CN111945034B - BCC-structure high-entropy alloy containing boron and preparation method thereof - Google Patents
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Abstract
The invention discloses a BCC structure high-entropy alloy containing boron, which belongs to the field of high-entropy alloy materials and comprises the following components in percentage by mass: aluminum: 5-15%; zirconium: 40-60%; niobium: 20-30%; molybdenum: 5-15%; vanadium: 0.1-5%, and the balance of boron element (0.01-3.0%) and inevitable impurities; aiming at the bottleneck problems that the existing typical BCC structure refractory high-entropy alloy such as TaNbMoW, TaNbMoWV and the like contains a large amount of high-density metal elements, has high alloy density, high cost and poor room temperature plasticity and is difficult to be used as a structural material, the invention provides a novel BCC structure refractory high-entropy alloy containing boron elements and a preparation method thereof, and the BCC structure refractory high-entropy alloy with toughness and toughness is prepared; the mixing enthalpy of the boron element, Mo, Nb and Zr is-34, -54 and-71 kJ/mol respectively, the element is partially polymerized to form boride by the negative mixing enthalpy with very high absolute value, the formation of the boride can strengthen the alloy by an Orowan mechanism, and the strength of the alloy is improved.
Description
Technical Field
The invention belongs to the field of high-entropy alloy materials, and particularly relates to a boron-containing high-entropy alloy and a preparation method thereof.
Background
High entropy alloys are alloy materials developed over the last decades, the concept of which was first proposed by Yeh et al 2004, generally obtained by melting a mixture of 4-13 different alloy elements, each of which generally accounts for about 5% -35%. High entropy alloys, also known as multi-component solid solution alloys, have microstructures that resemble a random disordered array of liquid or amorphous atoms. However, the multi-element mixing of the high-entropy alloy forms high mixing entropy (delta Smix) so that the high-entropy alloy becomes a thermodynamic stable phase (delta G < 0), which is the biggest difference between the high-entropy alloy and amorphous alloy, namely, the high-entropy effect formed by the multi-element alloy elements causes the stability of a high-temperature phase structure. The high-entropy alloy has four properties which are not possessed by the conventional alloy, namely a high-entropy effect on thermodynamics, a lattice distortion characteristic on a structure, a delayed effect on diffusion and a cocktail effect on performance. These four properties give high entropy alloys novel microstructures and easily adjustable multi-component performance characteristics and are therefore of great interest. Research shows that the high-entropy alloy may have better radiation resistance, corrosion resistance, mechanical property, phase structure stability and the like than the conventional alloy. The field has attracted the attention of the scientists in the united states, japan and the like, and has made some important advances, such as the research on ion irradiation of Ni-containing multicomponent alloys by the oak ridge laboratories Zhang and Jin in the united states, the university of michigan Lu in the united states, the research on electron irradiation in situ and the like by Nagase at the university of osaka in japan, and the like.
The density of boron (B) element is low, and the density level of the alloy can be obviously reduced by adding the boron (B) element into the high-entropy alloy. Meanwhile, boron is a non-metallic element and is easy to combine with other elements to form a second phase, for example, the mixing enthalpies of B element, Co, Cr, Fe and Ni are respectively-24, -31, -26 and-24 kJ/mol, the element is partially polymerized to form boride due to the high absolute value of negative mixing enthalpies, and the strength of the alloy is improved due to the formation of the boride. In addition, the addition of the B element can perform the function of grain refinement on the material, so that the yield strength and the plasticity level of the high-entropy alloy can be improved at the same time. However, most of the previous researches have focused on alloy systems such as FeCoNiCrMn with an FCC structure, and the application of the FeCoNiCrMn alloy system to refractory high-entropy alloys with a BCC structure is rarely reported. Therefore, the development of the boron-containing refractory high-entropy alloy with the BCC structure is of great significance to the development and application of high-performance alloy materials.
