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

Abstract

The present application relates to a radiation shielding high entropy alloy and its preparation method and application, and radiation shielding products. The preparation method of the radiation shielding high entropy alloy comprises the following steps: mixing tungsten and boron and then performing a first sintering in an inert gas atmosphere to obtain a tungsten-boron composite; mixing the tungsten-boron composite with aluminum, molybdenum, niobium and titanium and then performing a second sintering. The radiation shielding high entropy alloy prepared by the preparation method has good radiation shielding performance against both neutron radiation and gamma rays, and good high-temperature mechanical properties, as well as good wear resistance and corrosion resistance.

Description

Technical Field

[0001] The present application relates to the field of alloys, and particularly to a radiation shielding high-entropy alloy, a preparation method and application thereof, and a radiation shielding product. Background Art

[0002] The development and utilization of nuclear energy have received extensive attention. Pressurized water reactor nuclear power plants based on second- and third-generation nuclear power technologies are being increasingly applied. At the same time, fourth-generation advanced nuclear power technologies represented by sodium-cooled fast reactors and lead-cooled fast reactors have also received strong support and rapid development. The extensive application of future nuclear energy and the rapid and sustainable development of the nuclear power industry are inseparable from the innovation of radiation protection and radiation safety technologies.

[0003] For nuclear power plants, among many types of nuclear radiation, neutron radiation and γ-ray radiation are the most important, and the shielding requirements are also the most urgent. Traditional composite shielding materials include metal matrix composites, ceramic matrix composites, and polymer matrix composites, etc. However, these composite shielding materials have poor mechanical properties at medium and high temperatures.

[0004] High-entropy alloy (HEA) is a new alloy design concept that has gradually emerged in recent years. It is composed of 5 or more metal elements, and the atomic proportion of each constituent element is between 5% and 35%. It is difficult to specifically distinguish the solvent and solute in the disordered solid solution, and its composition is generally located at the center of the phase diagram, with a relatively high mixing entropy, and often tends to form simple solid solution phases such as body-centered cubic cell (BCC), face-centered cubic cell (FCC), and hexagonal close-packed cell (HCP), rather than intermetallic compounds or other complex ordered phases. This unique crystal structure makes high-entropy alloys exhibit many excellent properties different from traditional metal alloys, such as high strength, high room temperature toughness, good wear resistance, oxidation resistance, corrosion resistance, and thermal stability, etc. However, traditional high-entropy alloys cannot simultaneously meet good shielding of neutron radiation and γ-ray radiation. Summary of the Invention

[0005] Based on this, the present application provides a radiation shielding high-entropy alloy that has good radiation shielding performance for both neutron radiation and γ-ray, and has good high-temperature mechanical properties, as well as a preparation method and application thereof.

[0006] The technical solution of the present application to solve the above technical problems is as follows.

[0007] On the one hand, the present application provides a preparation method of a radiation shielding high-entropy alloy, including the following steps:

[0008] Mix tungsten element and boron element and conduct first sintering in an inert gas atmosphere to obtain a tungsten-boron composite; and

[0009] Mix the tungsten-boron composite with aluminum element, molybdenum element, niobium element, and titanium element and conduct second sintering.

[0010] In some of these embodiments, in the method for preparing a radiation shielding high-entropy alloy, the molar ratio of the tungsten element to the boron element is (0.5 to 2.0):1.

[0011] In some of these embodiments, in the method for preparing a radiation shielding high-entropy alloy, the molar ratio of the aluminum element, the molybdenum element, the niobium element, the titanium element to the tungsten-boron composite is (0.8 to 1.2):(0.5 to 1.0):(0.5 to 1.0):(0.8 to 1.2):1.

[0012] In some of these embodiments, in the method for preparing a radiation shielding high-entropy alloy, the tungsten element, the boron element, the aluminum element, the molybdenum element, the niobium element and the titanium element are all added in the form of powders.

[0013] In some of these embodiments, in the method for preparing a radiation shielding high-entropy alloy, the particle size of the tungsten element is 100 to 1000 mesh.

