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

Abstract

The present application relates to a radiation shielding high-entropy alloy, a preparation method therefor, a use thereof, and a radiation shielding product. The preparation method for the radiation shielding high-entropy alloy comprises the following steps: mixing elemental tungsten and elemental boron and then performing first sintering in an inert gas atmosphere, so as to obtain a tungsten-boron composite; and mixing the tungsten-boron composite with elemental aluminum, elemental molybdenum, elemental niobium and elemental titanium and then performing 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, has good high-temperature mechanical properties, and also has good wear resistance and corrosion resistance.

Description

Radiation shielding high entropy alloys, preparation methods and applications thereof, and radiation shielding products

[0001] Related applications

[0002] This application claims priority to Chinese patent application No. 202311565426.7, filed on November 22, 2023, entitled “Radiation Shielding High Entropy Alloy, Preparation Method and Application thereof, Radiation Shielding Products”, the entire text of which is hereby incorporated by reference. Technical Field

[0003] The present application relates to the field of alloys, and in particular to a radiation shielding high entropy alloy, a preparation method and application thereof, and radiation shielding products. Background Art

[0004] With the energy crisis and the increasingly urgent need for carbon neutrality, the development and utilization of nuclear energy has garnered widespread attention. Pressurized water reactors (PWRs), based on second- and third-generation nuclear power technologies, are increasingly being used. Meanwhile, advanced fourth-generation nuclear power technologies, represented by sodium-cooled fast reactors and lead-cooled fast reactors, are also receiving strong support and experiencing rapid development. The future widespread application of nuclear energy and the rapid and sustainable development of the nuclear power industry depend on innovations in radiation protection and safety technologies.

[0005] For nuclear power plants, neutron and gamma-ray radiation are the most significant of the various types of nuclear radiation, and the need for shielding is the most pressing. Traditional composite shielding materials include metal-based composites, ceramic-based composites, and polymer-based composites, but these materials suffer from poor mechanical properties at medium and high temperatures.

[0006] High-entropy alloys (HEAs) are a new alloy design concept that has emerged in recent years. They are composed of five or more metallic elements, with the atomic proportion of each element ranging from 5% to 35%. The disordered solid solution within these alloys makes it difficult to distinguish between solvent and solute. Their components are generally located at the center of the phase diagram, exhibiting high mixing entropy. They tend to form simple solid solution phases such as body-centered cubic (BCC), face-centered cubic (FCC), and hexagonal close-packed (HCP), rather than intermetallic compounds or other complex ordered phases. This unique crystal structure enables HEAs to exhibit many superior properties that distinguish them from traditional metal alloys, such as high strength, high room-temperature toughness, and excellent wear, oxidation, and corrosion resistance, as well as thermal stability. However, traditional HEAs cannot simultaneously provide effective shielding against neutron and gamma-ray radiation.

[0007] Summary of the Invention

[0008] Based on this, the present application provides a radiation shielding high entropy alloy having good radiation shielding performance against neutron radiation and gamma rays, and good high-temperature mechanical properties, as well as a preparation method and application thereof.

[0009] The technical solution of this application to solve the above technical problems is as follows.

[0010] On the one hand, the present application provides a method for preparing a radiation shielding high entropy alloy, comprising the following steps:

[0011] Mixing tungsten and boron and then performing a first sintering process under an inert gas atmosphere to obtain a tungsten-boron composite; and

[0012] The tungsten-boron composite is mixed with aluminum, molybdenum, niobium and titanium, and then subjected to a second sintering.

[0013] In some embodiments, in the method for preparing the radiation shielding high entropy alloy, the molar ratio of the tungsten element to the boron element is (0.5-2.0):1.

[0014] In some 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 and the tungsten-boron complex is (0.8-1.2):(0.5-1.0):(0.5-1.0):(0.8-1.2):1.

[0015] In some embodiments, in the method for preparing the 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 powder.

[0016] In some embodiments, in the method for preparing a radiation shielding high entropy alloy, the particle size of the tungsten element is 100-1000 mesh.

[0017] In some embodiments, in the method for preparing a radiation shielding high entropy alloy, the particle size of the boron element is 100-1000 mesh.

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

[0019] In some embodiments, in the method for preparing a radiation shielding high entropy alloy, the particle size of the molybdenum element is 150-500 mesh.

[0020] In some embodiments, in the method for preparing the radiation shielding high entropy alloy, the particle size of the niobium element is 150-500 mesh.

