a pure aluminum layer on the surface, showing that the treated scale is off-white and the untreated scale is yellow. Illustrating the early formation of TiNb in the original alloy 2 O 7 And Nb (Nb) 2 O 5 The oxide layer is inhibited due to excessive volume of such oxide generationThe swelling will cause premature cracking of the oxide layer, so the surface treatment effectively improves the adhesion of the oxide layer to the substrate. Meanwhile, due to metallurgical bonding in the deposition process, the surface of the alloy presents different oxidation rates, and oxidation in different areas is restricted, so that the oxidation resistance is effectively improved.
FIG. 3 is an XRD pattern of a TiNbMoAlSi alloy after surface remelting treatment and after in-situ deposition of a pure aluminum layer on the surface, showing that the alloy after surface remelting treatment is composed mainly of BCC solid solution and gamma- (Nb, ti) 5 Si 3 The alloy after surface deposition treatment mainly consists of BCC solid solution and beta- (Nb, ti) 5 Si 3 、γ-(Nb,Ti) 5 Si 3 、Al 5 Mo and Al 3 Ti multiphase composition.
The curve b in FIG. 4 is the oxidation kinetics curve of the refractory high-entropy alloy obtained in this example after surface remelting treatment at 1000℃for 36 hours after cyclic high-temperature oxidation, the curve a is the original (untreated) oxidation weight gain curve, and by comparison, it can be seen that the alloy weight gain after surface remelting treatment by this example is significantly reduced, the oxidation weight gain is reduced by-4.59% after 6 hours, the oxidation weight gain is reduced by-15.64% after 36 hours, and the oxidation weight gain for 36 hours is no more than 46.04mg/cm 2 . The curve c in FIG. 4 is the oxidation kinetics of the refractory high-entropy alloy obtained in this example after surface deposition treatment at 1000℃for 36 hours after cyclic high-temperature oxidation, as can be seen by comparison, the alloy obtained in this example has significantly reduced weight gain after surface deposition treatment by-71.33% after 6 hours, -20.19% after 36 hours, and no more than 43.56mg/cm for 36 hours 2 。
Fig. 5 is a microstructure of the TiNbMoAlSi alloy subjected to surface remelting in this example, and it can be seen that the sample structure after the electron beam surface remelting is significantly fine and uniform.
FIG. 6 is a view showing the structure of an oxidized section of TiNbMoAlSi alloy after cyclic high temperature oxidation for 6 hours before and after surface remelting treatment in this example, wherein the thickness of the oxidized layer is reduced from 88 μm to 63 μm. In combination with the analysis, the high-temperature oxidation resistance of the matrix alloy is obviously improved by the electron beam surface remelting treatment.
Fig. 7 is a microstructure of the TiNbMoAlSi alloy of this example after depositing a pure aluminum layer on the surface, and it can be seen that the sample after the electron beam surface deposition treatment has a fine and uniform structure and no microcrack. Meanwhile, due to the stirring action of the molten pool, the pure aluminum layer and the matrix alloy are subjected to metallurgical reaction, and a large number of equiaxed crystals formed by local chilling exist in the molten pool.
FIG. 8 is a view showing the structure of the oxidized section of TiNbMoAlSi alloy after cyclic high temperature oxidation for 6 hours before and after deposition of pure aluminum layer on the surface, wherein the thickness of the oxidized layer is reduced from the original 88 μm to 35 μm, and the thickness of the oxidized layer is remarkably reduced by-60.23%. In combination with the analysis, the high-temperature oxidation resistance of the matrix alloy is obviously improved by the treatment of depositing the pure aluminum layer on the surface of the electron beam.
In conclusion, the electron beam surface treatment method provided by the application can effectively improve the high-temperature oxidation resistance of the TiNbMoAlSi refractory high-entropy alloy. Meanwhile, the method can be suitable for surface treatment of samples with different sizes, the requirements of the shape and the size of an actual workpiece are well met, and the performance after surface treatment can meet different occasions of actual application. In addition, the density of the alloy is as low as 6g/cm 3 The effective oxidation resistance improving means in low-density matching can be better used for the aerospace field.
In the foregoing, the present application is merely preferred embodiments, which are based on different implementations of the overall concept of the application, and the protection scope of the application is not limited thereto, and any changes or substitutions easily come within the technical scope of the present application as those skilled in the art should not fall within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (10)
1. A method for improving high-temperature oxidation resistance of refractory high-entropy alloy is characterized by comprising the steps of carrying out electron beam surface remelting and electron beam fuse surface in-situ deposition of a pure aluminum layer on the refractory high-entropy alloy under a vacuum condition, and carrying out stress relief annealing after cooling.
2. The method of claim 1, wherein the electron beam surface remelting parameters: i b 20-30mA, V print The scanning distance is 1.5-2.0mm, the scanning times are 1 time, and the scanning path is unidirectional.
3. The method of claim 1, wherein the e-beam fuse surface in situ deposits pure aluminum layer parameters: i b 30-40mA, V print 500-700mm/min, scanning interval of 2.0-3.0mm, wire feeding speed V feed The scanning path is unidirectional and stays between tracks for 15-25s at 1.5-2.0 m/min.
