CN115838890B - Method for improving high-temperature oxidation resistance of AlCrMoTaTi refractory high-entropy alloy through microalloying - Google Patents
Method for improving high-temperature oxidation resistance of AlCrMoTaTi refractory high-entropy alloy through microalloying Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 85
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 235000013619 trace mineral Nutrition 0.000 claims abstract description 6
- 239000011573 trace mineral Substances 0.000 claims abstract description 6
- 230000004584 weight gain Effects 0.000 claims description 16
- 235000019786 weight gain Nutrition 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 229910000714 At alloy Inorganic materials 0.000 claims description 2
- 229910000905 alloy phase Inorganic materials 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
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- 239000000463 material Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
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Abstract
The invention discloses a high-entropy alloy for improving AlCrMoTaTi refractory by microalloyingA method for high-temperature oxidation resistance belongs to the technical field of high-temperature metal materials. The method is characterized in that trace elements M are added into AlCrMoTaTi refractory high-entropy alloy, wherein M is one of Si, Y and B, the addition amount of M is less than or equal to 1, the trace addition of the element M does not change the phase composition of a primary system, but the element M can be enriched in AlCrMoTaTi refractory high-entropy alloy grain boundaries to form a filling effect, when AlCrMoTaTi refractory high-entropy is oxidized at a high temperature of 1300 ℃, the element M can diffuse through the grain boundaries and fill oxide film gaps, the stability and adhesiveness of an oxide film are improved, after 10 hours of continuous oxidation, the oxidation weight of AlCrMoTaTi refractory high-entropy is reduced by more than 3 times, and the oxidation weight is less than or equal to 2mg/cm 2 。
Description
Technical Field
The invention relates to the technical field of high-temperature metal materials, in particular to a method for improving high-temperature oxidation resistance of AlCrMoTaTi refractory high-temperature alloy by microalloying.
Background
The service temperature of the new generation of advanced military aviation aircraft hot end component with high thrust weight ratio is over 1300 ℃, the service temperature of the traditional high-temperature alloy is not satisfied, and development of high-temperature materials with excellent high-temperature mechanical properties and high-temperature oxidation resistance is needed. Refractory high-entropy alloys become potential novel high-temperature materials by virtue of the high-melting point and high-temperature strength and toughness matching characteristics, but high-temperature oxidation resistance of high-entropy alloys completely composed of refractory elements is poor, so that even if the high-entropy alloys have good high-temperature performance, the high-temperature high-entropy alloys cannot be applied at high temperature.
Therefore, since 2010, a great deal of research work is carried out on the design and optimization of the oxidation resistance of refractory high-entropy alloy by students at home and abroad, but because the high-entropy alloy system is composed of multiple elements in nearly equal atomic proportion, all elements in the system can be oxidized theoretically, which leads to difficult generation of Al by refractory high-entropy alloy 2 O 3 Such sheetsInstead, a protective oxide forms a variety of complex composite oxides which are rare in conventional alloys and whose properties are not known, which also results in difficult design and improvement of the oxidation resistance properties of refractory high-entropy alloys. Until 2019, the German B.Gorr team designed AlCrMoTaTi high entropy alloy, which was found to produce CrTaO at 1300 DEG C 4 The composite oxide has excellent properties, so that the alloy has better oxidation resistance, and the weight gain of the composite oxide is about 6mg/cm after 10 hours of continuous operation 2 Provides guidance for developing a high-temperature oxidation resistant refractory high-entropy alloy system. However, the alloy was oxidized continuously at 1300℃for 10 hours and then 6mg/cm 2 The weight gain of the alloy still has a larger lifting space, and the deep optimization can be continued, so that the oxidation resistance of the alloy is further enhanced, and the application of the alloy in a high-temperature environment is promoted.
