CN111304512A - Medium-high entropy alloy material, preparation method and application thereof - Google Patents
Medium-high entropy alloy material, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a medium-high entropy alloy material, which is a solid solution alloy with a single-phase body-centered cubic structure, and at least comprises Mo, Ta and Ti elements. Also provides a preparation method and application thereof. The refractory medium-high entropy alloy disclosed by the invention has good thermal stability, good high-temperature oxidation resistance, quite high hardness and wear resistance and good solid solution capability. The invention adopts an innovative preparation method of powder briquetting and electric arc melting, solves the problems that the melting point difference among alloy components is overlarge and the common electric arc melting is difficult to uniformly melt the block raw material, and provides a simple and easy preparation method for the alloy material with large melting point difference.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a medium-high entropy alloy material, and a preparation method and application thereof.
Background
Superalloys are a class of metallic materials that operate for extended periods of time in high temperature environments (at least above 600 c). The high-temperature alloy needs to have excellent high-temperature strength, oxidation resistance, hot corrosion resistance and the like, and has important application in the fields of aerospace, energy and the like.
The nickel-based high-temperature alloy is widely applied in the field of aerospace, and about 40 percent of the high-temperature alloy is the nickel-based high-temperature alloy. The nickel-based high-temperature alloy mainly comprises Ni, Co, Cr, W, Mo, Re, Ru, Al, Ta, Ti and other elements, the matrix is nickel element with the content of more than 60 percent, the main working temperature range is 950-1100 ℃, and the nickel-based high-temperature alloy has higher strength, stronger oxidation resistance and corrosion resistance when being used in service in the temperature range. However, most nickel-based superalloys have a liquid phase formation temperature around 1400 ℃ limited by the melting point of nickel, and therefore, the operating temperature of non-single crystal nickel-based superalloys generally cannot exceed 1100 ℃, and 1200 ℃ is the service temperature limit of single crystal nickel-based superalloys.
In order to increase the alloy use temperature, the development of high temperature alloys based on refractory alloys is required. Among them, the niobium alloy with higher price has been verified and acknowledged in various countries after about 20 years of development, but some problems still need to be overcome, and the method is mainly divided into two aspects: 1, the oxidation resistance is poor, and the niobium alloy is difficult to avoid catastrophic oxidation behavior at high temperature; 2, compared with some high-strength nickel-based high-temperature alloys, the niobium alloy has the advantages of insufficient strength and creep resistance below 1100 ℃.
Therefore, the field of materials science is still searching for new superalloy systems. The medium-high entropy alloy is a novel alloy material which has attracted much attention in the field of materials in recent years. The traditional alloy is usually formed by taking a metal element as a basic component and mixing a small amount of other components, the mixing entropy of the traditional alloy is less than 0.693R (R is a gas constant R which is 8.314J/mol. K), and the traditional alloy belongs to a low-entropy alloy. When the proportion of the components incorporated in the conventional alloy is increased, the basic structure of the alloy is easily broken, and brittle intermetallic compounds and the like appear, so that the proportion of the components of the conventional alloy is limited. The medium-entropy alloy is formed by 2-4 elements in an equimolar or near-equimolar ratio to form a solid solution alloy, and the mixing entropy of the medium-entropy alloy is 0.693R-1.61R. The high-entropy alloy comprises 5 or more elements which form a solid solution alloy with an equimolar or near equimolar ratio, and the mixing entropy of the elements is above 1.61R. The high entropy of mixing can effectively reduce the Gibbs free energy of the system, thereby making the alloy system more stable. Research shows that in some alloy systems, when several different metal elements are mixed to form an alloy in a nearly equal molar ratio, a complex precipitated phase does not appear, but a single-phase solid solution is formed, so that the excellent overall performance can be maintained; and because the medium-high entropy alloy breaks through the component limitation of the traditional alloy, the medium-high entropy alloy is in the blank area of the traditional alloy development, and has wide prospect of finding new performance and new materials. Researches show that the medium-high entropy alloy has the unique properties of high entropy effect, delayed diffusion effect, lattice distortion effect, cocktail effect and the like. Due to the high entropy effect, the medium-high entropy alloy generally has good phase stability at high temperature; the nature and interaction of various elements make the medium-high entropy alloy present a complex effect, and Indian scientists firstly summarize the nature into a 'cocktail effect'. This gives the medium and high entropy alloy great advantages in terms of regulating properties: if oxidation-resistant elements such as aluminum and chromium are added into the alloy, the oxidation resistance of the alloy is improved; if a high melting point metal element is added to the alloy, the melting point and operating temperature of the alloy will increase.