4. The method of claim 1, wherein the annealing temperature is 350-450 ℃ for 2-4 hours.
5. The method of claim 1, wherein the refractory high-entropy alloy includes, but is not limited to, tiNbMoAlSi alloy.
6. The preparation method of the high-performance refractory high-entropy alloy is characterized by comprising the following steps of:
s1: according to TiNbMo 0.5 Al 0.225 Si x Weighing materials in atomic ratio with x less than or equal to 0.6, preparing alloy ingots by adopting non-consumable vacuum arc melting, obtaining a straight surface by linear cutting, and obtaining a pretreatment sample by grinding, polishing and cleaning;
s2: fixing the substrate and the sample on a workbench, sealing, vacuumizing, and treating the surface of the sample according to the method of any one of claims 1-5 to obtain the high-performance TiNbMoAlSi refractory high-entropy alloy.
7. The method of claim 6, wherein the vacuum is pulled in S2 to 7X 10 -2 Pa。
8. The high performance TiNbMoAlSi refractory high entropy alloy produced by the method of claim 6 or 7, wherein the pure aluminum layer of the alloy is metallurgically bonded to the substrate.
9. The high performance TiNbMoAlSi refractory high entropy alloy according to claim 8, wherein the alloy structure comprises BCC solid solution, β - (Nb, ti) 5 Si 3 、γ-(Nb,Ti) 5 Si 3 、Al 5 Mo and Al 3 Ti。
10. Use of the high performance TiNbMoAlSi refractory high entropy alloy produced by the method of claim 6 or 7 in hot end parts in aerospace applications.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310472602.6A CN116590634A (en) | 2023-04-27 | 2023-04-27 | Method for improving high-temperature oxidation resistance of refractory high-entropy alloy, high-performance refractory high-entropy alloy, and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310472602.6A CN116590634A (en) | 2023-04-27 | 2023-04-27 | Method for improving high-temperature oxidation resistance of refractory high-entropy alloy, high-performance refractory high-entropy alloy, and preparation and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116590634A true CN116590634A (en) | 2023-08-15 |
Family
ID=87607115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310472602.6A Pending CN116590634A (en) | 2023-04-27 | 2023-04-27 | Method for improving high-temperature oxidation resistance of refractory high-entropy alloy, high-performance refractory high-entropy alloy, and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116590634A (en) |
-
2023
- 2023-04-27 CN CN202310472602.6A patent/CN116590634A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Microstructure and mechanical properties of 308L stainless steel fabricated by laminar plasma additive manufacturing | |
| CN112570732B (en) | Method for reducing hot cracking sensitivity of laser additive manufacturing nickel-based high-temperature alloy | |
| Huang et al. | Arc deposition of wear resistant layer TiN on Ti6Al4V using simultaneous feeding of nitrogen and wire | |
| CN114411035B (en) | Precipitation strengthening type medium-entropy alloy suitable for laser additive manufacturing and preparation method thereof | |
| CN112095018B (en) | Method for controlling components in process of refining high-temperature alloy by electron beam | |
| CN112831698B (en) | Preparation method of aluminum alloy powder suitable for laser additive manufacturing | |
| Shulov et al. | Application of high-current pulsed electron beams for modifying the surface of gas-turbine engine blades | |
| CN106521384A (en) | Method used for improving Nb-Si based alloy oxidation resistance via electron beam remelting | |
| CN112410782A (en) | Heat treatment method for laser cladding coating material | |
| CN110846651A (en) | Ceramic-reinforced cobalt-based cladding material, coating and preparation method thereof | |
| Liu et al. | Laser cladding of Ni-based alloy on copper substrate | |
| CN114774752B (en) | High-strength high-toughness TiZrNbMoV refractory high-entropy alloy and preparation method thereof | |
| CN109536883B (en) | Method for improving high-temperature oxidation resistance of Ti-45Al-8.5Nb alloy | |
| Shuai et al. | Micro-crack formation and controlling of Inconel625 parts fabricated by selective laser melting | |
| CN113151764A (en) | Improve AlxMethod for high-temperature service performance of CoCrFeNi high-entropy alloy | |
| CN107790730B (en) | Method for preparing high-temperature oxidation-resistant coating on Nb-Si-based alloy | |
| CN116590634A (en) | Method for improving high-temperature oxidation resistance of refractory high-entropy alloy, high-performance refractory high-entropy alloy, and preparation and application thereof | |
| KR20140002010A (en) | Molybdenum material | |
| Wang et al. | Effect of Al2O3 particles on the corrosion behavior of molybdenum alloys in molten zinc | |
| Virtanen et al. | The effect of laser surface modification on the corrosion behaviour of Fe and Al base alloys | |
| CN114799216A (en) | Heat treatment method of titanium alloy | |
| CN113878263A (en) | Wire for TA15 titanium alloy additive manufacturing through electron beam fuses and preparation method | |
| CN109986061B (en) | Preparation method of multi-scale precipitated lamellar structure magnesium alloy | |
| JP2013086157A (en) | Manufacturing method for cu-ga alloy slab | |
| KR100537693B1 (en) | Fe- base heat-resistant alloy having improved the high temperature oxidation resistance and the method of making the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |