CN107805777B - Tungsten-boron layered material with ray and neutron comprehensive shielding effect - Google Patents
Tungsten-boron layered material with ray and neutron comprehensive shielding effect Download PDFInfo
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- CN107805777B CN107805777B CN201710847494.0A CN201710847494A CN107805777B CN 107805777 B CN107805777 B CN 107805777B CN 201710847494 A CN201710847494 A CN 201710847494A CN 107805777 B CN107805777 B CN 107805777B
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
- G21F1/08—Metals; Alloys; Cermets, i.e. sintered mixtures of ceramics and metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
- C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
- C23C8/68—Boronising
Abstract
The invention discloses a tungsten-boron layered material with a ray and neutron comprehensive shielding effect, and belongs to the technical field of shielding materials. The tungsten-boron layered material consists of tungsten or tungsten alloy and a boronizing layer, wherein the thickness of the boronizing layer is 38-45 mu m, boron exists in the boronizing layer in the form of boride, the tungsten alloy is an alloy consisting of Ni, Cu, Nb, Co, Mo, Cr or C elements and tungsten elements, and the mass percentage of tungsten is 85-99%. Compared with the traditional tungsten and alloy materials thereof, the special layered structure ensures that the tungsten-boron composite material has more obvious shielding effect on X rays, gamma rays and neutrons, and has the characteristics of high strength, high hardness, good conductivity, excellent corrosion resistance and the like.
Description
Technical Field
The invention relates to a tungsten-boron layered material with comprehensive ray and neutron shielding effect, belonging to the technical field of shielding materials.
Background
The development of nuclear science and technical industries brings great benefits to human beings, but also brings direct or indirect radiation hazards to human beings and the environment on which the human beings live. The reactor is the core part of a nuclear energy system, and nuclear fission can generate various radiation rays such as neutrons with different energy levels, gamma rays, secondary gamma rays, X rays and other high-energy rays, thereby causing damage to human bodies and the environment. In order to prevent or reduce the harm of radiation rays to human bodies and the environment, radiation protection is required, and the radiation protection mainly depends on the performance of a radiation-proof shielding material. The radiation-proof shielding material is mainly a material having a shielding effect on ionizing radiation such as neutrons, X rays, gamma rays and the like. The radiation-proof shielding material which is most widely applied at present is a material containing lead with high atomic number (such as lead, soft lead and organic lead glass) and barium (such as organic barium glass).
However, with the development of nuclear energy and various nuclear reactors, the demand for radiation-proof shielding materials is increasing. The single traditional shielding material is difficult to meet all protection requirements, for example, lead and lead compounds are toxic, serious environmental pollution is generated during preparation, use and abandonment, and the organic barium glass has the defects of low surface hardness, poor radiation protection performance and the like. However, many existing composite radiation-proof shielding materials are difficult to meet the comprehensive requirements of radiation protection on other properties, such as mechanical properties, radiation resistance and the like. In order to solve these drawbacks, it is an urgent problem to provide an environmentally friendly shielding material having mechanical strength and effective protection against nuclear radiation energy such as neutrons, X-rays, and γ -rays.
Disclosure of Invention
Aiming at the problem that the performance and the application range of the existing nuclear radiation shielding material cannot be considered at the same time, the invention provides the tungsten-boron layered material with the comprehensive shielding effect of rays and neutrons, which has the characteristics of mechanical strength, capability of effectively protecting neutrons, X rays, gamma rays and other nuclear radiation and environmental friendliness;
a tungsten-boron layered material with comprehensive ray and neutron shielding effect comprises tungsten or tungsten alloy and a boronizing layer, wherein the thickness of the boronizing layer is 38-45 mu m;
the tungsten alloy is an alloy consisting of Ni, Cu, Nb, Co, Mo, Cr or C and tungsten, wherein the mass percent of tungsten is 85-99%;
the tungsten-boron layered material is compounded by a boronizing method, and the boronizing agent comprises a boron supply agent, a reducing agent and an activating agent;
the boron donor is amorphous boron powder and borax, the reducing agent is aluminum powder, and the activating agent is sodium chloride or potassium chloride.
The preparation process of the tungsten-boron layered material with the comprehensive ray and neutron shielding effect comprises the following steps: firstly, cleaning the surface of a sample by using a detergent, and then polishing the surface of the sample by using abrasive paper to 2000 DEG＃. The boronizing agent comprises a boron donor (amorphous boron powder and borax) and a reducing agent (aluminum powder), a small amount of activating agent (sodium chloride) is added for increasing the fluidity of the molten boronizing agent, the agents are put into a ball mill according to the mass ratio of the boron powder to the borax to the reducing agent (aluminum powder) to the activating agent (sodium chloride) of 1:6:1: 1-1: 7:1:1 and are uniformly mixed, the cut tungsten or tungsten alloy base material is embedded into the boronizing agent and sealed in a corundum crucible, and high-temperature boronizing treatment is carried out for 10-15 hours under the process condition that the temperature is 1000-1300 ℃; and cooling the boronized sample at room temperature, and then putting the cooled boronized sample into hot water to remove the residual boronizing agent and other impurities on the surface of the sample, thereby obtaining the layered material with the comprehensive ray and neutron shielding effect.
The invention has the beneficial effects that: adding boron or boride into a pure tungsten or tungsten alloy matrix, and heating by using a boronizing process to obtain the tungsten-boron laminar ray and neutron shielding material while improving the mechanical property. The material has obvious shielding effect on X-rays, gamma-rays and neutrons, the shielding rate of the tungsten-boron laminar-shaped rays and neutron shielding material (the thickness is 20 mm) with the thickness of 40-43 mu m of the boronized layer on the X-rays with the energy of 65KeV, 118KeV and 250KeV is 98.46 percent, 99.63 percent and 90.25 percent respectively, and the shielding rate on the gamma-rays is 49.55 percent (the shielding rate on the gamma-rays is 49.55 percent)137Cs source) and 33.42%, (60Co source), the shielding rate of neutrons reaches 91.36%; the thickness of the boriding layer is 3The shielding rate of 9-42 mu m W-Co-B laminar ray and neutron shielding material (with the thickness of 20 mm) to X-ray with the energy of 65KeV, 118KeV and 250KeV reaches 75.36%, 78.42% and 68.95% respectively, and the shielding rate to gamma ray is 38.54% ((the thickness of the material is 20 mm))137Cs source) and 22.35%, (60Co source), the shielding rate of neutrons reaches 93.56%; the tungsten-boron layered material also has the characteristics of high strength, high hardness, good conductivity, excellent corrosion resistance and the like.
Drawings
FIG. 1 is a scanning electron microscope image of the surface topography of the tungsten-boron layered material of example 1;
FIG. 2 is a scanning electron micrograph of a tungsten-boron layered material of example 1;
FIG. 3 is a scanning electron microscope image of the surface topography of the W-Co alloy-B layered material of example 2;
FIG. 4 is a scanning electron micrograph of the tungsten-cobalt alloy-boron layered material of example 2.
Detailed Description
Example 1: the substrate of the embodiment is a pure tungsten substrate;
the method comprises the following steps of pretreating a pure tungsten matrix, wherein the treatment process comprises the following steps: removing oil on the surface, cleaning with deionized water, polishing with sand paper, cleaning with acetone, ultrasonically cleaning with deionized water, and sealing in absolute ethyl alcohol for later use; embedding the pretreated substrate into a boronizing agent (the boronizing agent comprises 70 mass percent of borax, 10 mass percent of aluminum powder, 10 mass percent of sodium chloride and 10 mass percent of boron powder), sealing the boronizing agent in a corundum crucible, putting the corundum crucible into a box furnace, carrying out high-temperature boronizing treatment for 15 hours at the temperature of 1000 ℃, taking out a boronizing sample, cooling the boronizing sample at room temperature, and putting the boronizing sample into hot water to remove the residual boronizing agent and other impurities on the surface of the boronizing sample so as to obtain the tungsten-boron layered material with the comprehensive shielding effect;
microstructure characteristics: the tungsten-boron layered material of the embodiment is subjected to surface treatment (grinding, polishing and corrosion), and the microstructure characteristics of the sample are observed and analyzed by adopting a scanning electron microscope, as shown in fig. 1, the alloy structure is uniformly distributed, and the interface condition of each phase is good;
the microstructure scanning electron microscope image of the borotungsten layered material of the embodiment is shown in fig. 2, and the thickness of the boronizing layer is 40-43 μm;
and (3) testing shielding performance: x-ray shielding performance detection is performed by using an MG452 type X-ray system, and X-ray energies are 65keV, 118keV and 250keV, respectively. The gamma ray shielding performance is tested by using a gamma ray irradiation standard device, and the radioactive source is137Cs (radiation energy 661 KeV) and60the Co (ray energy 1.25 MeV) neutron shielding experiment is detected by adopting a PTW-UNIDOS ionization chamber type standard dosimeter and an Am-Be neutron source moderation experiment device, the test results are shown in table 1, and the shielding rates of the tungsten-boron laminar ray and the neutron shielding material to X rays with the energy of 65KeV, 118KeV and 250KeV respectively reach 98.46%, 99.63% and 90.25% as can Be seen from table 1; the shielding rate to gamma rays is 49.55% ((137Cs source) and 33.42%, (60A Co source); the shielding rate of neutrons reaches 91.36%.
