CN111101045A - High-entropy alloy material and preparation method thereof - Google Patents
High-entropy alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of preparation of high-entropy alloy materials, and relates to a preparation method of a high-entropy alloy material, which comprises the following steps: (1) preparing a reactant: with Cr2O3、MnO2、Fe2O3、Co3O4NiO, CuO powder and Al powder are used as raw materials, and the raw materials are uniformly mixed to prepare a reactant; wherein, the mol ratio among the powder raw materials in the reactant is as follows: al, Cr2O3:MnO2:Fe2O3:Co2O3NiO, CuO, 11.34:1:2:1:1:2: 2; (2) reaction synthesis in a pressure vessel: placing the reactant in pressure container equipment, filling inert gas, igniting and inducing the reactant to react; and after the reaction is finished, obtaining two layers of naturally separated products, and stripping the upper layer of products to obtain the high-entropy alloy material. The preparation method realizes the rapid preparation of the high-entropy alloy by reasonably selecting the components of the combustion synthesis reaction and the atmosphere pressureAnd (4) preparing.
Description
Technical Field
The invention relates to the technical field of preparation of multi-principal-element high-entropy alloy materials, in particular to a CrMnFeCoNiCu high-entropy alloy and a preparation method thereof.
Technical Field
The high-entropy alloy generally contains 5 or more elements, the content of each element is within the range of 5-35%, and the atomic percentage content of all the constituent elements is basically equivalent. The high entropy effect caused by multiple elements effectively inhibits the appearance of intermetallic compounds, effectively reduces the brittleness of the alloy caused by multiple main elements, generally forms a simple face-centered or body-centered cubic structure, and is easy to obtain nano-structure materials.
The traditional preparation process of the high-entropy alloy generally adopts a heating melting method or an electrochemical deposition method for preparation, but the preparation method has higher selectivity on selected components, expensive equipment, longer preparation time and high energy consumption. The preparation is also attempted by adopting a combustion synthesis technology, but the general combustion synthesis is prepared by adopting an aluminothermic system, the reaction temperature is generally more than 3000K, when Co, Mn and other elements with lower boiling points exist in the system, steam volatilization and even melt splashing easily occur to cause component loss, the compactness of the cast ingot is poor, and the defects of air holes, slag inclusion and the like exist.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of CrMnFeCoNiCu high-entropy alloy, which is based on thermite reaction, wherein the reduction of alloy elements and the melting of alloy are realized by utilizing the thermite reaction of oxide powder corresponding to the alloy elements and Al powder, and meanwhile, the generated CrMnFeCoNiCu alloy melt and Al powder are used as raw materials2O3The difference of the density and the surface tension between the ceramic melts can quickly realize the CrMnFeCoNiCu metal-Al2O3Separating and densifying the ceramic melt, and cooling to obtain the CrMnFeCoNiCu high-entropy alloy material.
In one aspect, the invention provides a preparation method of a high-entropy alloy, which comprises the following steps:
(1) preparation of the reactants
With Cr2O3、MnO2、Fe2O3、Co3O4NiO, CuO powder and Al powder are used as raw materials, and the raw materials are uniformly mixed to prepare a reactant; wherein, the mol ratio among the powder raw materials in the reactant is as follows:
Al:Cr2O3:MnO2:Fe2O3:Co2O3:NiO:CuO＝11.34:1:2:1:1:2:2。
(2) reaction synthesis in pressure vessel
Putting the reactant into pressure container equipment, filling inert gas, igniting and inducing the reactant to react;
and after the reaction is finished, obtaining two layers of products which are naturally separated, and stripping the upper layer of products to obtain the CrMnFeCoNiCu high-entropy alloy material.
Alternatively, according to the preparation method of the high-entropy alloy, the inert gas is Ar gas.
Optionally, according to the preparation method of the high-entropy alloy, in the pressure vessel, the pressure of the Ar gas is 0.2 to 2.0 MPa.
Alternatively, according to the preparation method of the high-entropy alloy, the reaction of the reactant is induced in an ignition mode of electric heating.
Optionally, according to the preparation method of the high-entropy alloy, the grain size of the Al powder is 5-45 μm.
On the other hand, the invention also provides the high-entropy alloy prepared by the preparation method.
The invention has the beneficial effects that: the preparation method of the high-entropy alloy combines a combustion synthesis technology and an air pressure auxiliary technology, has no pollution in the preparation process, does not need additional energy to heat in the whole reaction process except the reaction initiated by a small amount of energy at the beginning, and belongs to the preparation technology of low-energy-consumption materials.