Disclosure of Invention
Aiming at the problem that the oxidation resistance of AlCrMoTaTi refractory high-entropy alloy needs to be further improved, the invention aims to provide a method for improving the high-temperature oxidation resistance of AlCrMoTaTi refractory high-entropy alloy by microalloying, wherein trace elements M are added into the AlCrMoTaTi refractory high-entropy alloy, the addition of M is less than or equal to 1 and is one of Si, Y and B, the trace addition of M does not change the phase composition of an original system, but can be enriched at a crystal phase or a crystal boundary of the AlCrMoTaTi refractory high-entropy alloy to form a filling effect, when AlCrMoTaTi refractory high-entropy is oxidized at a high temperature of 1300 ℃, the element M can diffuse through the crystal boundary and fill an oxidation film gap to improve the stability and adhesiveness of an oxidation film, and after 10 hours of continuous oxidation, the method can reduce the oxidation of the AlCrMoTaTi refractory high-entropy by more than 3 times and increase the weight by less than or equal to 2mg/cm after continuous oxidation 2 。
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for improving high-temperature oxidation resistance of AlCrMoTaTi refractory high-entropy alloy by microalloying is characterized in that trace element M is added into an original AlCrMoTaTi refractory high-entropy alloy system to form a new refractory high-entropy alloy with a chemical expression of (AlCrMoTaTi) 100-x M x M is one of Si, Y and B, and the addition amount of M0<x is less than or equal to 1, and the content of each element is atomic percent.
The addition of the microalloying element M will be enriched in a filled manner at the alloy crystalline phase or grain boundaries without changing the original phase structure.
When AlCrMoTaTi refractory high-entropy is oxidized at 1300 ℃, the element M can diffuse through grain boundary and fill oxide film gaps, so that the stability and adhesiveness of the oxide film are improved, and after 10 hours of continuous oxidation, the method can reduce the oxidation weight gain of AlCrMoTaTi refractory high-entropy by more than 3 times, wherein the oxidation weight gain is less than or equal to 2mg/cm 2 。
The invention has the advantages and beneficial effects as follows:
1. according to the method for improving the high-temperature oxidation resistance of the AlCrMoTaTi refractory high-entropy alloy by microalloying, the added microelements M (Si, Y and B) can be enriched at alloy crystal phase or crystal boundary in a filling manner, and the original phase structure is not changed.
2. The method for improving the high-temperature oxidation resistance of the AlCrMoTaTi refractory high-entropy alloy by microalloying of the invention can obtain a novel refractory high-entropy alloy (AlCrMoTaTi) 100-x M x The method has excellent 1300 ℃ oxidation resistance, the element M can diffuse through the grain boundary and fill the gaps of the oxide film, the stability and the adhesiveness of the oxide film are increased, after 10 hours of continuous oxidation, the method can reduce the high-entropy oxidation weight gain of AlCrMoTaTi refractory by more than 3 times, and the oxidation weight gain is less than or equal to 2mg/cm 2 。
Drawings
FIG. 1 shows the result of the microalloying process according to the invention (AlCrMoTaTi) 100-x M x Room temperature microstructure of the new refractory high entropy alloy and the original alloy; wherein: (a) M is B; (b) M is Y; (c) M is Si; (d) a master alloy AlCrMoTaTi.
FIG. 2 shows the result of the microalloying process according to the invention (AlCrMoTaTi) 100-x M x Sample surface state of the new refractory high entropy alloy and the original alloy after high temperature oxidation at 1300 ℃, wherein: 1-M is B element; 2-M is Y element; 3-M is Si element; 4-base alloy.
FIG. 3 shows a micro-alloyed side according to the inventionObtained by the method (AlCrMoTaTi) 100-x M x Continuous weight gain curve of the new refractory high entropy alloy and the original alloy after 10 hours of high temperature oxidation at 1300 ℃, wherein: a-M is B element; b-M is a Y element; c-M is Si element; d-base alloy.
FIG. 4 shows the result of the microalloying process according to the invention (AlCrMoTaTi) 100-x M x And (3) a new refractory high-entropy alloy, namely an EDS map of room-temperature tissue element distribution when M is B.
FIG. 5 shows the result of the microalloying process according to the invention (AlCrMoTaTi) 100-x M x And (3) a new refractory high-entropy alloy, namely an EDS map of room-temperature tissue element distribution when M is Y.
FIG. 6 shows the result of the microalloying process according to the invention (AlCrMoTaTi) 100-x M x And (3) a new refractory high-entropy alloy, namely an EDS map of room-temperature tissue element distribution when M is Si.
FIG. 7 shows the result of the microalloying process according to the invention (AlCrMoTaTi) 100-x M x And (3) a new refractory high-entropy alloy, wherein M is an oxide film element distribution EDS map after oxidation at a high temperature of 1300 ℃ when M is B.