[0014] In some of these embodiments, in the method for preparing a radiation shielding high-entropy alloy, the particle size of the boron element is 100 to 1000 mesh.

[0015] In some of these embodiments, in the method for preparing a radiation shielding high-entropy alloy, the particle size of the aluminum element is 150 to 500 mesh.

[0016] In some of these embodiments, in the method for preparing a radiation shielding high-entropy alloy, the particle size of the molybdenum element is 150 to 500 mesh.

[0017] In some of these embodiments, in the method for preparing a radiation shielding high-entropy alloy, the particle size of the niobium element is 150 to 500 mesh.

[0018] In some of these embodiments, in the method for preparing a radiation shielding high-entropy alloy, the particle size of the titanium element is 150 to 500 mesh.

[0019] In some of these embodiments, in the method for preparing a radiation shielding high-entropy alloy, the temperature of the first sintering is 1200°C to 1400°C.

[0020] In some of these embodiments, in the method for preparing a radiation shielding high-entropy alloy, the temperature of the second sintering is 1350°C to 1500°C, the pressure is 25 MPa to 32 MPa, and the time is 5 min to 15 min.

[0021] In some of these embodiments, in the method for preparing a radiation shielding high-entropy alloy, after the second sintering step, a step of providing a boron coating layer on the surface of the alloy obtained in the second sintering step is further included.

[0022] Correspondingly, the present application provides a radiation shielding high-entropy alloy prepared by the above preparation method.

[0023] On the other hand, the present application provides a radiation shielding high-entropy alloy, which includes a core layer, and the components of the core layer include tungsten, boron, aluminum, molybdenum, niobium and titanium.

[0024] In some embodiments, in the radiation shielding high-entropy alloy, by molar percentage, the core layer includes the following components: Al 16.00% - 30.00%, W 6.17% - 18.52%, Mo 10.20% - 24.39%, Nb 10.20% - 24.39%, Ti 16.00% - 30.00% and B 6.17% - 18.52%.

[0025] In some embodiments, in the radiation shielding high-entropy alloy, the radiation shielding high-entropy alloy further includes a boron coating layer disposed on the surface of the core layer.

[0026] In some embodiments, in the radiation shielding high-entropy alloy, the thickness of the boron coating layer is 2 μm - 50 μm.

[0027] The present application also provides an application of the above radiation shielding high-entropy alloy in the preparation of radiation shielding products.

[0028] The present application also provides a radiation shielding product, which includes the above radiation shielding high-entropy alloy.

[0029] Compared with the prior art, the preparation method of the radiation shielding high-entropy alloy of the present application has the following beneficial effects:

[0030] In the preparation method of the above radiation shielding high-entropy alloy, tungsten and boron are first mixed and then subjected to first sintering in an inert gas atmosphere, and then the tungsten-boron composite obtained after the first sintering is mixed with aluminum, molybdenum, niobium and titanium for second sintering, which can effectively avoid the segregation and aggregation of boron during the mixing process, thereby effectively improving the shielding performance of the radiation shielding high-entropy alloy against neutron radiation and γ-rays; and the obtained tungsten-boron compound has a small density difference from aluminum, molybdenum, niobium and titanium, thereby ensuring good mixing uniformity with aluminum, molybdenum, niobium and titanium, effectively promoting boron to play a neutron shielding role and tungsten to play a γ-ray shielding role, so that the prepared radiation shielding high-entropy alloy has good comprehensive radiation shielding performance against neutron radiation and γ-rays and good high-temperature mechanical properties; at the same time, since the obtained is a radiation shielding high-entropy alloy, it also has good wear resistance and corrosion resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] To more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the following will briefly introduce the accompanying drawings required for the description of the specific embodiments or the prior art. Obviously, the accompanying drawings in the following description are some embodiments of the present application. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0032] Figure 1 Appearance diagram of the radiation shielding high-entropy alloy A prepared for the example. Specific embodiments

[0033] Reference will now be provided in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation and not limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made to the invention without departing from the scope or spirit of the invention. For example, features described or illustrated as part of one embodiment can be used in another embodiment to yield a still further embodiment.