Example 2: the matrix of the embodiment is a tungsten-cobalt hard alloy matrix of YG 3X; the composition of the tungsten-cobalt hard alloy of YG3X is: the mass percent of WC is 97%, and the mass percent of Co is 3%;
pretreating a tungsten-cobalt hard alloy matrix with the grade of YG3X, wherein the treatment process comprises the following steps: removing oil on the surface, cleaning with deionized water, polishing with sand paper, cleaning with acetone, ultrasonically cleaning with deionized water, and sealing in absolute ethyl alcohol for later use; embedding the pretreated substrate into a boronizing agent (the boronizing agent comprises 70 mass percent of borax, 10 mass percent of aluminum powder, 10 mass percent of sodium chloride and 10 mass percent of boron powder), sealing the boronizing agent in a corundum crucible, putting the corundum crucible into a box furnace, carrying out high-temperature boronizing treatment for 10 hours at the temperature of 1000 ℃, taking out a boronizing sample, cooling the boronizing sample at room temperature, and putting the boronizing sample into hot water to remove the residual boronizing agent and other impurities on the surface of the boronizing sample so as to obtain the tungsten-boron layered material with the comprehensive shielding effect;
microstructure characteristics: the tungsten-boron layered material of the embodiment is subjected to surface treatment (grinding, polishing and corrosion), and the microstructure characteristics of the sample are observed and analyzed by adopting a scanning electron microscope, as shown in fig. 3, the alloy structure is uniformly distributed, and the interface condition of each phase is good;
the microstructure scanning electron microscope image of the borotungsten layered material of the embodiment is shown in fig. 4, and the thickness of the boronized layer is 39-42 μm;
and (3) testing shielding performance: x-ray shielding performance detection is performed by using an MG452 type X-ray system, and X-ray energies are 65keV, 118keV and 250keV, respectively. The gamma ray shielding performance is tested by using a gamma ray irradiation standard device, and the radioactive source is137Cs (radiation energy 661 KeV) and60the Co (ray energy 1.25 MeV) neutron shielding experiment is detected by adopting a PTW-UNIDOS ionization chamber type standard dosimeter and an Am-Be neutron source moderation experiment device, the test results are shown in table 1, and the shielding rates of the tungsten-cobalt alloy-boron laminar ray and the neutron shielding material to X rays with the energy of 65KeV, 118KeV and 250KeV reach 75.36%, 78.42% and 68.95% respectively from the table 1; the shielding rate to gamma rays is 38.54% ((137Cs source) and 22.35%, (60A Co source); the shielding rate of neutrons reaches 93.56%.
Example 3: the matrix of the embodiment adopts a tungsten-cobalt hard alloy matrix of YG 15; the YG15 alloy comprises the following components: the mass percent of WC is 85 percent, and the mass percent of Co is 15 percent;
pretreating a tungsten-cobalt hard alloy matrix with the grade of YG15, wherein the treatment process comprises the following steps: removing oil on the surface, cleaning with deionized water, polishing with sand paper, cleaning with acetone, ultrasonically cleaning with deionized water, and sealing in absolute ethyl alcohol for later use; embedding the pretreated substrate into a boronizing agent (the boronizing agent comprises 70 mass percent of borax, 10 mass percent of aluminum powder, 10 mass percent of sodium chloride and 10 mass percent of boron powder), sealing the boronizing agent in a corundum crucible, putting the corundum crucible into a box furnace, carrying out high-temperature boronizing treatment for 10 hours at the temperature of 1000 ℃, taking out a boronizing sample, cooling the boronizing sample at room temperature, and putting the boronizing sample into hot water to remove the residual boronizing agent and other impurities on the surface of the boronizing sample so as to obtain the tungsten-boron layered material with the comprehensive shielding effect;
microstructure characteristics: the tungsten-boron layered material of the embodiment is subjected to surface treatment (grinding, polishing and corrosion), the microstructure characteristics of the sample are observed and analyzed by adopting a scanning electron microscope, the alloy structure is uniformly distributed, and the interface condition of each phase is good;
observing the microstructure of the tungsten-boron layered material of the embodiment by using a scanning electron microscope, wherein the thickness of the boronizing layer is 40-43 mu m;
and (3) testing shielding performance: x-ray using MG452 type X-ray systemLine shielding performance was measured with X-ray energies of 65keV, 118keV and 250keV, respectively. The gamma ray shielding performance is tested by using a gamma ray irradiation standard device, and the radioactive source is137Cs (radiation energy 661 KeV) and60the Co (ray energy 1.25 MeV) neutron shielding experiment is detected by adopting a PTW-UNIDOS ionization chamber type standard dosimeter and an Am-Be neutron source moderation experiment device, the test results are shown in table 1, and the shielding rates of the tungsten-cobalt alloy-boron laminar ray and the neutron shielding material to X rays with the energy of 65KeV, 118KeV and 250KeV reach 62.36%, 64.42% and 59.95% respectively from the table 1; the shielding rate to gamma rays is 33.42% ((137Cs source) and 19.39%, (60A Co source); the shielding rate of neutrons reaches 88.63%.