Detailed Description
The invention is described in detail below with reference to the drawings and examples.
The invention relates to a method for improving high-temperature oxidation resistance of AlCrMoTaTi refractory high-entropy alloy by microalloying, which is characterized in that trace element M is added into an original AlCrMoTaTi refractory high-entropy alloy system to form a new refractory high-entropy alloy chemical expression (AlCrMoTaTi) 100-x M x M is one of Si, Y and B, the addition amount x of M is less than or equal to 1, and the contents are all atomic percent. The addition of the microalloying element M will be enriched in a filled manner at the alloy crystalline phase or grain boundaries without changing the original phase structure. When AlCrMoTaTi refractory high-entropy is oxidized at 1300 ℃, the element M can diffuse through grain boundary and fill oxide film gaps, so that the stability and adhesiveness of the oxide film are improved, and after 10 hours of continuous oxidation, the method can reduce the oxidation weight gain of AlCrMoTaTi refractory high-entropy by more than 3 times, wherein the oxidation weight gain is less than or equal to 2mg/cm 2 Greatly improves the high-temperature oxidation resistance of refractory high-entropy alloy.
Example 1:
in this embodiment, the refractory high-entropy alloy has the chemical expression (AlCrMoTaTi) 100-x M x M is B, the addition amount x is less than or equal to 1, at the moment, the room temperature microstructure of the new alloy is shown as a graph (a) in fig. 1 (d), the room temperature microstructure of the original AlCrMoTaTi refractory high-entropy alloy can be obtained through comparison of the room temperature microstructure and the room temperature microstructure, the original microstructure and the phase morphology of the alloy are not changed through trace addition of B element, and the surface morphology of the new alloy obtained by the microalloying method and the surface morphology of the original AlCrMoTaTi alloy after being oxidized for 10 hours at the high temperature of 1300 ℃ is shown in fig. 2, wherein the number 1 is the new alloy after the B element is added in the embodiment, the surface of a sample is unchanged, and no obvious oxidation product is formed. The curve a in FIG. 3 is a continuous weight gain curve obtained in this example, wherein the refractory high-entropy alloy is oxidized at 1300 ℃ for 10 hours, and the curve d is an oxidized weight gain curve of the original AlCrMoTaTi alloy, and it can be seen by comparison that after the element B is added in the microalloying method in this example, the oxidized weight gain of the new alloy is reduced by 3 times and no more than 2mg/cm 2 Greatly improves the oxidation resistance of the original alloy. Fig. 4 is a graph showing EDS distribution of room temperature structural elements of the alloy after adding B element in the microalloying method of the present embodiment, it is obvious that the B element is mainly enriched and filled in the crystalline phase position, and as can be seen from fig. 7, after high temperature oxidation at 1300 ℃, the B element is also enriched in the oxide film position in a filled form, which reduces the oxide film defect, improves the adhesiveness between the oxide film and the substrate, and proves that the addition of the B element can improve the oxidation resistance of the original AlCrMoTaTi alloy.
Example 2:
in this embodiment, the refractory high-entropy alloy has the chemical expression (AlCrMoTaTi) 100-x M x M is Y, the addition amount x is less than or equal to 1, and the room temperature microstructure of the new alloy is shown in fig. 1 (b), and the comparison shows that the trace addition of the Y element does not change the original structure and phase morphology of the alloy. The macroscopic observation of the surface morphology of the oxidized sample of FIG. 2 shows that the new alloy obtained in this example has no obvious oxidation product, and the EDS distribution diagram of the room temperature organization element of the alloy of FIG. 5The spectrum shows that the Y element is mainly enriched and filled in the grain boundary position, and the continuous weight increasing curve of the oxidation for 10 hours at 1300 ℃ in the graph of FIG. 3 shows that the oxidation weight increasing of the alloy is greatly reduced compared with d (original alloy) when the b curve is that the added element provided in the embodiment is Y, and the oxidation resistance is improved.