[0034] Accordingly, it is intended that the invention cover such modifications and variations that fall within the scope of the appended claims and their equivalents. Other objects, features, and aspects of the invention are disclosed in the following detailed description or are apparent therefrom. Those of ordinary skill in the art should understand that this discussion is only a description of exemplary embodiments and is not intended to limit the broader aspects of the invention.

[0035] Unless otherwise defined, 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 terms used in the description of the present invention in this specification are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0036] The term "comprising", "including" or any other variation thereof is intended to cover a non-exclusive inclusion, such that a process, method, article or apparatus comprising a series of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article or apparatus. Without further limitation, an element defined by the phrase "comprising a..." does not exclude the presence of additional identical elements in the process, method, article or apparatus comprising the element. The indefinite articles "a" and "an" preceding elements or components of the present invention do not limit the number requirement (i.e., the number of occurrences) of the elements or components. Thus, "a" or "an" should be read as including one or at least one, and the singular form of an element or component also includes the plural form unless the number clearly refers only to the singular form. The meaning of "a plurality" is at least two, such as two, three, etc., unless otherwise specifically defined.

[0037] In the description of the embodiments of the present invention, the weight of the relevant components mentioned not only can refer to the specific content of each component, but also can represent the proportional relationship of the weights between the components. Therefore, as long as the content of the relevant components in the description of the embodiments of the present invention is enlarged or reduced in proportion, it is within the scope disclosed in the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiments of the present invention can be mass units well-known in the chemical engineering field such as μg, mg, g, kg, etc.

[0038] Unless otherwise indicated in the operating examples or otherwise stated, all numbers used to represent the amounts of components, physical and chemical properties, etc. in the specification and claims are understood to be adjusted by the term "about" in all cases. For example, therefore, unless otherwise stated, the numerical parameters listed in the above specification and the appended claims are approximate values, and those skilled in the art can appropriately change these approximate values to obtain the desired characteristics by using the teachings disclosed herein. The use of numerical ranges expressed by endpoints includes all numbers within the range and any range within the range. For example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and so on.

[0039] During the research process, the technicians of the present application found that when directly using boron powder, obvious segregation and aggregation phenomena of boron powder would occur during the mixing process, resulting in unstable performance or local deterioration of the alloy material, and the addition ratio of boron powder was severely limited.

[0040] One embodiment of the present application provides a preparation method of a radiation shielding high-entropy alloy, including steps S10 to S20:

[0041] Step S10: Mix tungsten element and boron element and then perform first sintering in an inert gas atmosphere to obtain a tungsten boride composite.

[0042] By first mixing tungsten element and boron element and then performing first sintering in an inert gas atmosphere, the segregation and aggregation phenomena of boron element during the mixing process can be effectively avoided.

[0043] In some examples, in step S10, the molar ratio of tungsten element to boron element is (0.5 to 2.0):1.

[0044] It can be understood that the molar ratio of tungsten element to boron element includes but is not limited to 0.5:1, 1:1, 1.5:1, 2:1. In some examples, it can be within the range formed by any two of these point values as the end values. The same applies hereinafter.

[0045] In some examples, in step S10, the molar ratio of tungsten element to boron element is 2:1.

[0046] It can be understood that the inert gas includes, but is not limited to, helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn), and Og.

[0047] In some of these examples, in step S10, the inert gas atmosphere includes at least one of helium, neon, argon, krypton, and xenon.

[0048] It can be understood that after mixing elemental tungsten and elemental boron and performing the first sintering in a specific type of inert gas atmosphere, oxidation at high temperatures is avoided, enabling the formation of a uniform WB compound; if elemental tungsten and elemental boron are mixed and sintered in nitrogen, tungsten nitride will be formed, thereby introducing an impurity phase; if sintered in air, tungsten nitride and oxides will be formed, introducing an impurity phase.

[0049] Optionally, the inert gas atmosphere is argon.