Disclosure of Invention
Aiming at the bottleneck problems that the existing typical BCC structure refractory high-entropy alloy such as TaNbMoW, TaNbMoWV and the like contains a large amount of high-density metal elements, has high alloy density, high cost and poor room temperature plasticity and is difficult to be applied as a structural material, the invention provides the BCC structure refractory high-entropy alloy containing boron elements and the preparation method thereof, and the BCC structure refractory high-entropy alloy with toughness and toughness is prepared.
The BCC structure refractory high-entropy Al-Zr-Nb-Mo-V-B alloy containing boron elements comprises the following components in percentage by mass: aluminum: 5-15%; zirconium: 40-60%; niobium: 20-30%; molybdenum: 5-15%; vanadium: 0.1 to 5%, and the balance of boron element (0.01 to 3.0%) and inevitable impurities.
Further optimization and improvement, the alloy comprises the following components in percentage by mass: aluminum: 5-7%; zirconium: 40-50%; niobium: 20-30%; molybdenum: 5-10%; vanadium: 0.1 to 2.8%, and the balance of boron element (0.01 to 0.2%) and inevitable impurities.
Further optimization and improvement, the alloy comprises the following components in percentage by mass: aluminum: 7 percent; zirconium: 50 percent; niobium: 30 percent; molybdenum: 10 percent; vanadium: 2.8 percent, and the balance of boron element (0.2 percent) and inevitable impurities.
Further optimization and improvement, the alloy comprises the following components in percentage by mass: aluminum: 5-15%; zirconium: 40-60%; niobium: 20-30%; molybdenum: 5 to 14.89 percent; vanadium: 0.1 to 5%, and the balance of boron element (0.01 to 3.0%) and inevitable impurities.
Further optimization and improvement, the alloy comprises the following components in percentage by mass: aluminum: 5 percent; zirconium: 60 percent; niobium: 20 percent; molybdenum: 14.89 percent; vanadium: 0.1%, and the balance of boron (0.01%) and inevitable impurities.
Further optimization and improvement, the alloy comprises the following components in percentage by mass: aluminum: 5-15%; zirconium: 40-60%; niobium: 20-22%; molybdenum: 5-15%; vanadium: 0.1 to 5%, and the balance of boron element (0.01 to 3.0%) and inevitable impurities.
Further optimization and improvement, the alloy comprises the following components in percentage by mass: aluminum: 15 percent; zirconium: 40 percent; niobium: 22 percent; molybdenum: 15 percent; vanadium: 5 percent, and the balance of boron element (3.0 percent) and inevitable impurities.
Further optimization and improvement, the alloy comprises the following components in percentage by mass: aluminum: 5-10%; zirconium: 40-52%; niobium: 20-30%; molybdenum: 5-15%; vanadium: 0.1 to 1.5%, and the balance of boron element (0.01 to 1.5%) and inevitable impurities.
Further optimization and improvement, the alloy comprises the following components in percentage by mass: aluminum: 5-10%; zirconium: 40-52%; niobium: 20-30%; molybdenum: 5-15%; vanadium: 0.1 to 2.0%, and the balance of boron element (0.01 to 1.0%) and inevitable impurities.
The BCC structure refractory high-entropy Al-Zr-Nb-Mo-V-B alloy containing the boron element has the following compressive yield strength: 960-1440 MPa, elongation: 3 to 35 percent.
The preparation method of the boron-containing BCC structure refractory high-entropy Al-Zr-Nb-Mo-V-B alloy specifically comprises the following steps:
(1) preparing raw materials: weighing required alloy raw materials according to the refractory high-entropy Al-Zr-Nb-Mo-V-B alloy proportion containing boron elements;
(2) arc melting: under the protection of protective gas, Al, Zr, Nb, Mo, V and B powder are rapidly heated and melted, and in order to avoid the B powder from being blown away in the process of vacuumizing, the powder is coated by an Al foil; in order to obtain alloy ingots with uniform components, all samples are repeatedly smelted for five times, and the samples are turned over after each smelting. In order to avoid that the structure and the performance of the sample are possibly influenced to a certain extent due to the difference of smelting time and smelting current, the current is directly closed after all alloy elements are completely melted into liquid state in each smelting of the sample and the smelting is kept for 1 min. Ensure that the surface of all the samples after melting remains bright, i.e. no significant oxidation of the alloy occurs during the melting preparation.
