CN117758096A

CN117758096A - Radiation shielding high-entropy alloy, preparation method and application thereof, and radiation shielding product

Info

Publication number: CN117758096A
Application number: CN202311565426.7A
Authority: CN
Inventors: 刘峰; 李程鑫; 蒋丹枫; 李利; 刘夏杰
Original assignee: China Nuclear Power Technology Research Institute Co Ltd
Current assignee: China Nuclear Power Technology Research Institute Co Ltd
Priority date: 2023-11-22
Filing date: 2023-11-22
Publication date: 2024-03-26

Abstract

The application relates to a radiation shielding high-entropy alloy, a preparation method and application thereof, and a radiation shielding product. The preparation method of the radiation shielding high-entropy alloy comprises the following steps: mixing a tungsten simple substance and a boron simple substance, and then performing first sintering under an inert gas atmosphere to obtain a tungsten-boron compound; and mixing the tungsten-boron compound with an aluminum simple substance, a molybdenum simple substance, a niobium simple substance and a titanium simple substance, and then performing second sintering. The radiation shielding high-entropy alloy prepared by the preparation method has good radiation shielding performance on neutron radiation and gamma rays, good high-temperature mechanical performance, and good wear resistance and corrosion resistance.

Description

Radiation shielding high-entropy alloy, preparation method and application thereof, and radiation shielding product

Technical Field

The application relates to the field of alloys, in particular to a radiation shielding high-entropy alloy, a preparation method and application thereof, and a radiation shielding product.

Background

The development and utilization of nuclear energy are paid attention to, pressurized water reactor nuclear power plants and the like based on second and third generation nuclear power technologies are increasingly applied, and fourth generation advanced nuclear power technologies represented by sodium-cooled fast reactors, lead-cooled fast reactors and the like are also greatly supported and developed rapidly. The broad application of nuclear energy and the rapid sustainable development of nuclear power industry in the future are not separated from the innovations of radiation protection and radiation safety technologies.

Among the many nuclear radiation types used in nuclear power plants, neutron radiation and gamma radiation are the most important and shielding requirements are the most urgent. Traditional composite shielding materials comprise metal matrix composite materials, ceramic matrix composite materials, polymer matrix composite materials and the like, but the medium and high temperature mechanical properties of the composite shielding materials are poor.

The high-entropy alloy (HEA) is a new alloy design concept which is gradually raised in recent years, and is composed of 5 or more metal elements, wherein the atomic ratio of each element is 5% -35%, disordered solid solutions are difficult to specifically distinguish solvents and solutes, the components of the disordered solid solutions are also generally positioned at the center of a phase diagram, the disordered solid solutions have higher mixed entropy, and the disordered solid solutions are often prone to forming simple solid solution phases such as body centered cubic cells (BCC), face centered cubic cells (FCC) and close packed Hexagonal Cells (HCP), and non-intermetallic compounds or other complex ordered phases, and the unique crystal structure enables the high-entropy alloy to show a plurality of excellent performances different from the traditional metal alloy, such as high strength, high room temperature toughness, better abrasion resistance, oxidation resistance, corrosion resistance, thermal stability and the like. However, conventional high-entropy alloys cannot simultaneously satisfy better shielding of neutron radiation and gamma-ray radiation.

Disclosure of Invention

Based on the above, the application provides the radiation shielding high-entropy alloy which has better radiation shielding performance on the neutron radiation and the gamma rays and better high-temperature mechanical performance, and the preparation method and the application thereof.

The technical scheme for solving the technical problems is as follows.

In one aspect, the present application provides a method for preparing a radiation shielding high entropy alloy, comprising the steps of:

mixing a tungsten simple substance and a boron simple substance, and then performing first sintering under an inert gas atmosphere to obtain a tungsten-boron compound; and

And mixing the tungsten-boron compound with an aluminum simple substance, a molybdenum simple substance, a niobium simple substance and a titanium simple substance, and then performing second sintering.

In some embodiments, in the preparation method of the radiation shielding high-entropy alloy, the molar ratio of the tungsten simple substance to the boron simple substance is (0.5-2.0): 1.