[0021] In some embodiments, in the method for preparing a radiation shielding high entropy alloy, the particle size of the titanium element is 150-500 mesh.

[0022] In some embodiments, in the method for preparing a radiation shielding high entropy alloy, the temperature of the first sintering is 1200°C to 1400°C.

[0023] In some embodiments, in the method for preparing a radiation shielding high entropy alloy, the second sintering is performed at a temperature of 1350° C. to 1500° C., a pressure of 25 MPa to 32 MPa, and a time of 5 min to 15 min.

[0024] In some embodiments, the method for preparing a radiation shielding high entropy alloy further includes, after the second sintering step, providing a boron coating layer on the surface of the alloy obtained in the second sintering step.

[0025] Accordingly, the present application provides a radiation shielding high entropy alloy prepared by the above preparation method.

[0026] 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.

[0027] In some embodiments, in the radiation shielding high entropy alloy, the core layer includes the following components, based on molar percentage: Al 16.00% to 30.00%, W 6.17% to 18.52%, Mo 10.20% to 24.39%, Nb 10.20% to 24.39%, Ti 16.00% to 30.00% and B 6.17% to 18.52%.

[0028] 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.

[0029] In some embodiments, in the radiation shielding high entropy alloy, the thickness of the boron coating layer is 2 μm to 50 μm.

[0030] The present application also provides the use of the above-mentioned radiation shielding high entropy alloy in the preparation of radiation shielding products.

[0031] The present application also provides a radiation shielding product, comprising the above-mentioned radiation shielding high entropy alloy.

[0032] Compared with the prior art, the preparation method of the radiation shielding high entropy alloy of the present application has the following beneficial effects:

[0033] The preparation method of the above-mentioned radiation shielding high-entropy alloy is to first mix tungsten and boron elements and then perform a first sintering in an inert gas atmosphere, and then mix the tungsten-boron composite obtained after the first sintering with aluminum, molybdenum, niobium and titanium elements for a second sintering, which can effectively avoid the segregation and aggregation of boron elements during the mixing process, thereby effectively improving the shielding performance of the radiation shielding high-entropy alloy against neutron radiation and gamma rays; and the density of the obtained tungsten-boron compound is relatively small compared with that of aluminum, molybdenum, niobium and titanium, thereby ensuring good uniformity of mixing with aluminum, molybdenum, niobium and titanium, effectively promoting boron to play a neutron shielding role and tungsten to play a gamma-ray shielding role, so that the obtained radiation shielding high-entropy alloy has good comprehensive radiation shielding performance against neutron radiation and gamma 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

[0034] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the conventional technology, the following briefly introduces the drawings required for use in the embodiments or the conventional technology descriptions. Obviously, the drawings described below are merely embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on the disclosed drawings without any creative work.

[0035] FIG1 is an appearance diagram of the radiation shielding high entropy alloy A prepared in Example 1. DETAILED DESCRIPTION

[0036] The following will be combined with the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0037] The term "comprises", "comprising" or any other variant thereof is intended to cover non-exclusive inclusion, so that the process, method, article or equipment comprising a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or equipment. In the absence of further restrictions, the elements limited by the sentence "comprising a ..." do not exclude the presence of other identical elements in the process, method, article or equipment comprising the elements. The indefinite articles "a" and "an" before the elements or components of the present invention have no restriction on the quantity requirements (i.e., the number of occurrences) of the elements or components. Therefore, "a" or "a" should be interpreted as including one or at least one, and elements or components in the singular also include plural forms, unless the quantity obviously refers only to the singular form. The meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0038] The weights of the relevant components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the weight ratio between the components. Therefore, as long as the content of the relevant components is proportionally increased or decreased according to the description of the embodiments of the present invention, it is within the scope disclosed in the description of the embodiments of the present invention. Specifically, the weights mentioned in the description of the embodiments of the present invention may be mass units known in the chemical industry, such as μg, mg, g, and kg.

[0039] Except as shown in the operating examples or otherwise indicated, all numbers used in the specification and claims to express the amount of ingredients, physicochemical properties, etc. are understood to be adjusted by the term "about" in all cases. For example, therefore, unless otherwise indicated, the numerical parameters listed in the above specification and the appended claims are approximate values, and those skilled in the art will be able to appropriately change these approximate values ​​using the teachings disclosed herein to seek to obtain the desired properties. The use of numerical ranges expressed as 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, etc.

[0040] During the research process, the technical personnel of this application found that when boron powder is used directly, obvious boron powder segregation and aggregation will occur during the mixing process, resulting in unstable or localized deterioration of the alloy material performance, and the addition ratio of boron powder is severely limited.