The refractory medium-high entropy alloy refers to medium-high entropy alloy with main elements containing several refractory metals. The refractory medium-high entropy alloy is a novel high temperature alloy with great potential, and most of the NbMoTaW series and HfNbTaTiZr series refractory medium-high entropy alloys reported at present have good high temperature mechanical properties, but still have the defect of being not oxidation-resistant at high temperature like niobium-based high temperature alloys. The development of the oxidation-resistant refractory medium-high entropy alloy is one of the hot spots in the field of medium-high entropy alloys at present.
Disclosure of Invention
Therefore, the invention aims to overcome the defects of the conventional high-temperature medium-high entropy alloy and provide the medium-high entropy alloy capable of resisting high-temperature oxidation and the preparation method and application thereof.
Before setting forth the context of the present invention, the terms used herein are defined as follows:
the term "high entropy alloy" refers to: the entropy of the mixture of 5 or more elements in the solid solution alloy is above 1.61R.
The term "mid-entropy alloy" refers to: the entropy of mixing of the solid solution alloy formed by 2-4 elements in an equimolar or near-equimolar ratio is between 0.693R and 1.61R.
Wherein R is a gas constant, R is 8.314 J.K-1·mol-1。
In order to achieve the above object, a first aspect of the present invention provides a medium-high entropy alloy material, where the medium-high entropy alloy material is a solid solution alloy with a single-phase body-centered cubic structure, and the medium-high entropy alloy material at least includes Mo, Ta, and Ti elements; preferably, the medium-high entropy alloy material further comprises Cr and/or Al elements.
The medium-high entropy alloy material according to the first aspect of the present invention, wherein the medium-high entropy alloy material is selected from one or more of the following:
MoaTabTicwherein 30 ≤ a, b, c ≤ 40, and a + b + c ≤ 100;
MoaTabTicCrdwherein, 20 is less than or equal to a, b, c and d is less than or equal to 30, and a + b + c + d is 100;
MoaTabTicAlewherein 20 is less than or equal to a, b, c, e is less than or equal to 30, and a + b + c + e is 100;
MoaTabTicCrdAlewherein 15 ≤ a, b, c, d, e ≤ 25, and a + b + c + d + e ≤ 100;
wherein a, b, c, d and e are atomic percent.
The medium-high entropy alloy material according to the first aspect of the present invention, wherein an as-cast structure of the medium-high entropy alloy material is a dendrite.
The second aspect of the present invention provides a preparation method of the medium-high entropy alloy material described in the first aspect, and the preparation method may include the following steps:
(1) tabletting: weighing raw material simple substance powder according to atomic percentage, mixing and uniformly stirring, and tabletting the mixed powder into a powder block;
(2) smelting: and (3) smelting the powder block prepared in the step (1) in an argon atmosphere electric arc furnace with titanium adsorption to obtain an alloy ingot.
The production method according to the second aspect of the present invention, wherein in the step (1), the raw material purity of the elemental raw material powder is not less than 99.5%.
The preparation method according to the second aspect of the present invention, wherein in the step (1), the pressure of the tablet is 100 to 500MPa, preferably 200 to 400MPa, and most preferably 300 MPa; and/or
The tabletting time is 1-5 minutes, preferably 1-3 minutes, and most preferably 2 minutes.
The preparation method according to the second aspect of the present invention, wherein, in the step (2), the smelting current is 100 to 500 amperes, preferably 200 to 300 amperes, and most preferably 260 amperes; and/or the smelting step is carried out once or more times, preferably 4-5 times; the time for each melting is 15 seconds to 40 seconds, preferably 20 seconds.
The production method according to the second aspect of the present invention, wherein the method further comprises the steps of:
(3) cutting the alloy ingot obtained in the step (2);
preferably, the cutting method is wire cutting.
The third aspect of the invention provides a high-temperature-resistant oxidation-resistant material, which comprises the medium-high entropy alloy material and/or the medium-high entropy alloy material prepared according to the preparation method of the second aspect.
The fourth aspect of the invention provides application of the medium-high entropy alloy material and/or the medium-high entropy alloy material prepared by the preparation method in the first aspect in preparation of high-temperature materials, aviation materials, engine materials and/or structural materials.