In some embodiments, in the preparation method of the radiation shielding high-entropy alloy, the molar ratio of the aluminum simple substance, the molybdenum simple substance, the niobium simple substance, the titanium simple substance and the tungsten-boron compound is (0.8-1.2): 0.5-1.0): 0.8-1.2): 1.

In some embodiments, the method for preparing the radiation shielding high-entropy alloy comprises the step of adding the tungsten simple substance, the boron simple substance, the aluminum simple substance, the molybdenum simple substance, the niobium simple substance and the titanium simple substance in the form of powder.

In some embodiments, in the preparation method of the radiation shielding high-entropy alloy, the particle size of the tungsten simple substance is 100-1000 meshes.

In some embodiments, in the preparation method of the radiation shielding high-entropy alloy, the particle size of the boron simple substance is 100-1000 meshes.

In some embodiments, in the preparation method of the radiation shielding high-entropy alloy, the grain size of the aluminum simple substance is 150-500 meshes.

In some embodiments, in the preparation method of the radiation shielding high-entropy alloy, the particle size of the molybdenum simple substance is 150-500 meshes.

In some embodiments, in the preparation method of the radiation shielding high-entropy alloy, the particle size of the niobium simple substance is 150-500 meshes.

In some embodiments, in the preparation method of the radiation shielding high-entropy alloy, the particle size of the titanium simple substance is 150-500 meshes.

In some embodiments, in the method for preparing the radiation shielding high-entropy alloy, the temperature of the first sintering is 1200-1400 ℃.

In some embodiments, in the preparation method of the radiation shielding high-entropy alloy, the temperature of the second sintering is 1350 ℃ -1500 ℃, the pressure is 25 MPa-32 MPa, and the time is 5 min-15 min.

In some embodiments, the method for preparing a radiation shielding high-entropy alloy further comprises a step of providing a boron coating layer on the surface of the alloy obtained in the second sintering step after the second sintering step.

Correspondingly, the application provides a radiation shielding high-entropy alloy which is prepared by the preparation method.

In another aspect, the present application provides a radiation shielding high entropy alloy comprising a core layer having a composition comprising tungsten, boron, aluminum, molybdenum, niobium, and titanium.

In some of these embodiments, the core layer comprises the following components in mole percent in the radiation shielding high entropy alloy: 16.00% -30.00% of Al, 6.17% -18.52% of W, 10.20% -24.39% of Mo, 10.20% -24.39% of Nb, 16.00% -30.00% of Ti and 6.17% -18.52% of B.

In some of these embodiments, the radiation-shielding high-entropy alloy further includes a boron cladding layer disposed on a surface of the core layer.

In some of these embodiments, the boron cladding layer has a thickness of 2 μm to 50 μm in the radiation shielding high entropy alloy.

The application also provides application of the radiation shielding high-entropy alloy in preparing a radiation shielding product.

The present application also provides a radiation shielding article comprising the radiation shielding high entropy alloy described above.

Compared with the prior art, the preparation method of the radiation shielding high-entropy alloy has the following beneficial effects:

according to the preparation method of the radiation shielding high-entropy alloy, firstly, the tungsten simple substance and the boron simple substance are mixed and then subjected to first sintering in the inert gas atmosphere, and then the tungsten-boron compound obtained after the first sintering is mixed with the aluminum simple substance, the molybdenum simple substance, the niobium simple substance and the titanium simple substance to perform second sintering, so that segregation and aggregation phenomena of the boron simple substance in the mixing process can be effectively avoided, and the shielding performance of the radiation shielding high-entropy alloy on neutron radiation and gamma rays can be effectively improved; the density difference between the obtained tungsten-boron compound and aluminum, molybdenum, niobium and titanium is small, so that the uniformity of mixing with the aluminum, molybdenum, niobium and titanium is good, the neutron shielding effect of boron is effectively promoted, the gamma ray shielding effect of tungsten is effectively promoted, and the prepared radiation shielding high-entropy alloy has good comprehensive radiation shielding performance on neutron radiation and gamma rays and good high-temperature mechanical property; meanwhile, the prepared radiation shielding high-entropy alloy has better wear resistance and corrosion resistance.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

Fig. 1 is an external view of a radiation-shielding high-entropy alloy a prepared in the example.