The auxiliary air pressure used in the preparation method is generally between 0.2 and 2MPa, and the high-density CrMnFeCoNiCu high-entropy alloy material can be quickly prepared.
The CrMnFeCoNiCu high-entropy alloy material prepared by the invention has a typical nano structure, has a single face-centered cubic structure as a phase, and has no obvious defects of pores, slag inclusion, cracks and the like; wherein the content of each element is more than or equal to 5 percent and less than or equal to 35 percent.
Drawings
FIG. 1 is an XRD phase analysis diagram of a CrMnFeCoNiCu high-entropy alloy prepared by the preparation method of the invention;
FIG. 2 is an energy spectrum analysis diagram of the CrMnFeCoNiCu high-entropy alloy prepared by the preparation method of the invention.
Detailed Description
In order to better understand the present invention, the following further illustrate the contents of the present invention with reference to specific examples, but the present invention should not be construed as being limited to the following examples only.
In one aspect, the invention provides a preparation method of a high-entropy alloy, which comprises the following steps:
(1) preparation of the reactants
With Cr2O3、MnO2、Fe2O3、Co3O4NiO, CuO powder and Al powder are used as raw materials, and the raw materials are uniformly mixed to prepare a reactant; wherein, the mol ratio among the powder raw materials in the reactant is as follows:
Al:Cr2O3:MnO2:Fe2O3:Co2O3:NiO:CuO＝11.34:1:2:1:1:2:2。
(2) reaction synthesis in pressure vessel
Putting the reactant into pressure container equipment, filling inert gas, igniting and inducing the reactant to react;
after the reaction is finished, two layers of products (the upper layer is Al) which are naturally separated are obtained2O3A ceramic layer which is mainly used, and a CrMnFeCoNiCu high-entropy alloy ingot is arranged at the lower layer), and an upper-layer product is stripped to obtain the CrMnFeCoNiCu high-entropy alloy material.
In the above preparation method, the particle size of the Al powder is generally 5 to 45. The inert gas filled into the pressure container is Ar gas, and the pressure of the Ar gas is preferably 0.2-2.0MPa, so that the high-density CrMnFeCoNiCu high-entropy alloy material can be quickly prepared. Preferably, the reaction of the reactants is induced by means of electrically heated ignition.
The preparation method of the high-entropy alloy combines the traditional combustion synthesis technology and the air pressure auxiliary technology, and the combustion synthesis system is placed in a higher air pressure environment for carrying out. The alloy melting process is completed by means of self heat release of combustion reaction, and the low-viscosity high-temperature metal/ceramic mixed melt generated by the reaction is rapidly separated under higher air pressure, so that an alloy ingot is finally obtained. However, since the low boiling point elements such as Co and Mn are present in the system, in order to obtain a high purity and high density alloy ingot, it is necessary to suppress the volatilization of the above elements, and the boiling point of the substance is generally increased with the increase in the ambient pressure because of the ambient pressure. Synthesized in a high-pressure environment, the volatilization of Co and Mn components with low boiling points is inhibited, and pores and slag inclusion in the alloy cast ingot are reduced or eliminated. The process realizes the rapid preparation of the CrMnFeCoNiCu high-entropy alloy by reasonably selecting combustion synthesis reaction components and atmosphere pressure.
The high-entropy alloy obtained by the preparation method provided by the invention consists of six elements of Cr, Mn, Fe, Co, Ni and Cu, and the crystal structure of the high-entropy alloy is a face-centered cubic structure. Fig. 1 and fig. 2 respectively show an XRD phase analysis chart and an energy spectrum analysis chart of the CrMnFeCoNiCu high-entropy alloy prepared by the preparation method of the present invention. As can be seen from the graphs in FIGS. 1 and 2, the molar content of each element in the alloy is more than or equal to 5% and less than or equal to 35%, the phase composition is a single face-centered cubic structure, the grain size in the microstructure is 5-500 nm, and the alloy has obvious nanometer size characteristics and belongs to nanometer alloys.
In order to specifically describe the present invention, the applicant explains the high-entropy alloy of the present application and the preparation method thereof by the following examples. It should be understood that the following specific examples are illustrative of specific implementations of the invention only and are not to be construed as limiting the scope of the invention.