The purpose of the invention is realized by the following technical scheme:
the invention provides a high-entropy alloy material resistant to high-temperature oxidation, which comprises the following components in a general formula I when chromium and aluminum are not contained:
MoaTabTic(I) wherein, in the step (A),
a. b and c are atomic percent, and the variation range is as follows: 30 is less than or equal to a, b, c is less than or equal to 40, and a + b + c is 100.
When the alloy contains chromium and no aluminum, the composition is represented by the general formula II:
MoaTabTicCrd(II) wherein 20 ≦ a, b, c, d ≦ 30, and a + b + c + d ≦ 100.
When the alloy contains aluminum and no chromium, the composition is represented by formula III:
MoaTabTicAle(III) wherein 20 ≦ a, b, c, e ≦ 30, and a + b + c + e ≦ 100.
When the alloy contains chromium and aluminum, the composition is represented by formula IV:
MoaTabTicCrdAle(iv), wherein 15 ≦ a, b, c, d, e ≦ 25, and a + b + c + d + e is 100.
The medium-high temperature high-entropy alloy is a solid solution alloy with a single-phase body-centered cubic (BCC) structure.
The invention provides a preparation method of the medium-high entropy alloy, when the alloy does not contain aluminum, the alloy components are represented by a general formula I or a general formula II, and the preparation method comprises the following steps:
1) preparing materials: the raw material used in the method is a simple substance metal powder raw material. Respectively weighing simple substance metal powder of required components according to the alloy components, mixing and uniformly stirring the simple substance metal powder, and then pressing the mixed powder into a powder block with certain strength by using a tablet press and a tabletting mold.
2) Smelting: uniformly smelting the powder mixed block obtained in the step 1) in an electric arc furnace with an argon atmosphere adsorbed by titanium to obtain an alloy ingot.
3) And cutting the alloy ingot into required sizes by using a method such as wire cutting.
The purity of Mo, Ta, Ti and Cr powder raw materials used in the step 1) is not lower than 99.5%.
When the alloy includes aluminum, the alloy composition is represented by formula III, and the method of making includes the steps of:
1) preparing materials: the raw material used in the method is a simple substance metal powder raw material. Respectively weighing simple substance metal powder of required components according to the alloy components, wherein the metal aluminum can use particle raw materials with the size within 1mm to replace powder, mixing and uniformly stirring the powder, and then pressing the mixed powder into powder blocks with certain strength by using a tablet press and a tabletting mold.
2) Smelting: uniformly smelting the powder mixed block obtained in the step 1) in an electric arc furnace with an argon atmosphere adsorbed by titanium to obtain an alloy ingot.
3) And cutting the alloy ingot into required sizes by using a method such as wire cutting.
The purity of Mo, Ta, Ti, Cr and Al powder and particle raw materials used in the step 1) is not lower than 99.5%.
Compared with the traditional high-temperature alloy material, the material of the invention has the following advantages:
1. the invention adopts an innovative preparation method of powder briquetting and electric arc melting, solves the problems that the melting point difference among alloy components is overlarge and the common electric arc melting is difficult to uniformly melt the block raw material, and provides a simple and easy preparation method for the alloy material with large melting point difference.
2. The refractory medium-high entropy alloy has good thermal stability, can keep a single-phase BCC structure within 1000 ℃, and cannot reduce the performance thereof due to phase change
3. The refractory high-entropy alloys II, III and IV have good high-temperature oxidation resistance, do not undergo severe oxidation within the temperature range of 500-1000 ℃, and have oxidation resistance far stronger than that of the existing niobium-based alloy and most commercial high-temperature alloys proved by a thermogravimetric analysis method, so that the refractory high-entropy alloys II, III and IV have strong application potential in the fields of high-temperature operation, such as aviation, engines and the like.
4. The refractory medium-high entropy alloy disclosed by the invention has quite high hardness and wear resistance. The as-cast alloy has microhardness up to 600Hv or more, Young's modulus up to 200GPa or more, good mechanical properties and potential application as a structural material.
5. The medium-high entropy alloy has good solid solution capacity and low requirement on the accuracy of component proportion, can form single-phase solid solution alloy within the component range of the first aspect of the invention, has stable performance, is convenient for practical production and application, and leaves a larger component regulation and control range for subsequent development.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 shows the X-ray diffraction spectra of high entropy refractory alloy samples in bulk according to examples 1, 4, 7, 10 of the present invention.