Has the advantages that:
the boron-containing refractory high-entropy Al-Zr-Nb-Mo-V-B alloy provided by the invention is a tough and high-entropy alloy containing trace boron; the addition of boron obviously improves the strength and plasticity of the new high-entropy alloy. Firstly, boron has the function of grain refinement, and can refine the initial structure, so that the initial structure is more uniform. Secondly, the mixing enthalpy of the boron element, Mo, Nb and Zr is respectively-34, -54 and-71 kJ/mol, the element is partially polymerized to form boride by the negative mixing enthalpy with very high absolute value, the formation of the boride can strengthen the alloy by an Orowan mechanism, and the strength of the alloy is improved.
Detailed Description
The present invention will be described in further detail in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On the contrary, the invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details. The present invention will be further described with reference to the following embodiments.
Example 1
The refractory high-entropy Al-Zr-Nb-Mo-V-B alloy containing boron elements comprises the following specific alloy components: 7 at.% of Al, 50% of Zr, 30% of Nb, 10% of Mo, 2.8% of V, 0.2% of B, and the balance of inevitable impurity elements.
The preparation method of the boron-containing refractory high-entropy Al-Zr-Nb-Mo-V-B alloy comprises the following steps:
(1) preparing raw materials: weighing required alloy raw materials according to the refractory high-entropy Al-Zr-Nb-Mo-V-B alloy proportion containing boron elements, wherein the specific alloy components are as follows: 7 at.% Al, 50% Zr, 30% Nb, 10% Mo, 2.8% V, 0.2% B;
(2) arc melting: under the protection of protective gas, Al, Zr, Nb, Mo, V and B powder are rapidly heated and melted; in order to obtain alloy ingots with uniform components, all samples are repeatedly smelted for five times, and the samples are turned over after each smelting. In order to avoid that the structure and the performance of the sample are possibly influenced to a certain extent due to the difference of smelting time and smelting current, the current is directly closed after all alloy elements are completely melted into liquid state in each smelting of the sample and the smelting is kept for 1 min.
The mechanical property test of the boron-containing refractory high-entropy Al-Zr-Nb-Mo-V-B alloy ingot prepared by the embodiment shows that: the compressive yield strength is 1070 MPa, the plasticity is 35%, and good strength and plasticity matching characteristics are shown.
Example 2
The refractory high-entropy Al-Zr-Nb-Mo-V-B alloy containing boron elements comprises the following specific alloy components: 5 at.% of Al, 60% of Zr, 20% of Nb, 14.89% of Mo, 0.1% of V, 0.01% of B, and the balance of inevitable impurity elements.
The preparation method of the boron-containing refractory high-entropy Al-Zr-Nb-Mo-V-B alloy comprises the following steps:
(1) preparing raw materials: weighing required alloy raw materials according to the refractory high-entropy Al-Zr-Nb-Mo-V-B alloy proportion containing boron elements, wherein the specific alloy components are as follows: 5 at.% Al, 60% Zr, 20% Nb, 14.89% Mo, 0.1% V, 0.01% B;
(2) arc melting: under the protection of protective gas, Al, Zr, Nb, Mo, V and B powder are rapidly heated and melted; in order to obtain alloy ingots with uniform components, all samples are repeatedly smelted for five times, and the samples are turned over after each smelting. In order to avoid that the structure and the performance of the sample are possibly influenced to a certain extent due to the difference of smelting time and smelting current, the current is directly closed after all alloy elements are completely melted into liquid state in each smelting of the sample and the smelting is kept for 1 min.