[0041] One embodiment of the present application provides a method for preparing a radiation shielding high entropy alloy, comprising steps S10 to S20:

[0042] Step S10: mixing tungsten and boron, and then performing a first sintering process under an inert gas atmosphere to obtain a tungsten-boron composite.

[0043] By first mixing the tungsten element and the boron element and then performing the first sintering in an inert gas atmosphere, the segregation and aggregation of the boron element during the mixing process can be effectively avoided.

[0044] In some examples, in step S10 , the molar ratio of tungsten element to boron element is (0.5-2.0):1.

[0045] It is understood that the molar ratio of tungsten to boron includes but is not limited to 0.5:1, 1:1, 1.5:1, and 2:1. In some examples, the molar ratio may be within a range formed by any two of these values ​​as end values, and the same applies hereinafter.

[0046] In some examples, in step S10 , the molar ratio of tungsten to boron is 2:1.

[0047] It is 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.

[0048] In some examples, in step S10 , the inert gas atmosphere includes at least one of helium, neon, argon, krypton, and xenon.

[0049] It can be understood that after mixing tungsten and boron, the first sintering is carried out in a specific type of inert gas atmosphere to avoid oxidation at high temperature and to form a uniform WB compound; if tungsten and boron are mixed and sintered in nitrogen, tungsten nitride will be generated, thereby introducing an impurity phase; if sintered in air, tungsten nitride and oxide will be generated, thereby introducing an impurity phase.

[0050] Optionally, the inert gas atmosphere is argon.

[0051] In some examples, in step S10 , the temperature of the first sintering is 1200° C. to 1400° C.

[0052] 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, and 1400°C.

[0053] In some examples, in step S10 , the tungsten element and the boron element are mixed by mechanical mixing.

[0054] In some examples, in step S10 , after the first sintering step, the method further includes crushing the sintered product obtained by the first sintering step.

[0055] Furthermore, the crushing step also includes a grinding step.

[0056] It can be understood that after crushing and grinding, the tungsten-boron composite is tungsten-boron composite powder.

[0057] Furthermore, the particle size of the tungsten-boron composite is 100-200 meshes.

[0058] Step S20: mixing the tungsten-boron composite with aluminum, molybdenum, niobium and titanium, and then performing a second sintering.

[0059] The preparation method of the above-mentioned radiation shielding high-entropy alloy is to first mix tungsten and boron elements and then perform a first sintering in an inert gas atmosphere, and then mix the tungsten-boron composite obtained after the first sintering with aluminum, molybdenum, niobium and titanium elements for a second sintering, which can effectively avoid the segregation and aggregation of boron elements during the mixing process, thereby effectively improving the shielding performance of the radiation shielding high-entropy alloy against neutron radiation and gamma rays; and the density of the obtained tungsten-boron compound is relatively small compared with that of aluminum, molybdenum, niobium and titanium, thereby ensuring good uniformity of mixing with aluminum, molybdenum, niobium and titanium, effectively promoting boron to play a neutron shielding role and tungsten to play a gamma-ray shielding role, so that the obtained radiation shielding high-entropy alloy has good comprehensive radiation shielding performance against neutron radiation and gamma 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.

[0060] In some examples, in step S20 , the molar ratio of aluminum, molybdenum, niobium, titanium and tungsten-boron complex is (0.8-1.2):(0.5-1.0):(0.5-1.0):(0.8-1.2):1.

[0061] It can be understood that the amount of substance of the tungsten-boron complex is 1 unit, the amount of substance of the aluminum element includes but is not limited to 0.8, 1, 1.1, and 1.2 units; the amount of substance of the molybdenum element includes but is not limited to 0.5, 0.8, and 1 unit; the amount of substance of the niobium element includes but is not limited to 0.5, 0.8, and 1 unit; the amount of substance of the titanium element includes but is not limited to 0.8, 1, 1.1, and 1.2 units.

[0062] In some examples, in step S20 , the molar ratio of aluminum, molybdenum, niobium, titanium, and the tungsten-boron complex is 1:1:1:1:1.

[0063] By controlling the molar ratio of tungsten to boron, and the molar ratio of aluminum, molybdenum, niobium, titanium and the tungsten-boron complex, the molar contents of tungsten, boron, aluminum, molybdenum, niobium and titanium in the final radiation shielding high entropy alloy can be controlled.

