CN113969078B - Boron-based material modified rare earth oxide space n-gamma mixed field radiation shielding composite coating and preparation method thereof - Google Patents
Boron-based material modified rare earth oxide space n-gamma mixed field radiation shielding composite coating and preparation method thereof Download PDFInfo
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- CN113969078B CN113969078B CN202111139058.0A CN202111139058A CN113969078B CN 113969078 B CN113969078 B CN 113969078B CN 202111139058 A CN202111139058 A CN 202111139058A CN 113969078 B CN113969078 B CN 113969078B
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
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Abstract
The invention discloses a boron-based material modified rare earth oxide space n-gamma mixed field radiation shielding composite coating and a preparation method thereof, belonging to the technical field of functional material preparation. The invention solves the problems that the prior rare earth metal oxide can generate secondary radiation when being radiated, the rare earth metal oxide nano particles are easy to agglomerate, the wettability in resin is poor, the strength is poor when the rare earth metal oxide nano particles form a composite coating material with a resin substrate, the neutron radiation shielding performance is poor, and the like. According to the invention, a compact BN or BC film layer with controllable thickness is deposited on the outer surface of the rare earth oxide nano particles by a chemical vapor deposition method to form core-shell structure powder, and then the core-shell structure powder is compounded with a resin matrix to prepare the radiation-proof coating. The core-shell structure prepared by the invention greatly enhances the wettability and the dispersion uniformity of the rare earth oxide nanoparticles in the resin matrix, plays a role in enhancing the strength of the resin matrix, effectively shields gamma rays and neutrons, and reduces secondary radiation.
Description
Technical Field
The invention relates to a boron-based material modified rare earth oxide space n-gamma mixed field radiation shielding composite coating and a preparation method thereof, belonging to the technical field of functional material preparation.
Background
The traditional radiation shielding material is toxic, has serious pollution to the environment, has a weak absorption area for X-rays, has poor neutron shielding performance and has large mass. The rare earth oxide nano-particles have excellent X/gamma ray shielding capability, and in addition, the rare earth elements have special extra-nuclear electronic structure and special K absorption edge, which just make up the 'weak absorption region' of lead. And the reaction section of the material is large for n and gamma of thermal neutrons, and the material also has good shielding performance for slow neutrons and fast neutrons. The rare earth element has high atomic number, large electron density outside the nucleus, special structure and unique advantage for absorbing electron radiation, but the rare earth oxide nano particles have certain secondary radioactivity (bremsstrahlung radiation is generated by electrons and secondary gamma radiation is easily generated by neutrons), have weak shielding capability for neutron radiation and are easy to generate secondary radiation. And the rare earth oxide nanoparticles have the defects of large specific surface area, high surface energy, poor wetting property in a resin matrix and the like, and have the problems of poor uniformity, easy agglomeration and the like when being mixed with the resin matrix.
Disclosure of Invention
The invention provides a boron-based material modified rare earth oxide space n-gamma mixed field radiation shielding composite coating and a preparation method thereof, aiming at solving the problems that the existing rare earth oxide nanoparticles can generate secondary radiation when being radiated, the rare earth oxide nanoparticles are easy to agglomerate, the wettability in resin is poor, the strength is poor when the composite coating material is formed with a resin substrate, the neutron radiation shielding performance is poor, and the like.
The technical scheme of the invention is as follows:
a boron-based material modified rare earth oxide space n-gamma mixed field radiation shielded composite coating and a preparation method thereof are disclosed, the method comprises the following steps:
step 1, preparing core-shell structure powder;
depositing a BN or BC film layer on the outer surface of the rare earth metal oxide nano particles by adopting a vapor deposition method to obtain core-shell structure powder;
step 2, preparing a composite coating;
and (3) mixing the core-shell structure powder obtained in the step (1) with resin, grinding the mixture by using a three-roll grinder, coating the obtained slurry on the surface of the protected object after grinding, and drying the coated object to form the composite coating.
The rare earth metal oxide is one or two of gadolinium oxide and erbium oxide which are mixed according to any proportion, the average grain diameter of the rare earth metal oxide is 10-30 nm, and the thickness of a BN or BC film layer deposited on the outer surface of the rare earth metal oxide nano-particle is 30-50 nm.