Detailed Description

Reference now will be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one embodiment can be used on another embodiment to yield still a further embodiment.

Accordingly, it is intended that the present invention cover such modifications and variations as fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention will be disclosed in or be apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

The terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise. The meaning of "a plurality of" means at least two, e.g., two, three, etc., unless explicitly defined otherwise.

The weights of the relevant components mentioned in the description of the embodiments of the present invention may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present invention are scaled up or down within the scope of the disclosure of the embodiments of the present invention. Specifically, the weight described in the specification of the embodiment of the present invention may be mass units known in the chemical industry field such as μ g, mg, g, kg.

Except where shown or otherwise indicated in the operating examples, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth, used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, therefore, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be varied appropriately by those skilled in the art utilizing the teachings disclosed herein seeking to obtain the desired properties. The use of numerical ranges by endpoints includes all numbers subsumed within that range and any range within that range, e.g., 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, 5, and the like.

The technical staff of the application find that when the boron powder is directly adopted in the research process, obvious segregation and aggregation phenomena of the boron powder can occur in the mixing process, so that the performance of the alloy material is unstable or locally worsened, and the adding proportion of the boron powder is severely limited.

An embodiment of the application provides a preparation method of a radiation shielding high-entropy alloy, which comprises the following steps S10-S20:

step S10: and mixing the tungsten simple substance and the boron simple substance, and then performing first sintering under the inert gas atmosphere to obtain the tungsten-boron compound.

By mixing the tungsten simple substance and the boron simple substance first and then carrying out first sintering under the inert gas atmosphere, the segregation and aggregation phenomenon of the boron simple substance in the mixing process can be effectively avoided.

In some examples, in step S10, the molar ratio of the elemental tungsten to the elemental boron is (0.5-2.0): 1.

It is understood that the molar ratio of elemental tungsten to elemental boron includes, but is not limited to, 0.5:1, 1:1, 1.5:1, 2:1. The following holds true for the range that any two of these point values may be made up as end values in some examples.

In some examples, in step S10, the molar ratio of elemental tungsten to elemental boron is 2:1.

It is understood that inert gases include, but are not limited to, helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn), and Og.

In some examples, in step S10, the inert gas atmosphere includes at least one of helium, neon, argon, krypton, and xenon.

It can be understood that the tungsten simple substance and the boron simple substance are mixed and then subjected to first sintering under the inert gas atmosphere of a specific kind, so that oxidation at high temperature is avoided, and a uniform WB compound is formed; if the tungsten simple substance and the boron simple substance are mixed and sintered in nitrogen, tungsten nitride is generated, so that an impurity phase is introduced; sintering in air will produce tungsten nitride and oxide, introducing impurity phase.

Optionally, the inert gas atmosphere is argon.

In some examples, in step S10, the temperature of the first sintering is 1200 ℃ to 1400 ℃.

It is understood that the temperature of the first sintering includes, but is not limited to, 1200 ℃, 1220 ℃, 1250 ℃, 1280 ℃, 1300 ℃, 1320 ℃, 1350 ℃, 1380 ℃, 1400 ℃.

In some examples, in step S10, the method of mixing the elemental tungsten and the elemental boron is a mechanical mixing method.

In some examples, in step S10, after the first sintering step, a step of pulverizing a sintered product obtained by the first sintering is further included.

Further, the grinding step is also included after the grinding.

It can be understood that the tungsten-boron compound is tungsten-boron compound powder after being crushed and ground.

Further, the particle size of the tungsten-boron compound is 100-200 meshes.

Step S20: and mixing the tungsten-boron compound with an aluminum simple substance, a molybdenum simple substance, a niobium simple substance and a titanium simple substance, and then performing second sintering.

In some examples, in the step S20, the molar ratio of the aluminum simple substance, the molybdenum simple substance, the niobium simple substance, the titanium simple substance and the tungsten boron compound is (0.8-1.2): 0.5-1.0): 0.8-1.2): 1.

It is understood that the amount of the substance of the tungsten boron complex is 1 unit and the amount of the substance of the aluminum simple substance includes, but is not limited to, 0.8, 1, 1.1, 1.2 units; the amount of elemental molybdenum material includes, but is not limited to, 0.5, 0.8, 1 unit; the amount of elemental niobium species includes, but is not limited to, 0.5, 0.8, 1 units; the amount of the elemental titanium species includes, but is not limited to, 0.8, 1, 1.1, 1.2 units.