The mechanical property test of the boron-containing refractory high-entropy Al-Zr-Nb-Mo-V-B alloy ingot prepared by the embodiment shows that: the compressive yield strength is 960 MPa, and the plasticity is 17%.
Example 3
The refractory high-entropy Al-Zr-Nb-Mo-V-B alloy containing boron elements comprises the following specific alloy components: 15 at.% of Al, 40% of Zr, 22% of Nb, 15% of Mo, 5% of V, 3% of B, and the balance of inevitable impurity elements.
The preparation method of the boron-containing refractory high-entropy Al-Zr-Nb-Mo-V-B alloy comprises the following steps:
(1) preparing raw materials: weighing required alloy raw materials according to the refractory high-entropy Al-Zr-Nb-Mo-V-B alloy proportion containing boron elements, wherein the specific alloy components are as follows: 15 at.% Al, 40% Zr, 22% Nb, 15% Mo, 5% V, 3% B;
(2) arc melting: under the protection of protective gas, Al, Zr, Nb, Mo, V and B powder are rapidly heated and melted; in order to obtain alloy ingots with uniform components, all samples are repeatedly smelted for five times, and the samples are turned over after each smelting. In order to avoid that the structure and the performance of the sample are possibly influenced to a certain extent due to the difference of smelting time and smelting current, the current is directly closed after all alloy elements are completely melted into liquid state in each smelting of the sample and the smelting is kept for 1 min.
The mechanical property test of the boron-containing refractory high-entropy Al-Zr-Nb-Mo-V-B alloy ingot prepared by the embodiment shows that: the compressive yield strength is 1440 MPa, the plasticity is-2%, and the extremely high yield strength level is shown.
Example 4
The refractory high-entropy Al-Zr-Nb-Mo-V-B alloy containing boron elements comprises the following specific alloy components: 10 at.% of Al, 52% of Zr, 30% of Nb, 5% of Mo, 1.5% of V, 1.5% of B, and the balance of inevitable impurity elements.
The preparation method of the boron-containing refractory high-entropy Al-Zr-Nb-Mo-V-B alloy comprises the following steps:
(1) preparing raw materials: weighing required alloy raw materials according to the refractory high-entropy Al-Zr-Nb-Mo-V-B alloy proportion containing boron elements, wherein the specific alloy components are as follows: 10 at.% Al, 52% Zr, 30% Nb, 5% Mo, 1.5% V, 1.5% B;
(2) arc melting: under the protection of protective gas, Al, Zr, Nb, Mo, V and B powder are rapidly heated and melted; in order to obtain alloy ingots with uniform components, all samples are repeatedly smelted for five times, and the samples are turned over after each smelting. In order to avoid that the structure and the performance of the sample are possibly influenced to a certain extent due to the difference of smelting time and smelting current, the current is directly closed after all alloy elements are completely melted into liquid state in each smelting of the sample and the smelting is kept for 1 min.
The mechanical property test of the boron-containing refractory high-entropy Al-Zr-Nb-Mo-V-B alloy ingot prepared by the embodiment shows that: the compressive yield strength is 1130 MPa, the plasticity is-21%, and the extremely high yield strength level is shown.
Example 5
The refractory high-entropy Al-Zr-Nb-Mo-V-B alloy containing boron elements comprises the following specific alloy components: 10 at.% of Al, 52% of Zr, 20% of Nb, 15% of Mo, 2% of V, 1.0% of B, and the balance of inevitable impurity elements.
The preparation method of the boron-containing refractory high-entropy Al-Zr-Nb-Mo-V-B alloy comprises the following steps:
(1) preparing raw materials: weighing required alloy raw materials according to the refractory high-entropy Al-Zr-Nb-Mo-V-B alloy proportion containing boron elements, wherein the specific alloy components are as follows: 10 at.% Al, 52% Zr, 20% Nb, 15% Mo, 2% V, 1.0% B;
(2) arc melting: under the protection of protective gas, Al, Zr, Nb, Mo, V and B powder are rapidly heated and melted; in order to obtain alloy ingots with uniform components, all samples are repeatedly smelted for five times, and the samples are turned over after each smelting. In order to avoid that the structure and the performance of the sample are possibly influenced to a certain extent due to the difference of smelting time and smelting current, the current is directly closed after all alloy elements are completely melted into liquid state in each smelting of the sample and the smelting is kept for 1 min.