[0050] In some of these examples, in step S10, the temperature of the first sintering is 1200 °C to 1400 °C.

[0051] It can be understood that the temperature of the first sintering includes, but is not limited to, 1200 °C, 1220 °C, 1250 °C, 1280 °C, 1300 °C, 1320 °C, 1350 °C, 1380 °C, 1400 °C.

[0052] In some of these examples, in step S10, the method of mixing elemental tungsten and elemental boron is the mechanical mixing method.

[0053] In some of these examples, in step S10, after the first sintering step, it further includes a step of crushing the sintered product obtained from the first sintering.

[0054] Further, after crushing, it further includes a step of grinding.

[0055] It can be understood that after crushing and grinding, the tungsten-boron composite is tungsten-boron composite powder.

[0056] Further, the particle size of the tungsten-boron composite is 100 to 200 mesh.

[0057] Step S20: Mix the tungsten-boron composite with elemental aluminum, elemental molybdenum, elemental niobium, and elemental titanium and then perform the second sintering.

[0058] For the preparation method of the above-mentioned radiation shielding high-entropy alloy, tungsten and boron are first mixed and then subjected to the first sintering under an inert gas atmosphere. Then, the tungsten-boron composite obtained after the first sintering is mixed with aluminum, molybdenum, niobium, and titanium for the second sintering, which can effectively avoid the segregation and aggregation of boron during the mixing process, thereby effectively improving the shielding performance of the radiation shielding high-entropy alloy against neutron radiation and γ-rays. Moreover, the density difference between the obtained tungsten-boron compound and aluminum, molybdenum, niobium, and titanium is small, thus ensuring good uniformity in mixing with aluminum, molybdenum, niobium, and titanium, effectively promoting boron to play a neutron shielding role and tungsten to play a γ-ray shielding role, so that the prepared radiation shielding high-entropy alloy has good comprehensive radiation shielding performance against neutron radiation and γ-rays and good high-temperature mechanical properties. At the same time, since the obtained is a radiation shielding high-entropy alloy, it also has good wear resistance and corrosion resistance.

[0059] In some examples, in step S20, the molar ratio of aluminum, molybdenum, niobium, titanium to the tungsten-boron composite is (0.8~1.2):(0.5~1.0):(0.5~1.0):(0.8~1.2):1.

[0060] It can be understood that taking the amount of substance of the tungsten-boron composite as 1 unit, the amount of substance of aluminum includes but is not limited to 0.8, 1, 1.1, 1.2 units; the amount of substance of molybdenum includes but is not limited to 0.5, 0.8, 1 unit; the amount of substance of niobium includes but is not limited to 0.5, 0.8, 1 unit; the amount of substance of titanium includes but is not limited to 0.8, 1, 1.1, 1.2 units.

[0061] In some examples, in step S20, the molar ratio of aluminum, molybdenum, niobium, titanium to the tungsten-boron composite is 1:1:1:1:1.

[0062] By controlling the molar ratio of tungsten to boron and the molar ratio of aluminum, molybdenum, niobium, titanium to the tungsten-boron composite, the molar contents of tungsten, boron, aluminum, molybdenum, niobium, and titanium in the finally obtained radiation shielding high-entropy alloy can be controlled.

[0063] It can be understood that when the molar ratio of tungsten to boron is 2:1 and the molar ratio of aluminum, molybdenum, niobium, titanium to the tungsten-boron composite is 1:1:1:1:1, the molar content of boron in the finally prepared radiation shielding high-entropy alloy is about 6.7%.

[0064] In some examples, in the preparation method of the radiation shielding high-entropy alloy, the purity of tungsten, boron, aluminum, molybdenum, niobium, and titanium is ≥99.9%.

[0065] In some of these examples, in the method for preparing a radiation shielding high-entropy alloy, tungsten, boron, aluminum, molybdenum, niobium, and titanium are all added in the form of powders.