Example 4: the YG6A alloy substrate is selected as the substrate of the embodiment; the YG6A alloy had the following composition: the mass percent of WC is 92%, and the mass percent of Co is 8%;
pretreating a tungsten-cobalt hard alloy matrix with the grade of YG6A, wherein the treatment process comprises the following steps: removing oil on the surface, cleaning with deionized water, polishing with sand paper, cleaning with acetone, ultrasonically cleaning with deionized water, and sealing in absolute ethyl alcohol for later use; embedding the pretreated substrate into a boronizing agent (the boronizing agent comprises 70 mass percent of borax, 10 mass percent of aluminum powder, 10 mass percent of sodium chloride and 10 mass percent of boron powder), sealing the boronizing agent in a corundum crucible, putting the corundum crucible into a box furnace, carrying out high-temperature boronizing treatment for 10 hours at the temperature of 1000 ℃, taking out a boronizing sample, cooling the boronizing sample at room temperature, and putting the boronizing sample into hot water to remove the residual boronizing agent and other impurities on the surface of the boronizing sample so as to obtain the tungsten-boron layered material with the comprehensive shielding effect;
microstructure characteristics: the tungsten-boron layered material of the embodiment is subjected to surface treatment (grinding, polishing and corrosion), the microstructure characteristics of the sample are observed and analyzed by adopting a scanning electron microscope, the alloy structure is uniformly distributed, and the interface condition of each phase is good;
observing the microstructure of the tungsten-boron layered material of the embodiment by using a scanning electron microscope, wherein the thickness of the boronizing layer is 42-45 mu m;
and (3) testing shielding performance: x-ray shielding performance detection is performed by using an MG452 type X-ray system, and X-ray energies are 65keV, 118keV and 250keV, respectively. By gamma irradiationThe gamma ray shielding performance is tested by a radiation standard device, and the radioactive source is137Cs (radiation energy 661 KeV) and60co (ray energy 1.25 MeV) neutron shielding experiment is detected by adopting a PTW-UNIDOS ionization chamber type standard dosimeter and an Am-Be neutron source moderation experiment device, the test results are shown in table 1,
TABLE 1 Shielding Performance Table for tungsten-boron layered Material having a thickness of 20mm
As can be seen from table 1, the X-ray shielding rates of the wc-ba layered radiation and neutron shielding material at 65KeV, 118KeV and 250KeV reached 70.26%, 72.64% and 62.96%, respectively; the shielding rate to gamma rays is 38.54% ((137Cs source) and 20.89%, (60A Co source); the shielding rate of neutrons reaches 90.44%.
Claims (1)
1. A tungsten-boron layered material with comprehensive ray and neutron shielding effect is characterized in that: the material consists of tungsten or tungsten alloy and a boronizing layer, wherein the thickness of the boronizing layer is 38-45 mu m; the tungsten alloy is an alloy consisting of Ni, Cu, Nb, Co, Mo, Cr or C and tungsten, wherein the mass percent of tungsten is 85-99%;
the preparation process of the tungsten-boron layered material comprises the following steps:
the method comprises the following steps of pretreating a pure tungsten or tungsten alloy matrix, wherein the pretreatment process comprises the following steps: surface degreasing, deionized water cleaning, sand paper polishing, acetone cleaning and deionized water ultrasonic cleaning; the boronizing agent comprises a boron donor, a reducing agent and an activating agent, the boron donor, the reducing agent and the activating agent are put into a ball mill according to the mass ratio of 1:6:1: 1-1: 7:1:1 and are uniformly mixed, the cut tungsten or tungsten alloy base material is embedded into the boronizing agent and is sealed in a corundum crucible, and high-temperature boronizing treatment is carried out for 10-15 hours under the process condition that the temperature is 1000-1300 ℃; and cooling the taken boronizing sample at room temperature, and then putting the cooled boronizing sample into hot water to remove the residual boronizing agent and other impurities on the surface to obtain the layered material with the comprehensive ray and neutron shielding effect, wherein the boronizing agent is amorphous boron powder and borax, the reducing agent is aluminum powder, and the activating agent is sodium chloride.
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