CN111945033B - High-entropy alloy with neutron poison characteristic and preparation method thereof - Google Patents
High-entropy alloy with neutron poison characteristic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics, which belongs to the field of high-entropy alloy materials and comprises the following components in percentage by mass: aluminum: 5-15%; niobium: 20-30%; zirconium: 37-60%; molybdenum: 4.99-15%; hafnium: 1-20%, and the balance of boron and inevitable impurities; the invention provides a high-entropy alloy based on an Al-Nb-Zr-Mo-Hf-B system, and fully considers the special action of an element B, so that the structural function integration of the high-entropy alloy is realized.
Description
Technical Field
The invention belongs to the field of high-entropy alloy materials, and particularly relates to a high-entropy alloy with neutron poison characteristics and a preparation method thereof.
Background
The high-entropy alloy is a brand-new alloy design idea, and the high-entropy alloy has huge development potential due to simple phase composition and excellent comprehensive performance. Currently, most researches on high-entropy alloys are focused on the classical system of FeCoNiCrMn and the derived single-phase FCC high-entropy alloy system composed of transition group elements with equal atomic ratio or near equal atomic ratio. However, many studies show that the FCC system high-entropy alloy has the characteristic of low yield strength, and phase separation occurs after long-term aging at medium temperature, so that the structure stability is poor. On the other hand, typical BCC refractory high-entropy alloys such as tanbbow and tanbbowv contain a large amount of high-density metal elements, have high alloy density, high cost and poor room temperature plasticity, and are difficult to be applied as structural materials. Fortunately, the rich alloy components of the high-entropy alloy provide a wide space for realizing high strength and toughness and mechanical properties. Recent research shows that elements such as Zr, Ti, Hf and Al with certain content can be added into alloy systems such as Nb, Mo, Ta and W to realize excellent plasticity while maintaining high strength, and meanwhile, matching among the alloy elements shows good high entropy forming capacity.
In the aspect of thermal neutron absorption characteristics, the absorption cross section of boron to thermal neutrons is close to 750 bar, which is about 7 times of Hf and is more than 500 times of that of the traditional concrete material. That is, boron is a highly efficient thermal neutron absorber. Due to the characteristic of boron, the related products containing boron are widely applied to military fields such as military protection, nuclear weapons, nuclear industry and the like. Boron (B), generally used as a trace alloying element, boron-aluminum alloys are effective neutron shielding materials, and boron steel is used as a control rod in reactors. But also has some exploration in the strengthening and toughening of the boron-containing high-entropy alloy. For example, ChenRuizu et al, Harbin university, found that the compressive yield strength of the alloy can be increased from 178MPa to 714MPa by adding B, Y elements in the CoCrFeMnNi high-entropy alloy in a composite manner, and the increase is as much as-300%. However, the study of adding B element into the refractory high-entropy Al-Nb-Zr-Mo-Hf alloy matrix with BCC structure is rarely reported.
In addition, since other studies do not sufficiently consider the neutron poison characteristics of the B-containing high-entropy alloy, the addition amount of the B element tends to have a large randomness. Therefore, the high-entropy alloy based on the Al-Nb-Zr-Mo-Hf-B system is developed, and the special effect of the B element is fully considered, so that the high-strength and high-toughness mechanical property and the multifunctional characteristic of neutron absorption of the high-entropy alloy are realized, and the high-entropy alloy has important significance for the development and application of high-end nuclear materials.
Disclosure of Invention
The invention provides a high-entropy alloy based on an Al-Nb-Zr-Mo-Hf-B system, and fully considers the special action of an element B, so that the structural function integration of the high-entropy alloy is realized.
The Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with the neutron poison characteristic comprises the following components in percentage by mass: aluminum: 5-15%; niobium: 20-30%; zirconium: 37-60%; molybdenum: 4.99-15%; hafnium: 1-20%, and the balance of boron and inevitable impurities.
The technical scheme is further improved and optimized, and the weight ratio of aluminum: 5-15%; niobium: 20-30%; zirconium: 40-60%; molybdenum: 5-15%; hafnium: 9.8-20%, and the balance of boron and inevitable impurities.