[0064] It can be understood that when the molar ratio of tungsten element to boron element is 2:1, and the molar ratio of aluminum element, molybdenum element, niobium element, titanium element and tungsten-boron complex is 1:1:1:1:1, the molar content of boron in the final radiation shielding high entropy alloy is about 6.7%.

[0065] In some examples, in the method for preparing the radiation shielding high entropy alloy, the purity of tungsten, boron, aluminum, molybdenum, niobium, and titanium is ≥99.9%.

[0066] In some examples, in the method for preparing the radiation shielding high entropy alloy, tungsten, boron, aluminum, molybdenum, niobium, and titanium are all added in the form of powder.

[0067] That is, in some examples, the method for preparing a radiation shielding high entropy alloy includes the following steps:

[0068] The tungsten powder and the boron powder are mixed and then first sintered in an inert gas atmosphere to obtain a tungsten-boron composite;

[0069] The tungsten-boron composite is mixed with aluminum powder, molybdenum powder, niobium powder and titanium powder and then subjected to a second sintering.

[0070] In some of the examples, in the method for preparing the radiation shielding high entropy alloy, the particle size of the tungsten element is 100 to 1000 mesh.

[0071] In some examples, in the method for preparing the radiation shielding high entropy alloy, the particle size of the boron element is 100 to 1000 mesh.

[0072] In some of the examples, in the method for preparing the radiation shielding high entropy alloy, the particle size of the aluminum element is 150 to 500 mesh.

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

[0074] In some of the examples, in the method for preparing the radiation shielding high entropy alloy, the particle size of the niobium element is 150 to 500 mesh.

[0075] In some of the examples, in the method for preparing the radiation shielding high entropy alloy, the particle size of the titanium element is 150 to 500 mesh.

[0076] It can be understood that the second sintering method includes but is not limited to spark plasma sintering, vacuum arc sintering, etc.

[0077] In some examples, in step S20 , spark plasma sintering is selected as the second sintering.

[0078] It can be understood that the spark plasma sintering is performed using an SPS spark plasma sintering furnace.

[0079] In some examples, in step S20 , the temperature of the second sintering is 1350° C. to 1500° C.

[0080] 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, and 1500°C.

[0081] In some examples, in step S20 , the pressure of the second sintering is 25 MPa to 32 MPa.

[0082] 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.

[0083] In some examples, in step S20 , the second sintering time is 5 minutes to 15 minutes.

[0084] It can be understood that the time for the second sintering includes but is not limited to 5 minutes, 6 minutes, 8 minutes, 10 minutes, 12 minutes, and 15 minutes.

[0085] In some examples, in step S20 , the second sintering is performed at a temperature of 1400° C. to 1500° C., at a pressure of 28 MPa to 30 MPa, and for a time of 8 min to 12 min.

[0086] In some specific examples, in step S20, the temperature of the second sintering is 1450°C.

[0087] In some examples, before the second sintering step, step S20 further includes ball milling the mixture of the tungsten-boron composite with aluminum, molybdenum, niobium, and titanium.

[0088] In some examples, in step S20, the parameters of ball milling are: rotation 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.

[0089] It will be understood that the ball milling speed includes but is not limited to 300r / min, 310r / min, 320r / min, 330r / min, 340r / min, 350r / min, 360r / min, 380r / min, 400r / min, 420r / min, 450r / 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 20h, 30h, 40h, 50h, 60h, 70h, 80h, 90h, 100h.

[0090] Optionally, the parameters of ball milling are: rotation 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.

[0091] In some examples, in step S20 , a mixture of the tungsten-boron composite and aluminum, molybdenum, niobium, and titanium is placed in a zirconia ceramic jar for ball milling.

[0092] Furthermore, the ceramic pot may be selected from zirconia ceramic pots.

[0093] Further, ball milling is performed under an inert gas atmosphere. Alternatively, ball milling is performed under argon gas conditions.

[0094] Furthermore, a planetary ball mill is used to perform mechanical alloying high-energy ball milling.

[0095] In some examples, the method for preparing the radiation shielding high entropy alloy further includes step S30 after step S20:

[0096] A boron coating layer is provided on the surface of the alloy obtained in the second sintering step.

[0097] In some examples, in step S30, a boron-rich layer is formed on the surface of the alloy obtained in the second sintering step by using an embedding boronizing method.

[0098] By setting a boron-rich layer on the surface of the alloy obtained in the second sintering step, the absorption of neutrons in a complex neutron / gamma-ray radiation environment is effectively improved, and the neutron absorption rate is increased, thereby further improving the shielding performance of the radiation shielding high entropy alloy against neutron irradiation in a complex neutron / gamma-ray radiation environment.