Example 1
With Al, Cr2O3、MnO2、Fe2O3、Co3O4NiO and CuO powder are used as raw materials, and the molar ratio of the raw materials of the powder is as follows: al, Cr2O3:MnO2:Fe2O3:Co2O3NiO, CuO, is 11.34:1:2:1:1:2: 2. Fully and uniformly mixing the powder raw materials and drying to obtain a reactant, putting the prepared powder into a graphite crucible, putting the crucible into a pressure container, introducing Ar gas with the pressure of 0.5MPa into the pressure container, and initiating a synthesis reaction in an electric ignition mode; after the reaction is finished, a product which is naturally divided into two layers can be obtained, wherein the upper layer is made of Al2O3Mainly ceramic, the lower layer is made of CrMnFeCoNiCu high-entropy alloy material, and the ceramic is peeledSeparating the aluminum oxide on the upper layer to obtain the CrMnFeCoNiCu high-entropy alloy material. The obtained high-entropy alloy material is composed of Cr, Mn, Fe, Co, Ni and Cu elements, and the content of each element is more than or equal to 5% and less than or equal to 35%; the grain size of the alloy is 50-300 nm and the alloy density is 7.53g/cm through observation of a scanning electron microscope, X-ray diffraction analysis and transmission electron microscope analysis3。
Example 2
With Al, Cr2O3、MnO2、Fe2O3、Co3O4NiO and CuO powder are used as raw materials, and the molar ratio of the raw materials of the powder is as follows: al, Cr2O3:MnO2:Fe2O3:Co2O3NiO, CuO, is 11.34:1:2:1:1:2: 2. The powder raw materials are fully and uniformly mixed and dried to obtain a reactant, the prepared powder is put into a graphite crucible, the crucible is placed in a pressure container, 1.5MPa of Ar gas is introduced into the pressure container, and a synthesis reaction is initiated in an electric ignition mode; after the reaction is finished, a product which is naturally divided into two layers can be obtained, wherein the upper layer is made of Al2O3Mainly ceramic, the lower layer is made of CrMnFeCoNiCu high-entropy alloy material, and the aluminum oxide on the upper layer is stripped to obtain the CrMnFeCoNiCu high-entropy alloy material. The obtained high-entropy alloy material is composed of Cr, Mn, Fe, Co, Ni and Cu elements, and the content of each element is more than or equal to 5% and less than or equal to 35%; through observation by a scanning electron microscope, X-ray diffraction analysis and transmission electron microscope analysis, the grain size of the alloy is 50-300 nm, and the alloy density is 7.81g/cm3。
Example 3
With Al, Cr2O3、MnO2、Fe2O3、Co3O4NiO and CuO powder are used as raw materials, and the molar ratio of the raw materials of the powder is as follows: al, Cr2O3:MnO2:Fe2O3:Co2O3NiO, CuO, is 11.34:1:2:1:1:2: 2. Mixing the above powder materials, drying to obtain reactant, placing the prepared powder into graphite crucible, and placing the crucible under pressureIn the container, 2.0MPa of Ar gas is introduced into the pressure container, and the synthesis reaction is initiated in an electric ignition mode; after the reaction is finished, a product which is naturally divided into two layers can be obtained, wherein the upper layer is made of Al2O3Mainly ceramic, the lower layer is made of CrMnFeCoNiCu high-entropy alloy material, and the aluminum oxide on the upper layer is stripped to obtain the CrMnFeCoNiCu high-entropy alloy material. The obtained high-entropy alloy material is composed of Cr, Mn, Fe, Co, Ni and Cu elements, and the content of each element is more than or equal to 5% and less than or equal to 35%; through observation by a scanning electron microscope, X-ray diffraction analysis and transmission electron microscope analysis, the grain size of the alloy is 50-300 nm, and the alloy density is 8.07g/cm3。
Claims (6)
1. A preparation method of a high-entropy alloy material comprises the following steps:
(1) preparation of the reactants
With Cr2O3、MnO2、Fe2O3、Co3O4NiO, CuO powder and Al powder are used as raw materials, and the raw materials are uniformly mixed to prepare a reactant; wherein, the mol ratio among the powder raw materials in the reactant is as follows:
Al:Cr2O3:MnO2:Fe2O3:Co2O3:NiO:CuO＝11.34:1:2:1:1:2:2；
(2) reaction synthesis in pressure vessel
Putting the reactant into pressure container equipment, filling inert gas, igniting and inducing the reactant to react;
and after the reaction is finished, obtaining two layers of products which are naturally separated, and stripping the upper layer of products to obtain the CrMnFeCoNiCu high-entropy alloy material.
2. The method of claim 1, wherein: the inert gas is Ar gas.
3. The method of claim 2, wherein: in the pressure container, the pressure of Ar gas is 0.2-2.0 MPa.
4. The method of claim 1, wherein: the reaction of the reactants is induced by ignition by electrical heating.
5. The production method according to any one of claims 1 to 4, characterized in that: the particle size of the Al powder is 5-45 mu m.
6. A high entropy alloy characterized by: the high-entropy alloy is prepared by the preparation method of any one of claims 1 to 5.
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