Example 3:
in this embodiment, the refractory high-entropy alloy has the chemical expression (AlCrMoTaTi) 100-x M x M is Si, the addition amount x is less than or equal to 1, at the moment, the room temperature microstructure of the new alloy is shown in a graph (c) of fig. 1, the trace addition of Si element does not change the original structure and phase morphology of the alloy, the EDS distribution spectrum of the room temperature microstructure element of the alloy of fig. 6 shows that the Si element is mainly enriched and filled in the crystal phase position, and the macroscopic observation of the surface morphology of the oxidized sample of fig. 2 shows that the new alloy obtained in the embodiment has no obvious oxidation product. As can be seen from the continuous weight gain curve of FIG. 3, which is obtained by oxidizing at 1300 ℃ for 10 hours, the c curve, i.e. the added element proposed in the embodiment, is Si, the oxidation weight gain of the alloy is also reduced compared with d (original alloy), and the oxidation resistance is improved.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (3)
1. A method for improving high-temperature oxidation resistance of AlCrMoTaTi refractory high-entropy alloy by microalloying is characterized by comprising the following steps: the method is to add trace element M into AlCrMoTaTi refractory high-entropy alloy system to obtain a new refractory high-entropy alloy with chemical expression (AlCrMoTaTi) 100-x M x M is one of Si, Y and B, and the addition amount of M is 0<x is less than or equal to 1, and the content of each element is atomic percent.
2. The method for improving the high-temperature oxidation resistance of the AlCrMoTaTi refractory high-temperature alloy by microalloying according to claim 1, which is characterized in that: the trace element M is enriched at alloy crystal phase or crystal boundary in a filling mode after being added, so that the original high-entropy alloy phase structure is not changed.
3. The method for improving the high-temperature oxidation resistance of the AlCrMoTaTi refractory high-temperature alloy by microalloying according to claim 1, which is characterized in that: when AlCrMoTaTi refractory high-entropy alloy added with element M is oxidized at high temperature of 1300 ℃, the element M can diffuse through grain boundary and fill oxide film gaps, so that the stability and adhesiveness of the oxide film are improved, after continuous oxidation for 10 hours, the method can reduce the oxidation weight gain of AlCrMoTaTi refractory high-entropy by more than 3 times, and the oxidation weight gain is less than or equal to 2mg/cm 2 。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101842922B1 (en) * | 2016-12-26 | 2018-03-29 | 국방과학연구소 | Ti-Al BASE ALLOY CONTAINING MISCH METAL |
| KR101884442B1 (en) * | 2017-02-10 | 2018-08-01 | 서울대학교산학협력단 | High entropy alloy overcoming strength-ductility trade-off |
| CN109023002A (en) * | 2018-08-15 | 2018-12-18 | 北京理工大学 | A kind of silicon solution strengthening VNbMoTaSi high-entropy alloy and preparation method thereof |
| CN111304512A (en) * | 2020-03-30 | 2020-06-19 | 中国科学院物理研究所 | Medium-high entropy alloy material, preparation method and application thereof |
| CN113046614A (en) * | 2021-03-08 | 2021-06-29 | 西南交通大学 | NbMoHfTiZrAlSi refractory high-entropy alloy and preparation method thereof |
| CN115198158A (en) * | 2022-06-13 | 2022-10-18 | 西北工业大学 | Anti-oxidation refractory high-entropy alloy and preparation method thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101842922B1 (en) * | 2016-12-26 | 2018-03-29 | 국방과학연구소 | Ti-Al BASE ALLOY CONTAINING MISCH METAL |
| KR101884442B1 (en) * | 2017-02-10 | 2018-08-01 | 서울대학교산학협력단 | High entropy alloy overcoming strength-ductility trade-off |
| CN109023002A (en) * | 2018-08-15 | 2018-12-18 | 北京理工大学 | A kind of silicon solution strengthening VNbMoTaSi high-entropy alloy and preparation method thereof |
| CN111304512A (en) * | 2020-03-30 | 2020-06-19 | 中国科学院物理研究所 | Medium-high entropy alloy material, preparation method and application thereof |
| CN113046614A (en) * | 2021-03-08 | 2021-06-29 | 西南交通大学 | NbMoHfTiZrAlSi refractory high-entropy alloy and preparation method thereof |
| CN115198158A (en) * | 2022-06-13 | 2022-10-18 | 西北工业大学 | Anti-oxidation refractory high-entropy alloy and preparation method thereof |
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