[0099] In some examples, in step S30 , the boronizing temperature is 1000° C. to 1200° C., and the boronizing time is 4 hours to 24 hours.

[0100] It can be understood that the boronizing temperature includes but is not limited to 1000℃, 1050℃, 1100℃, 1120℃, 1150℃, 0℃, and 1200℃, and the boronizing time includes but is not limited to 4h, 8h, 10h, 15h, 20h, and 24h.

[0101] In some examples, in step S30 , argon gas protection is used in the embedding boronizing method.

[0102] In some examples, in step S30, the boronizing raw materials of the embedding boronizing method include boron powder and a boronizing accelerator.

[0103] Furthermore, the penetration enhancer includes rare metal oxides.

[0104] Furthermore, the penetration enhancer includes at least one of yttrium oxide and lanthanum oxide.

[0105] Accordingly, one embodiment of the present application provides a radiation shielding high entropy alloy prepared by the above-mentioned preparation method.

[0106] 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.

[0107] In some embodiments, in the radiation shielding high entropy alloy, the core layer includes the following components, based on molar percentage: 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%.

[0108] It will be understood that, in terms of 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%.

[0109] The radiation shielding high entropy alloy WMoNbAlTiB provided in the present application has boron elements that interact with tungsten, aluminum, molybdenum, niobium and titanium, so that the B content added to the radiation shielding high entropy alloy can be relatively high, up to more than 10%, so that the radiation shielding high entropy alloy has good radiation shielding performance against neutron radiation and gamma rays at the same time, and good high-temperature mechanical properties, as well as good wear resistance and corrosion resistance.

[0110] Ni is easily corroded by lead-bismuth alloys (primary coolant in lead-based reactors). Under accident conditions, the lead-bismuth alloy may overflow and corrode shielding structures, making Ni-containing materials unsuitable for shielding in lead-bismuth environments or for shielding structures within lead-bismuth reactors. The radiation shielding high-entropy alloys in this application do not contain Ni and can be used for shielding in lead-bismuth environments or for shielding structures within lead-bismuth reactors.

[0111] In some embodiments, the radiation shielding high entropy alloy further comprises a boron coating layer disposed on the surface of the core layer.

[0112] In this way, the shielding performance of radiation shielding high entropy alloys against neutron irradiation in complex neutron / γ-ray radiation environments can be further improved.

[0113] In some embodiments, in the radiation shielding high entropy alloy, the thickness of the boron coating layer is 2 μm to 50 μm.

[0114] 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, and 50 μm.

[0115] One embodiment of the present application provides the use 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.

[0116] In some embodiments, the radiation shielding products include but are not limited to radiation protection clothing, radiation protection shields, radiation protection helmets, etc.

[0117] The above-mentioned radiation shielding high entropy alloy is used to prepare radiation shielding products, which have good shielding performance against neutron radiation and gamma ray radiation, and can also give the radiation shielding products good high-temperature mechanical properties, wear resistance and corrosion resistance.

[0118] In some embodiments, the material of the radiation shielding product can be the above-mentioned radiation shielding high entropy alloy, that is, the radiation shielding product can be 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.

[0119] The present application will be described in further detail below in conjunction with specific implementation methods, but the implementation methods of the present application are not limited thereto.

[0120] Example 1

[0121] (1) Tungsten powder with a particle size of 500 mesh and boron powder with a particle size of 300 mesh were mixed in a molar ratio of 2:1, mixed evenly by mechanical alloying, and then sintered at 1250°C under argon gas, crushed, and ground to obtain tungsten-boron composite powder;

[0122] (2) Tungsten-boron composite powder was 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 in a molar ratio of 1:1:1:1:1, and placed in a zirconia ceramic jar. Argon was filled into the ceramic jar to ensure positive pressure in the jar. Mechanical alloying and high-energy ball milling were performed using a planetary ball mill. The ball milling parameters were: speed 400 r / min, ball-to-material ratio 10:1, and ball milling time 40 h.

[0123] (3) The ball-milled mixed powder is placed into a mold and subjected to spark plasma sintering in an SPS spark plasma sintering furnace. The sintering parameters are: sintering temperature of 1450°C, sintering pressure of 28 MPa, and holding time of 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 shown in FIG1 .