In some examples, in step S20, the molar ratio of elemental aluminum, elemental molybdenum, elemental niobium, elemental titanium, and tungsten boron complex is 1:1:1:1.

The molar content of tungsten element, boron element, aluminum element, molybdenum element, niobium element and titanium element in the finally obtained radiation shielding high-entropy alloy can be controlled by controlling the molar ratio of the tungsten element to the boron element and the molar ratio of the aluminum element, the molybdenum element, the niobium element and the tungsten-boron compound.

It can be understood that when the molar ratio of the simple substance of tungsten to the simple substance of boron is 2:1, and the molar ratio of the simple substance of aluminum, the simple substance of molybdenum, the simple substance of niobium, the simple substance of titanium to the complex of tungsten and boron is 1:1:1:1:1, the molar content of boron in the finally prepared radiation shielding high-entropy alloy is about 6.7%.

In some examples, in the preparation method of the radiation shielding high-entropy alloy, the purity of the tungsten simple substance, the boron simple substance, the aluminum simple substance, the molybdenum simple substance, the niobium simple substance and the titanium simple substance is more than or equal to 99.9%.

In some examples, in the method for preparing the radiation shielding high-entropy alloy, the tungsten simple substance, the boron simple substance, the aluminum simple substance, the molybdenum simple substance, the niobium simple substance and the titanium simple substance are added in the form of powder.

That is, in some examples, the method of preparing the radiation shielding high entropy alloy includes the steps of:

mixing tungsten powder and boron powder, and performing first sintering under inert gas atmosphere to obtain a tungsten-boron compound;

and mixing the tungsten-boron compound with aluminum powder, molybdenum powder, niobium powder and titanium powder, and then performing second sintering.

In some examples, in the preparation method of the radiation shielding high-entropy alloy, the particle size of the tungsten simple substance is 100-1000 meshes.

In some examples, in the preparation method of the radiation shielding high-entropy alloy, the particle size of the boron simple substance is 100-1000 meshes.

In some examples, in the preparation method of the radiation shielding high-entropy alloy, the particle size of the aluminum simple substance is 150-500 meshes.

In some examples, in the preparation method of the radiation shielding high-entropy alloy, the particle size of the molybdenum simple substance is 150-500 meshes.

In some examples, in the preparation method of the radiation shielding high-entropy alloy, the particle size of the niobium simple substance is 150-500 meshes.

In some examples, in the preparation method of the radiation shielding high-entropy alloy, the particle size of the titanium simple substance is 150-500 meshes.

It is understood that the second sintering means include, but are not limited to, spark plasma sintering, vacuum arc melting, and the like.

In some examples, in step S20, the second sintering is discharge plasma sintering.

It is understood that the spark plasma sintering is performed using an SPS discharge plasma sintering furnace.

In some examples, in step S20, the temperature of the second sintering is 1350 ℃ to 1500 ℃.

It is understood that the temperature of the second sintering includes, but is not limited to 1350 ℃, 1380 ℃, 1400 ℃, 1420 ℃, 1450 ℃, 1480 ℃, 1500 ℃.

In some examples, in step S20, the pressure of the second sintering is 25 MPa to 32 MPa.

It is understood that the pressure of the second sintering includes, but is not limited to, 25 MPa, 26 MPa, 27 MPa, 28 MPa, 29 MPa, 30 MPa, 31 MPa, 32 MPa.

In some examples, in step S20, the second sintering time is 5 min to 15 min.

It is understood that the time for the second sintering includes, but is not limited to, 5 min, 6 min, 8 min, 10 min, 12 min, 15 min.

In some examples, in step S20, the temperature of the second sintering is 1400 ℃ to 1500 ℃, the pressure is 28 MPa to 30 MPa, and the time is 8 min to 12 min.

In some specific examples thereof, in step S20, the temperature of the second sintering is 1450 ℃.

In some examples, step S20 further includes a step of ball milling a mixture obtained by mixing the tungsten boron compound with the elemental aluminum, the elemental molybdenum, the elemental niobium, and the elemental titanium, before the second sintering step.