[0066] That is, in some examples, the method for preparing a radiation shielding high-entropy alloy includes the following steps:

[0067] Mix tungsten powder and boron powder and conduct a first sintering under an inert gas atmosphere to obtain a tungsten-boron composite;

[0068] Mix the tungsten-boron composite with aluminum powder, molybdenum powder, niobium powder, and titanium powder and then conduct a second sintering.

[0069] In some of these examples, in the method for preparing a radiation shielding high-entropy alloy, the particle size of tungsten is 100 - 1000 mesh.

[0070] In some of these examples, in the method for preparing a radiation shielding high-entropy alloy, the particle size of boron is 100 - 1000 mesh.

[0071] In some of these examples, in the method for preparing a radiation shielding high-entropy alloy, the particle size of aluminum is 150 - 500 mesh.

[0072] In some of these examples, in the method for preparing a radiation shielding high-entropy alloy, the particle size of molybdenum is 150 - 500 mesh.

[0073] In some of these examples, in the method for preparing a radiation shielding high-entropy alloy, the particle size of niobium is 150 - 500 mesh.

[0074] In some of these examples, in the method for preparing a radiation shielding high-entropy alloy, the particle size of titanium is 150 - 500 mesh.

[0075] It can be understood that the method of the second sintering includes but is not limited to spark plasma sintering, vacuum arc melting, etc.

[0076] In some of these examples, in step S20, spark plasma sintering is selected for the second sintering.

[0077] It can be understood that spark plasma sintering is carried out using an SPS spark plasma sintering furnace.

[0078] In some of these examples, in step S20, the temperature of the second sintering is 1350°C - 1500°C.

[0079] It can be understood that the temperature of the second sintering includes but is not limited to 1350°C, 1380°C, 1400°C, 1420°C, 1450°C, 1480°C, 1500°C.

[0080] In some of these examples, in step S20, the pressure of the second sintering is 25 MPa to 32 MPa.

[0081] It can be 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, and 32 MPa.

[0082] In some of these examples, in step S20, the time of the second sintering is 5 min to 15 min.

[0083] It can be understood that the time of the second sintering includes but is not limited to 5 min, 6 min, 8 min, 10 min, 12 min, and 15 min.

[0084] In some of these examples, in step S20, the temperature of the second sintering is 1400 °C to 1500 °C, the pressure is 28 MPa to 30 MPa, and the time is 8 min to 12 min.

[0085] In some specific examples, in step S20, the temperature of the second sintering is 1450 °C.

[0086] In some of these examples, in step S20, before performing the second sintering step, it further includes a step of ball-milling a mixture obtained by mixing a tungsten boride composite with aluminum, molybdenum, niobium, and titanium.

[0087] In some of these examples, in step S20, the parameters of the ball-milling are: rotational speed 300 r / min to 450 r / min, ball-to-material ratio 4:1 to 15:1, and ball-milling time 20 h to 100 h.

[0088] It can be understood that the rotational speed of the ball-milling includes but is 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, the ball-to-material ratio includes but is not limited to 4:1, 5:1, 6:1, 7:1, 8:1, 10:1, 12:1, 14:1, 15:1, and the ball-milling time includes but is not limited to 20 h, 30 h, 40 h, 50 h, 60 h, 70 h, 80 h, 90 h, 100 h.

[0089] Optionally, the parameters of the ball-milling are: rotational speed 350 r / min to 450 r / min, ball-to-material ratio 8:1 to 12:1, and ball-milling time 30 h to 60 h.

[0090] In some of these examples, in step S20, the mixture obtained by mixing the tungsten boron composite with aluminum, molybdenum, niobium and titanium is loaded into a zirconia ceramic pot for ball milling.

[0091] Further, the ceramic pot can be selected from zirconia ceramic pots.

[0092] Further, the ball milling is carried out in an inert gas atmosphere. Optionally, the ball milling is carried out under argon conditions.

[0093] Further, a planetary ball mill is used for mechanical alloying high energy ball milling.

[0094] In some of these examples, in the method for preparing a radiation shielding high entropy alloy, after step S20, it further includes step S30:

[0095] A boron coating layer is provided on the surface of the alloy obtained in the second sintering step.