The technical scheme is further improved and optimized, and the weight ratio of aluminum: 5 percent; niobium: 30 percent; zirconium: 40 percent; molybdenum: 15 percent; hafnium: 9.8 percent, and the balance of boron and inevitable impurities.
The technical scheme is further improved and optimized, and the weight ratio of aluminum: 5 to 14 percent; niobium: 20-30%; zirconium: 37-60%; molybdenum: 4.99-15%; hafnium: 1-20%, and the balance of boron and inevitable impurities.
The technical scheme is further improved and optimized, and the weight ratio of aluminum: 14 percent; niobium: 20 percent; zirconium: 60 percent; molybdenum: 4.99 percent; hafnium: 1% and the balance of boron and inevitable impurities.
The technical scheme is further improved and optimized, and the weight ratio of aluminum: 5-11%; niobium: 22-30%; zirconium: 40-60%; molybdenum: 5-15%; hafnium: 1-20%, and the balance of boron and inevitable impurities.
The technical scheme is further improved and optimized, and the weight ratio of aluminum: 11 percent; niobium: 22 percent; zirconium: 40 percent; molybdenum: 5 percent; hafnium: 20 percent, and the balance of boron and inevitable impurities.
The technical scheme is further improved and optimized, and the weight ratio of aluminum: 5-15%; niobium: 20-30%; zirconium: 37-60%; molybdenum: 5-15%; hafnium: 1 to 12.5 percent, and the balance of boron and inevitable impurities.
The technical scheme is further improved and optimized, and the weight ratio of aluminum: 5-10%; niobium: 20-30%; zirconium: 49-60%; molybdenum: 5-10%; hafnium: 1-10%, and the balance of boron and inevitable impurities.
The Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with the neutron poison characteristic has the tensile yield strength: 1028 to 1474 MPa, elongation: 6 to 28 percent.
The invention relates to a preparation method of an Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics, which specifically comprises the following steps:
(1) preparing raw materials: weighing required alloy raw materials according to the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy proportion;
(2) arc melting: under the protection of protective gas, rapidly heating and melting Al, Zr, Nb, Mo, Zr-Hf intermediate alloy and B powder; 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 tissue structure and the performance of the sample caused by the difference of smelting time and smelting current, each sample is directly closed after all alloy elements are completely melted into liquid state in each smelting process 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 Al-Nb-Zr-Mo-Hf-B system high-entropy alloy provided by the invention is a nuclear material with integrated structure and function, and due to the addition of Al element, compared with the traditional BCC structure refractory high-entropy alloys TaNbMoW and TaNbMoWV, the extensibility at room temperature is greatly improved; in addition, boron has the effect of grain refinement, can refine the initial state structure, and simultaneously can greatly improve the yield strength level of the high-entropy alloy of the system due to the formation of a large amount of boride, and simultaneously keeps better plastic deformation capability, the elongation can reach 28 percent at most, and the high-entropy alloy has good industrial application prospect; more importantly, the high-entropy alloy containing the B element can also strongly absorb thermal neutrons in a reactor, thereby providing an optimal candidate material with high toughness and high neutron absorption characteristics for parts with special purposes in the military industry. Therefore, the high-entropy alloy based on the Al-Nb-Zr-Mo-Hf-B system provided by the invention realizes the neutron poison characteristic of the high-entropy alloy by fully considering the special action of the B element, and has important significance for the development and application of high-end nuclear materials.
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
An Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics comprises the following specific alloy components: 5 at.% of Al, 40% of Zr, 30% of Nb, 15% of Mo, 9.8% of Hf, 0.2% of B, and the balance of inevitable impurity elements.
The preparation method of the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy comprises the following steps:
(1) preparing raw materials: weighing required alloy raw materials according to the proportion of the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy;
(2) arc melting: under the protection of protective gas, rapidly heating and melting Al, Zr, Nb, Mo, Zr-Hf intermediate alloy and B powder; 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 the smelting time and the smelting current, after all alloy elements are completely melted into liquid state in each smelting process of the sample, the current is directly closed after the smelting is kept for 1 min.