Further, the operation process of the vapor deposition in step 1 is as follows: the method comprises the following steps of (1) carrying out contact reaction on rare earth metal oxide nanoparticles and reaction gas at the temperature of 550-750 ℃, wherein the reaction time is 30-120 min, and depositing and coating a BN or BC film on the surfaces of the rare earth metal oxide nanoparticles;
wherein the residence time of the reaction gas is 0.15-0.35 s, the reaction pressure is 3.5-5.5 kpa, and the diluent gas is inert gas with the purity of 99.999% or hydrogen with the purity of 99.999%.
Further defined, the reaction gas is composed of BX3、N2、H2And NH3And (4) forming.
Further, the flow rates of the gases in the reaction are: BX3Is 15 v/ml.min-1、N2Is 105 v/ml.min-1、H2Is 15 v/ml.min-1And NH3Is 65 v/ml.min-1Or BX3Is 20 v/ml.min-1、N2Is 100 v/ml.min-1、H2Is 20 v/ml.min-1And NH3Is 60 v/ml.min-1Or BX3Is 25 v/ml.min-1、N2Is 95 v/ml.min-1、H2Is 25 v/ml.min-1And NH3Is 55 v/ml.min-1。
To a further limit, BX3Is boron chloride, boron bromide or boron iodide.
Further limiting, the grinding treatment time in the step 2 is 5-10 min.
And (3) further limiting, wherein the adding amount of the composite powder in the step (2) is 10-80% of the total mass of the composite powder and the resin.
Further limiting, the drying treatment temperature in the step 2 is 30-80 ℃.
Further limiting, in the step 2, the resin is epoxy resin, cyanate ester, polyurethane or high hydrogen polyethylene.
Further limiting, the slurry coating mode in the step 2 is a spraying method, a spin coating method or a blade coating method.
The invention has the following beneficial effects: according to the invention, a layer of compact BN or BC film with controllable thickness is deposited on the outer surface of the rare earth oxide nano particles by a chemical vapor deposition method to form core-shell structure powder, and then the core-shell structure powder is compounded with a resin matrix to prepare the radiation-proof coating. Has the following advantages:
(1) according to the invention, a layer of BN or BC film is deposited on the outer surface of the rare earth oxide nano particles, so that the wettability and the dispersion uniformity of the rare earth oxide nano particles in a resin matrix are greatly enhanced, and the strength of the resin matrix is enhanced;
(2) after the core-shell structure composite particles prepared by the invention are dispersed in a resin matrix, a multilayer alternate structure of different materials can be formed on a microstructure, so that alternate penetration of rays in the materials is realized, the materials have better shielding capability of X rays, gamma rays and neutrons, and secondary particles are effectively shielded and reduced.
Drawings
FIG. 1 is a photograph of a boron nitride modified gadolinium oxide composite coating;
FIG. 2 is a microstructure of boron nitride modified gadolinium oxide at different magnifications.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
Example 1:
(A) and ultrasonically cleaning the nano gadolinium oxide powder by using absolute ethyl alcohol, and drying.
(B) B, placing the nano gadolinium oxide powder treated in the step A into a tube furnace, vacuumizing the tube furnace, heating to 650 ℃, then opening 2 quartz vent pipes, wherein mixed gas BCl is introduced into one path of the quartz vent pipes3、N2And H2The other path is introduced with NH3. The flow of the introduced gas is QBCL3Is 20 v/ml.min-1、QNH3Is 60v/ml min-1、QN2Is 100v/ml min-1、QH2＝20v/ml·min-1；
The system pressure was maintained at 4.5Kpa, the reaction gas residence time was 0.25S, and the deposition time was 70 min.
(C) And mixing the modified powder material with epoxy resin, wherein the mass fraction of the powder is 50%, and the mass fraction of the epoxy resin is 50%. And pouring the mixed powder and resin into a three-roll grinder, and grinding and stirring for 10 min. And (4) blade-coating the uniformly stirred slurry on the polyimide film in a blade-coating manner. Drying in a vacuum drying oven at 30 deg.C for 3h to obtain the film material.