[0096] In some of these examples, in step S30, a boron-rich layer is provided on the surface of the alloy obtained in the second sintering step by the pack cementation method.

[0097] By providing a boron-rich layer on the surface of the alloy obtained in the second sintering step, the absorption of neutrons in a complex neutron / γ-ray radiation environment is effectively improved, the neutron absorption rate is increased, and thus the shielding performance of the radiation shielding high entropy alloy against neutron irradiation in a complex neutron / γ-ray radiation environment is further improved.

[0098] In some of these examples, in step S30, the boron cementation temperature is 1000°C to 1200°C, and the boron cementation time is 4 h to 24 h.

[0099] It can be understood that the boron cementation temperature includes but is not limited to 1000°C, 1050°C, 1100°C, 1120°C, 1150°C, 0°C, 1200°C, and the boron cementation time includes but is not limited to 4 h, 8 h, 10 h, 15 h, 20 h, 24 h.

[0100] In some of these examples, in step S30, argon protection is used in the pack cementation method.

[0101] In some of these examples, in step S30, the boron cementation raw materials in the pack cementation method include boron powder and an accelerating agent.

[0102] Further, the accelerating agent includes rare metal oxides.

[0103] Even further, the accelerating agent includes at least one of yttrium oxide and lanthanum oxide.

[0104] Correspondingly, an embodiment of the present application provides a radiation shielding high entropy alloy prepared by the above preparation method.

[0105] On the other hand, the present application provides a radiation shielding high-entropy alloy, which includes a core layer, and the components of the core layer include tungsten, boron, aluminum, molybdenum, niobium and titanium.

[0106] In some embodiments of the radiation shielding high-entropy alloy, by molar percentage, the core layer includes the following components: Al 16.00% - 30.00%, W 6.17% - 18.52%, Mo 10.20% - 24.39%, Nb 10.20% - 24.39%, Ti 16.00% - 30.00% and B 6.17% - 18.52%.

[0107] It can be understood that by molar percentage, Al includes but is not limited to 16.00%, 18.00%, 20.00%, 22.00%, 25.00%, 28.00%, 30.00%; 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 B 6.17%, 8%, 10%, 15%, 18.52%.

[0108] In the radiation shielding high-entropy alloy WMoNbAlTiB provided by the present application, the boron element interacts with tungsten, aluminum, molybdenum, niobium and titanium, which can make the content of B added in the radiation shielding high-entropy alloy relatively high, up to more than 10%. As a result, the radiation shielding high-entropy alloy has good radiation shielding performance for both neutron radiation and γ-rays, good high-temperature mechanical properties, as well as good wear resistance and corrosion resistance.

[0109] Ni is easily corroded by lead-bismuth alloys (the primary coolant of lead-based reactors). Under accident conditions, the lead-bismuth alloy may overflow and corrode the shielding structure, making Ni-containing materials unable to be used for shielding in lead-bismuth environments or the shielding structure inside lead-bismuth reactors. The radiation shielding high-entropy alloy of the present application does not contain Ni and can be used for shielding in lead-bismuth environments or the shielding structure inside lead-bismuth reactors.

[0110] In some embodiments of the radiation shielding high-entropy alloy, the radiation shielding high-entropy alloy further includes a boron coating layer disposed on the surface of the core layer.

[0111] In this way, the shielding performance of the radiation shielding high-entropy alloy against neutron irradiation in a complex neutron / γ-ray radiation environment can be further improved.

[0112] In some of these embodiments, in the radiation shielding high-entropy alloy, the thickness of the boron coating layer is 2 μm to 50 μm.

[0113] It can be understood that the thickness of the boron coating layer includes but is not limited to 2 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm.

[0114] One embodiment of the present application provides the application of the above-mentioned radiation shielding high-entropy alloy in the preparation of radiation shielding products. Another embodiment of the present application provides a radiation shielding product, the material of which includes the above-mentioned radiation shielding high-entropy alloy.

[0115] In some of these embodiments, the radiation shielding products include but are not limited to radiation protection clothing, radiation protection covers, radiation protection helmets, etc.