The mechanical property test of the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy ingot prepared by the embodiment shows that: the compressive yield strength is 1154 MPa, the plasticity is 28%, and the good strength and plasticity matching characteristics are shown.
Example 2
An Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics comprises the following specific alloy components: 14at.% of Al, 60% of Zr, 20% of Nb, 4.99% of Mo, 1% of Hf, 0.01% of B, and the balance of inevitable impurity elements.
The preparation method of the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy comprises the following steps:
(1) preparing raw materials: weighing required alloy raw materials according to the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy proportion;
(2) arc melting: under the protection of protective gas, rapidly heating and melting Al, Zr, Nb, Mo, Zr-Hf intermediate alloy and B powder; 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 the smelting time and the smelting current, after all alloy elements are completely melted into liquid state in each smelting process of the sample, the current is directly closed after the smelting is kept for 1 min.
The mechanical property test of the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy ingot prepared by the embodiment shows that: the compressive yield strength is 1028 MPa, and the plasticity is 19%.
Example 3
An Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics comprises the following specific alloy components: 11at.% of Al, 22% of Zr, 40% of Nb, 5% of Mo, 20% of Hf, 2% of B, and the balance of inevitable impurity elements.
The preparation method of the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy comprises the following steps:
(1) preparing raw materials: weighing required alloy raw materials according to the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy proportion;
(2) arc melting: under the protection of protective gas, rapidly heating and melting Al, Zr, Nb, Mo, Zr-Hf intermediate alloy and B powder; 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 the smelting time and the smelting current, after all alloy elements are completely melted into liquid state in each smelting process of the sample, the current is directly closed after the smelting is kept for 1 min.
The mechanical property test of the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy ingot prepared by the embodiment shows that: compressive yield strength: 1474 MPa, plasticity: and 6 percent, the steel plate shows extremely high yield strength level.
Example 4
An Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics comprises the following specific alloy components: 15 at.% of Al, 37% of Zr, 30% of Nb, 5% of Mo, 12.5% of Hf, 0.5% of B, and the balance of inevitable impurity elements.
The preparation method of the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy comprises the following steps:
(1) preparing raw materials: weighing required alloy raw materials according to the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy proportion;
(2) arc melting: under the protection of protective gas, rapidly heating and melting Al, Zr, Nb, Mo, Zr-Hf intermediate alloy and B powder; 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 the smelting time and the smelting current, after all alloy elements are completely melted into liquid state in each smelting process of the sample, the current is directly closed after the smelting is kept for 1 min.
The mechanical property test of the Al-Nb-Zr-Mo-Hf-B system ingot prepared in the embodiment shows that: the compressive yield strength is 1338MPa, the plasticity is-22%, and the extremely high yield strength level and the good plasticity are shown.
Example 5
An Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics comprises the following specific alloy components: 10 at.% of Al, 49% of Zr, 20% of Nb, 10% of Mo, 10% of Hf, 1% of B, and the balance of inevitable impurity elements.
The preparation method of the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics in the embodiment comprises the following steps:
(1) preparing raw materials: weighing required alloy raw materials according to the high-entropy alloy proportion of an Al-Nb-Zr-Mo-Hf-B system with neutron poison characteristics;
(2) arc melting: under the protection of protective gas, rapidly heating and melting Al, Zr, Nb, Mo, Zr-Hf intermediate alloy and B powder; 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 the smelting time and the smelting current, after all alloy elements are completely melted into liquid state in each smelting process of the sample, the current is directly closed after the smelting is kept for 1 min.
The mechanical property test of the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy ingot with the neutron poison characteristic prepared in the embodiment shows that: the compressive yield strength is 1371 MPa, the plasticity is 17%, and good strong plasticity matching is shown.