Fig. 2 shows scanning electron micrographs of high entropy refractory alloy samples in bulk according to examples 1, 4, 7, 10 of the present invention.
Fig. 3 shows a physical diagram of the high-entropy refractory alloy samples in the bulk of the blocks of examples 1, 4, 7 and 10 of the invention after being oxidized for 10 hours in an air atmosphere of 500-1000 degrees.
FIG. 4 shows thermogravimetric analysis curves of samples of high-entropy refractory alloys in blocks of examples 1, 4, 7 and 10 of the present invention at 1000 ℃ in an air atmosphere, with an initial temperature of room temperature and a heating rate of 20 ℃ per minute, and then held at 1000 ℃ for 5 hours.
Fig. 5 shows the X-ray diffraction patterns measured after oxidation at 600 to 1000 degrees for 10 hours for high entropy refractory alloy samples in bulk of examples 1, 4, 7, 10 of the present invention for analysis of the oxide composition on the surface of the samples.
Fig. 6 shows a scanning electron microscope cross-sectional view of an oxide layer of a high-entropy refractory alloy sample after 900 or 1000 degrees oxidation in a bulk according to examples 1, 4, 7 and 10 of the present invention and a corresponding elemental analysis diagram.
Detailed Description
The invention is further illustrated by the following specific examples, which, however, are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
This section generally describes the materials used in the testing of the present invention, as well as the testing methods. Although many materials and methods of operation are known in the art for the purpose of carrying out the invention, the invention is nevertheless described herein in as detail as possible. It will be apparent to those skilled in the art that the materials and methods of operation used in the present invention are well within the skill of the art, provided that they are not specifically illustrated.
The reagents and instrumentation used in the following examples are as follows:
reagent:
metal powder, available from alfa corporation, having a purity of over 99.9% and a particle size of 20-100 microns.
The instrument comprises the following steps:
electric arc furnace, available from physical corporation; model WK series non-consumable vacuum arc furnace;
XRD, available from bruker, model Bruke D8;
SEM, from Feina corporation, model Phenom XL;
thermogravimetric analyzer, from nai chi corporation, model nai chi STA449F 3.
Example 1
This example illustrates the preparation of a MoTaTi alloy.
Preparing the MoTaTi alloy. Accurately weighing Mo, Ta and Ti metal powder with the purity of 99.9% by using an electronic balance, wherein the total mass is 6 g, and the molar ratio is 1: 1: pouring the weighed three metal powders into the same small beaker, and stirring the three metal powders for 10 minutes by using a fine metal rod (or uniformly stirring the three metal powders in other modes) to ensure that the three metal powders are basically uniformly mixed. And pouring the mixed powder into a tabletting mold, then pressing the powder by using a tabletting machine, keeping the pressure at 300MPa for about 2 minutes, and removing the pressure. And taking the pressed raw materials out of the tabletting mold, wherein the powder raw materials are changed into cylindrical blocks and have certain strength and cannot be easily cracked or scattered. The above tabletting procedure was repeated until all the powder material was pressed into a block. And putting the prepared powder blocks into an electric arc furnace with titanium adsorption and argon atmosphere, smelting for 4-5 times by using 260 amperes of current, wherein the smelting time is 20 seconds each time, so that all the blocks are uniformly smelted to form an alloy ingot.
The X-ray diffraction (XRD) results of the alloy are shown in FIG. 1, and it can be seen that the alloy has a substantially single-phase body-centered cubic (BCC) structure and a few diffraction peaks of laves phase are present.
The scanning electron micrograph of the alloy is shown in fig. 2, from which it can be seen that the microstructure of the alloy is typical of dendrites.