[0116] The above-mentioned radiation shielding high-entropy alloy is used to prepare radiation shielding products, which has good shielding performance against neutron radiation and γ-ray radiation, and can also endow the radiation shielding products with good high-temperature mechanical properties, wear resistance and corrosion resistance.

[0117] In some of these embodiments, the material of the radiation shielding product can be the above-mentioned radiation shielding high-entropy alloy, that is, the radiation shielding product is directly prepared using the above-mentioned radiation shielding high-entropy alloy. In other embodiments, the material of the radiation shielding product can include other materials in addition to the above-mentioned radiation shielding high-entropy alloy.

[0118] The following further describes the present application in detail in conjunction with specific embodiments, but the embodiments of the present application are not limited thereto.

[0119] Example 1

[0120] (1) Tungsten powder with a particle size of 500 mesh and boron powder with a particle size of 300 mesh are mixed according to a molar ratio of 2:1. After being uniformly mixed by mechanical alloying, it is placed under argon conditions and sintered for the first time at 1250 °C, and after being crushed and ground, tungsten-boron composite powder is obtained;

[0121] (2) The tungsten-boron composite powder is mixed with aluminum powder with a particle size of 500 mesh, molybdenum powder with a particle size of 1000 mesh, niobium powder with a particle size of 500 mesh, and titanium powder with a particle size of 800 mesh according to a molar ratio of 1:1:1:1:1, and is loaded into a zirconia ceramic pot. Argon is filled into the ceramic pot to ensure positive pressure in the pot, and mechanical alloying high-energy ball milling is carried out using a planetary ball mill. The ball milling parameters are: rotation speed 400 r / min, ball-to-material ratio 10:1, and ball milling time 40 h;

[0122] (3) Load the ball-milled mixed powder into a sizing die and perform spark plasma sintering using a spark plasma sintering furnace. The sintering parameters are: sintering temperature 1450 °C, sintering pressure 28 MPa, holding time 10 min, to obtain a radiation shielding high-entropy alloy. The molar ratio of W, B, Mo, Nb, Al, and Ti in the radiation shielding high-entropy alloy is 2 / 3:1 / 3:1:1:1:1. The appearance of the radiation shielding high-entropy alloy A is as shown in Figure 1 shown;

[0123] (4) Adopt the pack boriding method to boronize the surface of the radiation shielding high-entropy alloy A, and form a dense boron-rich coating layer on the surface of the radiation shielding high-entropy alloy A to obtain the radiation shielding high-entropy alloy B. Among them, boron powder and the promoting agent yttrium oxide are used as the boronizing raw materials, and argon protection is adopted. The boronizing temperature is 1000 °C to 1200 °C, and the boronizing holding time is 4 h to 24 h. After the holding is completed, the furnace is cooled.

[0124] Example 2

[0125] It is basically the same as Example 1, except that in step (1), the molar ratio of tungsten powder to boron powder is 1:2, that is, the molar ratio of W, B, Mo, Nb, Al, and Ti in the radiation shielding high-entropy alloy A obtained in Example 2 is 1 / 3:2 / 3:1:1:1:1.

[0126] The radiation shielding high-entropy alloys B prepared in each example were respectively tested for the shielding performance of neutrons and γ-rays in accordance with the relevant requirements of GBZ / T 147-2002 "Determination of the Attenuation Performance of X-ray Protective Materials", and the yield strength tests at 25 °C and 800 °C were respectively carried out in accordance with GB / T 228.1-2021 (Metallic materials - Tensile testing - Part 1: Method of test at room temperature) and GB / T 228.2-2015 (Metallic materials - Tensile testing - Part 2: Method of test at elevated temperature). The test results are shown in Table 1.

[0127] Table 1

[0128]

[0129] As can be seen from Table 1, the B-containing WMoNbAlTi radiation shielding high-entropy alloy prepared by the present invention has significantly better comprehensive shielding capabilities for neutrons and γ-rays than traditional high-entropy alloys, and at the same time has good room-temperature mechanical properties and excellent medium- and high-temperature mechanical properties, and is suitable for structural parts or equipment with shielding requirements in medium- and high-temperature service environments, or to meet the complex requirements of comprehensive neutron / γ-ray shielding protection.