In some examples, in step S20, the parameters of ball milling are: the rotating speed is 300 r/min-450 r/min, the ball-material ratio is 4:1-15:1, and the ball milling time is 20-100 h.

It will be appreciated that the rotational speeds of ball milling include, but are not limited to, 300 r/min, 310 r/min, 320 r/min, 330 r/min, 340 r/min, 350 r/min, 360 r/min, 380 r/min, 400 r/min, 420 r/min, 450 r/min, ball to ball ratios including, but not limited to, 4:1, 5:1, 6:1, 7:1, 8:1, 10:1, 12:1, 14:1, 15:1, and ball milling times including, but not limited to, 20 h, 30 h, 40 h, 50 h, 60 h, 70 h, 80 h, 90 h, 100 h.

Optionally, the ball milling parameters are: the rotating speed is 350-r/min to 450-r/min, the ball-material ratio is 8:1-12:1, and the ball milling time is 30-60 h.

In some examples, in step S20, a mixture obtained by mixing a tungsten-boron compound with an aluminum simple substance, a molybdenum simple substance, a niobium simple substance and a titanium simple substance is put into a zirconia ceramic pot for ball milling.

Further, the ceramic tank may be selected from zirconia ceramic tanks.

Further, ball milling was performed under an inert gas atmosphere. Optionally, ball milling is performed under argon.

Further, a planetary ball mill is adopted for mechanical alloying high-energy ball milling.

In some examples, the method for preparing the radiation shielding high-entropy alloy further includes, after the step S20 is finished, a step S30:

and (3) arranging a boron coating layer on the surface of the alloy obtained in the second sintering step.

In some examples, in step S30, a boron-rich layer is provided on the surface of the alloy obtained in the second sintering step by using an embedding boronizing method.

And a boron-rich layer is arranged on the surface of the alloy obtained in the second sintering step, so that the absorption of the neutron in the complex neutron/gamma ray radiation environment is effectively improved, and the neutron absorptivity is improved, and the shielding performance of the radiation shielding high-entropy alloy for the neutron irradiation in the complex neutron/gamma ray radiation environment is further improved.

In some examples, in step S30, the boronizing temperature is 1000 ℃ to 1200 ℃ and the boronizing time is 4 hours to 24 hours.

It is understood that the boronizing temperatures include, but are not limited to, 1000 ℃, 1050 ℃, 1100 ℃, 1120 ℃, 1150 ℃, 0 ℃, 1200 ℃, and the boronizing times include, but are not limited to, 4 h, 8 h, 10 h, 15 h, 20 h, 24 h.

In some examples, in step S30, argon protection is used in the embedding boronizing method.

In some examples, in step S30, the boronizing raw material of the embedded boronizing method includes boron powder and a penetration enhancer.

Further, the permeation enhancer includes a rare metal oxide.

Still further, the permeation enhancer comprises at least one of yttria and lanthana.

Accordingly, an embodiment of the present application provides a radiation shielding high-entropy alloy, which is prepared by the preparation method.

In another aspect, the present application provides a radiation shielding high entropy alloy comprising a core layer comprising components of tungsten, boron, aluminum, molybdenum, niobium, and titanium.

It is understood that Al includes, but is not limited to, 16.00%, 18.00%, 20.00%, 22.00%, 25.00%, 28.00%, 30.00% by mole; w includes, but is not limited to, 6.17%, 8%, 10%, 15%, 18.52%; mo includes, but is not limited to, 10.20%, 15%, 18%, 20%, 24.39%; nb includes, but is not limited to, 10.20%, 15%, 18%, 20%, 24.39%; ti includes, but is not limited to, 16.00%, 18.00%, 20.00%, 22.00%, 25.00%, 28.00%, 30.00%, and B6.17%, 8%, 10%, 15%, 18.52%.

The interaction of the boron element with tungsten, aluminum, molybdenum, niobium and titanium can enable the content of B added in the radiation shielding high-entropy alloy to be higher and to be more than 10%, so that the radiation shielding high-entropy alloy has good radiation shielding performance on neutron radiation and gamma rays, good high-temperature mechanical performance and good wear resistance and corrosion resistance.