Compared with the existing material, the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics 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 Al-Nb-Zr-Mo-Hf-B system high-entropy alloy is increased from 1028 MPa of alloy with the content of 0.01B to maximum 1474 MPa, and the increase range is 43 percent;
2. under the condition of trace boron element alloying (0.5 at.%), the Al15-Zr37-Nb30-Mo5-Hf12.5-B0.5 as-cast high-entropy alloy shows excellent strength and plastic matching characteristics, and has the following compressive yield strength: 1338MPa, plasticity: 22 percent, which is superior to most of the refractory high-entropy alloys developed at present;
3. under the condition of low boron alloying (1.0-2.0 at.%), Al10-Zr49-Nb20-Mo10-Hf10-B1.0 and Al11-Zr40-Nb22-Mo5-Hf20-B2 as-cast high-entropy alloys all show higher strength and better plasticity level, and compressive yield strength: 1371-1474 MPa, plasticity: 6-17%, and has a great engineering application value;
4. due to the addition of a certain content of B element, the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy can also strongly absorb thermal neutrons in a reactor, thereby providing the best candidate material with high toughness and high neutron absorption characteristics for parts with special purposes in the military industry, and realizing the functional characteristics of neutron poison and the like of structural materials.
Claims (9)
1. The preparation method of the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with the neutron poison characteristic is characterized by comprising the following components in percentage by mass: aluminum: 5-15%; niobium: 20-30%; zirconium: 37-60%; molybdenum: 4.99-15%; hafnium: 1-20%, and the balance of boron and inevitable impurities;
the preparation method comprises the following steps:
(1) preparing raw materials: weighing required alloy raw materials according to the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy proportion;
(2) arc melting: under the protection of protective gas, rapidly heating and melting Al, Zr, Nb, Mo, Zr-Hf intermediate alloy and B powder; 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 tissue structure and the performance of the sample caused by the difference of smelting time and smelting current, each sample is directly closed after all alloy elements are completely melted into liquid state in each smelting process and 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;
tensile yield strength of the high-entropy alloy: 1028 to 1474 MPa, elongation: 6 to 28 percent.
2. The method for preparing the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics according to claim 1, wherein the weight ratio of aluminum: 5-15%; niobium: 20-30%; zirconium: 40-60%; molybdenum: 5-15%; hafnium: 9.8-20%, and the balance of boron and inevitable impurities.
3. The method for preparing the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics according to claim 2, wherein the weight ratio of aluminum: 5 percent; niobium: 30 percent; zirconium: 40 percent; molybdenum: 15 percent; hafnium: 9.8 percent, and the balance of boron and inevitable impurities.
4. The method for preparing the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics according to claim 1, wherein the weight ratio of aluminum: 5 to 14 percent; niobium: 20-30%; zirconium: 37-60%; molybdenum: 4.99-15%; hafnium: 1-20%, and the balance of boron and inevitable impurities.
5. The method for preparing the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics according to claim 4, wherein the weight ratio of aluminum: 14 percent; niobium: 20 percent; zirconium: 60 percent; molybdenum: 4.99 percent; hafnium: 1% and the balance of boron and inevitable impurities.
6. The method for preparing the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics according to claim 1, wherein the weight ratio of aluminum: 5-11%; niobium: 22-30%; zirconium: 40-60%; molybdenum: 5-15%; hafnium: 1-20%, and the balance of boron and inevitable impurities.
7. The method for preparing the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics according to claim 6, wherein the weight ratio of aluminum: 11 percent; niobium: 22 percent; zirconium: 40 percent; molybdenum: 5 percent; hafnium: 20 percent, and the balance of boron and inevitable impurities.
8. The method for preparing the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics according to claim 1, wherein the weight ratio of aluminum: 5-15%; niobium: 20-30%; zirconium: 37-60%; molybdenum: 5-15%; hafnium: 1 to 12.5 percent, and the balance of boron and inevitable impurities.
9. The method for preparing the Al-Nb-Zr-Mo-Hf-B system high-entropy alloy with neutron poison characteristics according to claim 1, wherein the weight ratio of aluminum: 5-10%; niobium: 20-30%; zirconium: 49-60%; molybdenum: 5-10%; hafnium: 1-10%, and the balance of boron and inevitable impurities.
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