[0124] (4) Boronizing the surface of radiation shielding high entropy alloy A by embedded boronizing method, forming a dense boron-rich coating layer on the surface of radiation shielding high entropy alloy A, and obtaining radiation shielding high entropy alloy B; wherein, boron powder and yttrium oxide as a boronizing raw material, argon gas protection is used, the boronizing temperature is 1000℃~1200℃, the boronizing holding time is 4h~24h, and the furnace is cooled after the holding is completed.

[0125] Example 2

[0126] 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.

[0127] The radiation shielding high entropy alloy B prepared in each embodiment was tested for neutron and gamma-ray shielding performance in accordance with the relevant requirements of GBZ / T 147-2002 "Determination of attenuation properties of X-ray shielding materials", and the yield strength was tested at 25°C and 800°C in accordance with GB / T 228.1-2021 (Tensile test of metallic materials Part 1: Room temperature test method) and GB / T 228.2-2015 (Tensile test of metallic materials Part 2: High temperature test method). The test results are shown in Table 1.

[0128] Table 1

[0129] As can be seen from Table 1, the WMoNbAlTi radiation shielding high-entropy alloy containing B element prepared in the present application has significantly better comprehensive shielding capabilities for neutrons and gamma rays than traditional high-entropy alloys. It also has good room temperature mechanical properties and very good medium and high temperature mechanical properties. It is suitable for structural parts or equipment with shielding requirements in medium and high temperature service environments, or meets the complex needs of neutron / gamma ray comprehensive shielding protection.

[0130] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0131] The above-described embodiments merely represent several implementation methods of the present application. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that a person of ordinary skill in the art may make various modifications and improvements without departing from the spirit of the present application, and these modifications and improvements fall within the scope of protection of the present application. Therefore, the scope of protection of the present patent application shall be determined by the appended claims.

Claims

1. A method for preparing a radiation shielding high entropy alloy, comprising the following steps: Mixing tungsten and boron and performing a first sintering in an inert gas atmosphere to obtain a tungsten-boron composite; and The tungsten-boron composite is mixed with aluminum, molybdenum, niobium and titanium and then subjected to a second sintering.

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

1.

3. The preparation method according to any one of claims 1 to 2, wherein: The molar ratio of the aluminum element, the molybdenum element, the niobium element, the titanium element and the tungsten-boron composite is (0.8-1.2):(0.5-1.0):(0.5-1.0):(0.8-1.2):

1.

4. The preparation method according to any one of claims 1 to 3, wherein 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 powder.

5. The preparation method according to any one of claims 1 to 4, wherein The particle size of the tungsten single substance is 100 to 1000 meshes.

6. The preparation method according to any one of claims 1 to 5, wherein: The particle size of the boron element is 100 to 1000 meshes.

7. The preparation method according to any one of claims 1 to 6, wherein: The particle size of the aluminum element is 150 to 500 meshes.

8. The preparation method according to any one of claims 1 to 7, wherein: The particle size of the molybdenum element is 150-500 meshes.

9. The preparation method according to any one of claims 1 to 8, wherein: The particle size of the niobium single substance is 150-500 meshes.

10. The preparation method according to any one of claims 1 to 9, wherein: The particle size of the titanium element is 150-500 meshes.

11. The preparation method according to any one of claims 1 to 10, wherein: The first sintering temperature is 1200°C to 1400°C.

12. The preparation method according to any one of claims 1 to 11, wherein: The second sintering is performed at a temperature of 1350° C. to 1500° C., a pressure of 25 MPa to 32 MPa, and a time of 5 min to 15 min.

13. The preparation method according to any one of claims 1 to 12, wherein: After performing the second sintering step, the method further includes providing a boron coating layer on the surface of the alloy obtained in the second sintering step.

14. A radiation shielding high entropy alloy, wherein: The compound is prepared by the preparation method according to any one of claims 1 to 13.

15. A radiation shielding high entropy alloy, comprising a core layer, wherein components of the core layer include tungsten, boron, aluminum, molybdenum, niobium and titanium.

16. The radiation shielding high entropy alloy of claim 15, wherein: In terms of mole 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%.

17. The radiation shielding high entropy alloy according to any one of claims 15 to 16, wherein: The radiation shielding high entropy alloy further includes a boron coating layer disposed on the surface of the core layer.

18. The radiation shielding high entropy alloy of claim 17, wherein: The thickness of the boron coating layer is 2 μm to 50 μm.

19. Use of the radiation shielding high entropy alloy according to any one of claims 14 to 18 in the preparation of radiation shielding products.

20. A radiation shielding product comprising the radiation shielding high entropy alloy according to any one of claims 14 to 18.

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