Ni is easy to be corroded by lead-bismuth alloy and the like (a loop coolant of a lead-based stack), and the lead-bismuth alloy can overflow and corrode a shielding structure under an accident condition, so that a Ni-containing material cannot be used for shielding in a lead-bismuth environment or a lead-bismuth in-stack shielding structure. The radiation shielding high-entropy alloy does not contain Ni, and can be used for shielding in a lead-bismuth environment or a lead-bismuth in-pile shielding structure.

Therefore, the shielding performance of the radiation shielding high-entropy alloy for neutron irradiation in a complex neutron/gamma ray radiation environment can be further improved.

It is understood that the thickness of the boron cladding layer includes, but is not limited to, 2 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm.

An embodiment of the present application provides an application of the radiation shielding high-entropy alloy in preparing a radiation shielding product. Another embodiment of the present application provides a radiation shielding article comprising the radiation shielding high entropy alloy described above.

In some of these embodiments, the radiation shielding article includes, but is not limited to, radiation protective apparel, radiation protective covers, radiation protective helmets, and the like.

The radiation shielding high-entropy alloy is used for preparing a radiation shielding product, has good shielding performance on neutron radiation and gamma-ray radiation, and can also endow the radiation shielding product with good high-temperature mechanical performance, wear resistance and corrosion resistance.

In some embodiments, the radiation-shielding article may be made of the radiation-shielding high-entropy alloy described above, i.e., the radiation-shielding article is directly made of the radiation-shielding high-entropy alloy described above. In other embodiments, the material of the radiation shielding article may include other materials in addition to the radiation shielding high entropy alloy described above.

The present application will be described in further detail with reference to the following specific embodiments, but embodiments of the present application are not limited thereto.

Example 1

(1) Mixing tungsten powder with the particle size of 500 meshes and boron powder with the particle size of 300 meshes according to the molar ratio of 2:1, uniformly mixing by using a mechanical alloying method, placing the mixture under argon condition, performing first sintering at 1250 ℃, and crushing and grinding to obtain tungsten-boron composite powder;

(2) Mixing tungsten-boron composite powder with aluminum powder with the particle size of 500 meshes, molybdenum powder with the particle size of 1000 meshes, niobium powder with the particle size of 500 meshes and titanium powder with the particle size of 800 meshes according to the mol ratio of 1:1:1:1:1, filling the mixture into a zirconia ceramic tank, filling argon into the ceramic tank, ensuring positive pressure in the tank, and carrying out mechanical alloying high-energy ball milling by adopting a planetary ball mill, wherein the ball milling parameters are as follows: rotational speed 400 r/min, ball-to-material ratio 10:1, ball milling time 40 h;

(3) Loading the ball-milled mixed powder into a shaping mold, and performing spark plasma sintering by using an SPS discharge plasma sintering furnace, wherein the sintering parameters are as follows: the sintering temperature is 1450 ℃, the sintering pressure is 28 MPa, and the heat preservation time is 10 min, so that the radiation shielding high-entropy alloy is obtained, wherein the molar ratio of W, B, mo, nb, al, ti in the radiation shielding high-entropy alloy is 2/3:1/3:1:1:1:1, and the appearance of the radiation shielding high-entropy alloy A is shown in figure 1;

(4) Adopting an embedding boriding method to boriding the surface of the radiation shielding high-entropy alloy A, and forming a compact boron-rich coating layer on the surface of the radiation shielding high-entropy alloy A to obtain a radiation shielding high-entropy alloy B; wherein, boron powder and a permeation promoter yttrium oxide are used as boronizing raw materials, argon is adopted for protection, the boronizing temperature is 1000-1200 ℃, the boronizing heat preservation time is 4-24 hours, and the furnace is cooled after the heat preservation is finished.

Example 2

Substantially the same as in example 1, except that in the step (1), the molar ratio of tungsten powder to boron powder was 1:2, i.e., the molar ratio of W, B, mo, nb, al, ti in the radiation-shielding high-entropy alloy a obtained in example 2 was 1/3:2/3:1:1:1:1.