[0130] The technical features of the above-described embodiments may be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0131] The above-described embodiments only represent several implementation manners of the present application, which are convenient for understanding the technical solutions of the present application specifically and in detail, but should not be construed as a limitation on the protection scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several deformations and improvements can be made, and these all belong to the protection scope of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the protection scope of the appended claims of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the content of the appended claims, and the description and drawings can be used to explain the content of the claims.

Claims

1. A preparation method of a radiation-shielding high-entropy alloy, characterized in that, It includes the following steps: Mix tungsten and boron elements and conduct the first sintering in an inert gas atmosphere to obtain a tungsten-boron composite; and Mix the tungsten-boron composite with aluminum, molybdenum, niobium, and titanium elements and conduct the second sintering; The molar ratio of the tungsten element to the boron element is (0.5 - 2.0):1, and the molar ratio of the aluminum element, the molybdenum element, the niobium element, the titanium element to the tungsten-boron composite is (0.8 - 1.2):(0.5 - 1.0):(0.5 - 1.0):(0.8 - 1.2):

1.

2. The preparation method according to claim 1, characterized in that, The molar ratio of the aluminum element, the molybdenum element, the niobium element, the titanium element to the tungsten-boron composite is 1:1:1:1:

1.

3. The preparation method according to any one of claims 1 to 2, characterized in that, The tungsten element, the boron element, the aluminum element, the molybdenum element, the niobium element, and the titanium element are all added in the form of powders.

4. The preparation method according to claim 3, characterized in that, The preparation method satisfies at least one of the following characteristics (1) - (6): (1) The particle size of the tungsten element is 100 - 1000 mesh; (2) The particle size of the boron element is 100 - 1000 mesh; (3) The particle size of the aluminum element is 150 - 500 mesh; (4) The particle size of the molybdenum element is 150 - 500 mesh; (5) The particle size of the niobium element is 150 - 500 mesh; (6) The particle size of the titanium element is 150 - 500 mesh.

5. The preparation method according to any one of claims 1 to 2 and 4, characterized in that, The temperature of the first sintering is 1200°C - 1400°C.

6. The preparation method according to any one of claims 1 to 2 and 4, characterized in that, The temperature of the second sintering is 1350°C - 1500°C, the pressure is 25 MPa - 32 MPa, and the time is 5 min - 15 min.

7. The preparation method according to any one of claims 1 to 2 and 4, characterized in that, After the second sintering step, it further includes the step of setting a boron coating layer on the surface of the alloy obtained in the second sintering step.

8. A radiation-shielding high-entropy alloy, characterized in that, Prepared by the preparation method according to any one of claims 1 - 7.

9. The radiation shielding high-entropy alloy according to claim 8, characterized in that, The radiation shielding high-entropy alloy includes a core layer, and the components of the core layer include tungsten, boron, aluminum, molybdenum, niobium, and titanium.

10. The radiation shielding high-entropy alloy according to claim 9, wherein By molar percentage, the core layer includes the following components: Al 16.00% - 30.00%, W 6.17% - 18.52%, Mo 10.20% - 24.39%, Nb 10.20% - 24.39%, Ti 16.00% - 30.00%, and B 6.17% - 18.52%.

11. The radiation-shielding high-entropy alloy according to any one of claims 9 to 10, wherein The radiation shielding high-entropy alloy further includes a boron coating layer provided on the surface of the core layer.

12. The radiation shielding high-entropy alloy according to claim 11, wherein, The thickness of the boron coating layer is 2 μm - 50 μm.

13. Use of the radiation shielding high-entropy alloy according to any one of claims 8 - 12 in the preparation of radiation shielding products.

14. A radiation shielding article, characterized in that, It includes the radiation shielding high-entropy alloy according to any one of claims 8 - 12.

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