The alloy was oxidized in an air atmosphere at 500 deg.C, 600 deg.C, 700 deg.C, 800 deg.C, 900 deg.C, 1000 deg.C for 10 hours, the sample size was 2.5mm 1mm, and the change in the degree of oxidation was shown in FIG. 3, from which it was seen that the sample began to show significant oxidative discoloration above 700 deg.C, the surface of the sample oxidized at 900 deg.C was covered with white oxide, and the sample oxidized at 1000 deg.C had been completely oxidized to ceramic and exhibited cracking. The alloy was subjected to thermogravimetric analysis in an air atmosphere, initially warmed from room temperature to 1000 ℃ at a rate of 20 ℃/min, and then held at 1000 ℃ for 5 hours, with the mass change as shown in FIG. 4, and the final mass increase of 21.8mg/cm2。
The XRD analysis of the oxide of the sample oxidized at high temperature is shown in figure 5, the diffraction peaks corresponding to the oxide are respectively marked, and the main component of the oxide is TiO2And MoTiTa8O25。
SEM observation of the cross section of the oxide layer of the sample oxidized at 900 ℃ for 10 hours, SEM photograph and EDS composition analysis are shown in FIG. 6, and the thickness of the oxide layer is about 400 μm.
Examples 2 to 3
This example illustrates the preparation of a MoTaTi alloy.
Preparation of a refractory Medium entropy alloy Mo according to the method of example 135Ta35Ti30And Mo30Ta30Ti40The difference is only that the raw material proportion is adjusted. The lattice structure, alloy structure, microhardness and high temperature oxidation behavior are shown in table 1.
Example 4
This example illustrates the preparation of a MoTaTiCr alloy.
Accurately weighing Mo, Ta, Ti and Cr metal powder with the purity of 99.9% by using an electronic balance, wherein the total mass is 6 g, and the molar ratio is 1: 1: 1: 1, pouring the weighed four metal powders into the same small beaker, and stirring the mixture for 10 minutes by using a fine metal rod (or uniformly stirring the mixture by other methods) to ensure that the mixture is basically uniformly mixed. And pouring the mixed powder into a tabletting mold, then pressing the powder by using a tabletting machine, keeping the pressure at 300MPa for about 2 minutes, and removing the pressure. The compacted material is removed from the tableting die where the powdered material becomes a cylindrical mass. The above tabletting procedure was repeated until all the powder material was pressed into a block. And putting the prepared powder blocks into an electric arc furnace with titanium adsorption and argon atmosphere, smelting for 4-5 times by using 260 amperes of current, wherein the smelting time is 20 seconds each time, so that all the blocks are uniformly smelted to form an alloy ingot.
The scanning electron micrograph of the alloy is shown in fig. 2, from which it can be seen that the microstructure of the alloy is typical of dendrites.
The alloy is oxidized for 10 hours at 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃ and 1000 ℃ respectively under the air atmosphere, the size of a sample is 2.5mm x 1mm, the change of the oxidation degree is shown in figure 3, the sample starts to obviously oxidize and discolor at the temperature of above 700 ℃, the temperature is increased from 700 ℃ to 1000 ℃, and the color of an oxide layer is gradually deepened. The alloy was subjected to thermogravimetric analysis in an air atmosphere, initially warmed from room temperature to 1000 ℃ at a rate of 20 ℃/min, and then held at 1000 ℃ for 5 hours, with the mass change as shown in FIG. 4, and the final mass increase of 0.93mg/cm2。
The XRD analysis of the oxide of the sample oxidized at high temperature is shown in figure 5, the diffraction peaks corresponding to the oxide are respectively marked, and the main component of the oxide is TiO2、CrTaO4And MoTiTa8O25。
SEM observation of the cross section of the oxide layer of the sample oxidized at 1000 ℃ for 10 hours, SEM photograph and EDS composition analysis are shown in FIG. 6, and the oxide layer thickness was measured to be about 5 to 15 μm.
Examples 5 to 6
This example illustrates the preparation of a MoTaTiCr alloy.
Preparation of a refractory Medium entropy alloy Mo according to the method of example 430Ta30Ti20Cr20And Mo20Ta20Ti30Cr30The difference is only that the raw material proportion is adjusted. The lattice structure, alloy structure, microhardness and high temperature oxidation behavior are shown in table 1.
Example 7
This example illustrates the preparation of a MoTaTiAl alloy.
Accurately weighing Mo, Ta and Ti metal powder with the purity of 99.9 percent and Al metal particles by using an electronic balance, wherein the total mass is 6 g, and the molar ratio is 1: 1: 1: 1, pouring the weighed metal powder and the particles into the same small beaker, and stirring the mixture for 10 minutes by using a fine metal rod (or uniformly stirring the mixture by other methods) to ensure that the mixture is basically uniformly mixed. And pouring the mixed powder and the Al metal particles into a tabletting mold, then pressing the powder by using a tabletting machine, keeping the pressure at 300MPa for about 2 minutes, and removing the pressure. The compacted material is removed from the tableting die where the powdered material becomes a cylindrical mass. The above tabletting procedure was repeated until all the powder material was pressed into a block. And putting the prepared powder blocks into an electric arc furnace with titanium adsorption and argon atmosphere, smelting for 4-5 times by using 260 amperes of current, wherein the smelting time is 20 seconds each time, so that all the blocks are uniformly smelted to form an alloy ingot.