The mechanical property test of the boron-containing refractory high-entropy Al-Zr-Nb-Mo-V-B alloy ingot prepared by the embodiment shows that: the compressive yield strength is 1260 MPa, the plasticity is 23%, and an extremely high yield strength level is shown.
Compared with the existing material, the boron-containing BCC structure refractory high-entropy Al-Zr-Nb-Mo-V-B alloy and the preparation method thereof provided by the invention have the following advantages:
1. under the condition of trace boron alloying, the yield strength of the refractory high-entropy Al-Zr-Nb-Mo-V-B alloy is improved to maximum 1440 MPa from 960 MPa of the alloy with the content of 0.01B, and the improvement amplitude is 50 percent;
2. under the condition of trace boron element alloying (to 0.2 at.%), Al7-Zr50-Nb30-Mo10-V2.8-B0.2 as-cast high-entropy alloy shows excellent strength and plastic matching characteristics, and compressive yield strength: 1070 MPa, plasticity: 35 percent, which is superior to most of refractory high-entropy alloys developed at present;
3. under the condition of low boron alloying (1.0-1.5 at.%), the Al10-Zr52-Nb20-Mo15-V2.0-B1.0 and Al10-Zr52-Nb30-Mo5-V1.5-B1.5 as-cast high-entropy alloys all show higher strength and excellent plasticity level, and compressive yield strength: 1130-1260 MPa, plasticity: 21-23% and has great engineering application value.
Claims (1)
1. A preparation method of BCC structure high-entropy alloy containing boron elements is characterized by comprising the following steps: the components by mass percent are as follows: aluminum: 7 percent; zirconium: 50 percent; niobium: 30 percent; molybdenum: 10 percent; vanadium: 2.8 percent, the balance being 0.2 percent of boron element and inevitable impurities;
the preparation method of the high-entropy alloy comprises the following steps:
(1) preparing raw materials: weighing required alloy raw materials according to the refractory high-entropy Al-Zr-Nb-Mo-V-B alloy proportion containing boron elements;
(2) arc melting:
under the protection of protective gas, Al, Zr, Nb, Mo, V and B powder are rapidly heated and melted, and in order to avoid the B powder from being blown away in the process of vacuumizing, the powder is coated by an Al foil; in order to obtain alloy ingots with uniform components, all samples are repeatedly smelted for five times, and the samples are turned over after each smelting; in order to avoid the influence on the structure and the performance of the sample caused by the difference of smelting time and smelting current, after all alloy elements are completely melted into liquid state in each smelting of the sample, the current is directly closed after the smelting is kept for 1 min; ensuring that the surfaces of all samples after smelting are kept bright, namely, the alloy is not obviously oxidized in the smelting preparation process;
the compressive yield strength of the high-entropy alloy is 1070 MPa, and the plasticity is 35%.
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| US20170314097A1 (en) * | 2016-05-02 | 2017-11-02 | Korea Advanced Institute Of Science And Technology | High-strength and ultra heat-resistant high entropy alloy (hea) matrix composites and method of preparing the same |
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| KR101884442B1 (en) * | 2017-02-10 | 2018-08-01 | 서울대학교산학협력단 | High entropy alloy overcoming strength-ductility trade-off |
| CN110306094A (en) * | 2018-03-20 | 2019-10-08 | 斯沃奇集团研究和开发有限公司 | High-entropy alloy for external module |
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| CN110093546A (en) * | 2019-04-01 | 2019-08-06 | 昆明理工大学 | A kind of AlFeMoNbZr core involucrum high entropy alloy material and preparation method thereof |
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