The radiation shielding high-entropy alloy B prepared in each example was subjected to neutron and gamma ray shielding performance tests according to the relevant requirements of GBZ/T147-2002 "determination of attenuation Properties of X-ray protective materials", and yield strength tests at 25℃and 800℃were carried out according to GB/T228.1-2021 (section 1 of tensile test of metallic materials: room temperature test method) and GB/T228.2-2015 (section 2 of tensile test of metallic materials: high temperature test method), respectively, and the test results are shown in Table 1.

TABLE 1

As can be seen from Table 1, the B-element-containing WMoNbAlTi radiation shielding high-entropy alloy prepared by the method has obviously better comprehensive neutron and gamma-ray shielding capacity than the traditional high-entropy alloy, and also has better room temperature mechanical property and good medium-high temperature mechanical property, is suitable for structural members or equipment with shielding requirements in medium-high temperature service environments, or meets the complex requirements of comprehensive neutron/gamma-ray shielding protection.

The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.

The above examples merely represent a few embodiments of the present application, which facilitate a specific and detailed understanding of the technical solutions of the present application, but are not to be construed as limiting the scope of the invention. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. It should be understood that those skilled in the art, based on the technical solutions provided in the present application, can obtain technical solutions through logical analysis, reasoning or limited experiments, all fall within the protection scope of the claims attached in the present application. The scope of the patent application is therefore intended to be limited by the content of the appended claims, the description and drawings being presented to the extent that the claims are defined.

Claims

1. The preparation method of the radiation shielding high-entropy alloy is characterized by comprising the following steps of:

2. The method according to claim 1, wherein the molar ratio of the elemental tungsten to the elemental boron is (0.5 to 2.0): 1.

3. The method according to claim 1, wherein the molar ratio of the elemental aluminum, the elemental molybdenum, the elemental niobium, the elemental titanium, and the tungsten boron compound is (0.8 to 1.2): (0.5 to 1.0): (0.8 to 1.2): 1.

4. The method according to any one of claims 1 to 3, wherein the elemental tungsten, the elemental boron, the elemental aluminum, the elemental molybdenum, the elemental niobium, and the elemental titanium are added in the form of powder.

5. The production method according to claim 4, wherein the production method satisfies at least one of the following characteristics (1) to (6):

(1) The particle size of the tungsten simple substance is 100-1000 meshes;

(2) The grain size of the boron simple substance is 100-1000 meshes;

(3) The grain diameter of the aluminum simple substance is 150-500 meshes;

(4) The particle size of the molybdenum simple substance is 150-500 meshes;

(5) The grain size of the niobium simple substance is 150-500 meshes;

(6) The particle size of the titanium simple substance is 150-500 meshes.

6. The method according to any one of claims 1 to 3 and 5, wherein the temperature of the first sintering is 1200 ℃ to 1400 ℃.

7. The method according to any one of claims 1 to 3 and 5, wherein the second sintering temperature is 1350 ℃ to 1500 ℃, the pressure is 25 MPa to 32 MPa, and the time is 5 min to 15 min.

8. The method according to any one of claims 1 to 3 and 5, further comprising a step of providing a boron coating layer on the surface of the alloy obtained in the second sintering step after the second sintering step.

9. A radiation shielding high entropy alloy, characterized in that it is prepared by the preparation method according to any one of claims 1 to 8.

10. A radiation shielding high entropy alloy, comprising a core layer, the composition of the core layer comprising tungsten, boron, aluminum, molybdenum, niobium, and titanium.

11. The radiation-shielding high-entropy alloy of claim 10, wherein the core layer comprises, in mole percent, the following components:

16.00% -30.00% of Al, 6.17% -18.52% of W, 10.20% -24.39% of Mo, 10.20% -24.39% of Nb, 16.00% -30.00% of Ti and 6.17% -18.52% of B.

12. The radiation-shielding high-entropy alloy according to any one of claims 10 to 11, further comprising a boron cladding layer disposed on a surface of the core layer.

13. The radiation-shielding high-entropy alloy of claim 12, wherein the boron cladding layer has a thickness of 2 μιη to 50 μιη.

14. Use of a radiation-shielding high-entropy alloy according to any one of claims 9 to 13 for the preparation of a radiation-shielding article.

15. A radiation shielding article comprising the radiation shielding high entropy alloy of any one of claims 9-13.