The scanning electron micrograph and elemental analysis of the alloy are shown in fig. 2, from which it can be seen that the microstructure of the alloy is a typical dendrite.
The alloy is oxidized for 10 hours in the air atmosphere of 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃ and 1000 ℃ respectively, the size of a sample is 2.5mm 1mm, the change of the oxidation degree is shown in figure 3, the sample starts to obviously oxidize and discolor at the temperature of above 700 ℃, the temperature is increased from 700 ℃ to 900 ℃, the color of an oxidation layer is gradually deepened, and the color of the oxidation layer starts to partially turn white when the temperature is increased to 1000 ℃. The alloy was subjected to thermogravimetric analysis in an air atmosphere, initially at 20 ℃ from room temperatureThe temperature was raised to 1000 ℃ at a rate of one minute and then held at 1000 ℃ for 5 hours, the change in mass being shown in FIG. 4, with a final mass increase of 2.39mg/cm2。
The XRD analysis of the oxide of the sample oxidized at high temperature is shown in figure 5, the diffraction peaks corresponding to the oxide are respectively marked, and the main component of the oxide is TiO2、Al2O3And MoTiTa8O25。
SEM observation of the cross section of the oxide layer of the sample oxidized at 1000 ℃ for 10 hours, SEM photograph and EDS composition analysis are shown in FIG. 6, and the oxide layer thickness was measured to be about 30 to 60 μm.
Examples 8 to 9
This example illustrates the preparation of a MoTaTiAl alloy.
Preparation of a refractory Medium entropy alloy Mo according to the method of example 730Ta30Ti25Al15And Mo25Ta25Ti20Al30The difference is only that the raw material proportion is adjusted. The lattice structure, alloy structure, microhardness and high temperature oxidation behavior are shown in table 1. It is noted that example 8 shows that when the alloy component is MoaTabTicAldWhen the aluminum content is reduced from 25 percent to 15 percent, the high-temperature oxidation resistance of the aluminum alloy is greatly reduced, which shows that the change of the aluminum alloy has a remarkable influence on the performance of the aluminum alloy.
Example 10
This example illustrates the preparation of a MoTaTiCrAl alloy.
Accurately weighing Mo, Ta, Ti and Cr metal powder with the purity of 99.9 percent and Al metal particles by using an electronic balance, wherein the total mass is 6 g, and the molar ratio is 1: 1: 1: 1: 1, pouring the weighed metal powder into the same small beaker, and stirring the metal powder for 10 minutes by using a fine metal rod (or uniformly stirring the metal powder by other methods) to ensure that the metal powder is basically uniformly mixed. And pouring the mixed powder and the Al metal particles into a tabletting mold, then pressing the powder by using a tabletting machine, keeping the pressure at 300MPa for about 2 minutes, and removing the pressure. The compacted material is removed from the tableting die where the powdered material becomes a cylindrical mass. The above tabletting procedure was repeated until all the powder material was pressed into a block. And putting the prepared powder blocks into an electric arc furnace with titanium adsorption and argon atmosphere, smelting for 4-5 times by using 260 amperes of current, wherein the smelting time is 20 seconds each time, so that all the blocks are uniformly smelted to form an alloy ingot.
The scanning electron micrograph and elemental analysis of the alloy are shown in fig. 2, from which it can be seen that the microstructure of the alloy is a typical dendrite.
The alloy is oxidized for 10 hours at 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃ and 1000 ℃ respectively under the air atmosphere, the size of a sample is 2.5mm x 1mm, the change of the oxidation degree is shown in figure 3, the sample starts to obviously oxidize and discolor at the temperature of above 700 ℃, the temperature is increased from 700 ℃ to 1000 ℃, and the color of an oxide layer is gradually deepened. The alloy was subjected to thermogravimetric analysis in an air atmosphere, initially warmed from room temperature to 1000 ℃ at a rate of 20 ℃/min, and then held at 1000 ℃ for 5 hours, with the mass change as shown in FIG. 4, and the final mass increase of 1.39mg/cm2。
The XRD analysis of the oxide of the sample oxidized at high temperature is shown in figure 5, the diffraction peaks corresponding to the oxide are respectively marked, and the main component of the oxide is TiO2、Al2O3And CrTaO4。
SEM observation of the cross section of the oxide layer of the sample oxidized at 1000 ℃ for 10 hours, SEM photograph and EDS composition analysis are shown in FIG. 6, and the thickness of the oxide layer is measured to be about 10 to 20 μm.
Examples 11 to 12
This example illustrates the preparation of a MoTaTiCrAl alloy.
Refractory high-entropy alloy Mo prepared according to the method of example 1025Ta25Ti20Cr20Al10And Mo25Ta25Ti20Cr10Al20The difference is only that the raw material proportion is adjusted. The lattice structure, alloy structure, microhardness and high temperature oxidation behavior are shown in table 1.
TABLE 1 lattice structure, alloy structure, microhardness, pyro-oxidation behavior, and entropy mixing of the mid-to-high entropy alloy materials prepared in examples 1-12
Although the present invention has been described to a certain extent, it is apparent that appropriate changes in the respective conditions may be made without departing from the spirit and scope of the present invention. It is to be understood that the invention is not limited to the described embodiments, but is to be accorded the scope consistent with the claims, including equivalents of each element described.
Claims (10)
1. The medium-high entropy alloy material is characterized in that the medium-high entropy alloy material is a solid solution alloy with a single-phase body-centered cubic structure, and the medium-high entropy alloy material at least comprises Mo, Ta and Ti elements; preferably, the medium-high entropy alloy material further comprises Cr and/or Al elements.
2. The medium-high entropy alloy material according to claim 1, wherein the medium-high entropy alloy material is selected from one or more of the following:
MoaTabTicwherein 30 ≤ a, b, c ≤ 40, and a + b + c ≤ 100;
MoaTabTicCrdwherein, 20 is less than or equal to a, b, c and d is less than or equal to 30, and a + b + c + d is 100;
MoaTabTicAlewherein 20 is less than or equal to a, b, c, e is less than or equal to 30, and a + b + c + e is 100;
MoaTabTicCrdAlewherein 15 ≤ a, b, c, d, e ≤ 25, and a + b + c + d + e ≤ 100;
wherein a, b, c, d and e are atomic percent.
3. The medium-high entropy alloy material according to claim 1 or 2, wherein an as-cast structure of the medium-high entropy alloy material is a dendrite.
4. A method for producing a high entropy alloy material in accordance with any one of claims 1 to 3, characterized in that the method includes the steps of:
(1) tabletting: weighing raw material simple substance powder according to atomic percentage, mixing and uniformly stirring, and tabletting the mixed powder into a powder block;
(2) smelting: and (3) smelting the powder block prepared in the step (1) in an argon atmosphere electric arc furnace with titanium adsorption to obtain an alloy ingot.
5. The method according to claim 4, wherein in the step (1), the raw material purity of the elementary raw material powder is not lower than 99.5%.
6. The process according to claim 4 or 5, wherein in step (1), the pressure of the compressed tablet is 100 to 500MPa, preferably 200 to 400MPa, and most preferably 300 MPa; and/or
The tabletting time is 1-5 minutes, preferably 1-3 minutes, and most preferably 2 minutes.
7. The process according to any one of claims 4 to 6, wherein in step (2), the smelting current is 100 to 500 amps, preferably 200 to 300 amps, most preferably 260 amps; and/or
The smelting step is carried out once or for multiple times, preferably 4-5 times; the time for each melting is 15 seconds to 40 seconds, preferably 20 seconds.
8. The method according to any one of claims 4 to 7, characterized in that it further comprises the steps of:
(3) cutting the alloy ingot obtained in the step (2);
preferably, the cutting method is wire cutting.
9. A high-temperature-resistant oxidation-resistant material, which comprises the medium-high entropy alloy material as defined in any one of claims 1 to 3 and/or the medium-high entropy alloy material obtained by the preparation method as defined in any one of claims 4 to 8.
10. Use of the high-entropy alloy material as defined in any one of claims 1 to 3 and/or the high-entropy alloy material produced by the production method as defined in any one of claims 4 to 8 for producing high-temperature materials, aerospace materials, engine materials and/or structural materials.
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