The film material is subjected to performance test, and the results are as follows:
by using241Am (60Kev) source was irradiated to the composite coating material for 10 seconds, and the following data were obtained.
The test data show that the linear attenuation coefficient of the modified composite coating of the embodiment is obviously higher than that of the unmodified coating material, and the modified composite coating is241The energy of the Am source is attenuated to one tenth of the original energy by only 0.365cm, and the n-gamma mixed field ray irradiation can be effectively resisted.
Example 2:
(A) and ultrasonically cleaning the nano gadolinium oxide powder by using absolute ethyl alcohol, and drying.
(B) B, placing the nano gadolinium oxide powder treated in the step A into a tube furnace, vacuumizing the tube furnace, heating to 700 ℃, then opening 2 quartz vent pipes, wherein mixed gas BCl is introduced into one path of the quartz vent pipes3、N2And H2The other path is introduced with NH3. The flow rate of the introduced gas is QBX3Is 15 v/ml.min-1、QNH3Is 65 v/ml.min-1、QN2Is 105 v/ml.min-1、QH2Is 15 v/ml.min-1；
The system pressure was maintained at 3.5Kpa, the reactant gas residence time was 0.2S, and the deposition time was 90 min.
(C) And mixing the modified powder material with epoxy resin, wherein the mass fraction of the powder is 50%, and the mass fraction of the epoxy resin is 50%. And pouring the mixed powder and resin into a three-roll grinder, and grinding and stirring for 10 min. And (4) blade-coating the uniformly stirred slurry on the polyimide film in a blade-coating manner. Drying in a vacuum drying oven at 30 deg.C for 3h to obtain the film material.
The composite coating was subjected to performance testing, with the following results:
by using241Am (60Kev) source was irradiated to the composite coating material for 10 seconds, and the following data were obtained.
The test data show that the linear attenuation coefficient of the modified composite coating of the embodiment is obviously higher than that of the unmodified coating material, and the modified composite coating is241The energy of the Am source is attenuated to one tenth of the original energy and only needs 0.348cm, and the n-gamma mixed field ray irradiation can be effectively resisted.
Example 3:
(A) and ultrasonically cleaning the nano erbium oxide powder by using absolute ethyl alcohol, and drying.
(B) B, placing the nano gadolinium oxide powder treated in the step A into a tube furnace, vacuumizing the tube furnace, heating to 650 ℃, then opening 2 quartz vent pipes, wherein mixed gas BCl is introduced into one path of the quartz vent pipes3、N2、H2The other path is introduced with NH3. The flow of the introduced gas is QBCL3Is 20 v/ml.min-1、QNH3Is 60v/ml min-1、QN2Is 100 v/ml.min-1、QH2Is 20 v/ml.min-1；
The system pressure was maintained at 3.0Kpa, the reactant gas residence time was 0.35S, and the deposition time was 110 min.
(C) And mixing the modified powder material with epoxy resin, wherein the mass fraction of the powder is 50%, and the mass fraction of the epoxy resin is 50%. And pouring the mixed powder and resin into a three-roll grinder, and grinding and stirring for 10 min. And (4) blade-coating the uniformly stirred slurry on the polyimide film in a blade-coating manner. Drying in a vacuum drying oven at 30 deg.C for 3h to obtain the film material.
The composite coating was subjected to performance testing, with the following results:
by using241Am (60Kev) source was irradiated to the composite coating material for 10 seconds, and the following data were obtained.
The test data show that the linear attenuation coefficient of the modified composite coating of the embodiment is obviously higher than that of the unmodified coating material, and the modified composite coating is241The energy of the Am source is attenuated to one tenth of the original energy by only 0.227cm, and the n-gamma mixed field ray irradiation can be effectively resisted.
Claims (7)
1. A preparation method of a boron-based material modified rare earth oxide space n-gamma mixed field radiation shielding composite coating is characterized by comprising the following steps:
step 1, preparing core-shell structure powder;
depositing a BN or BC film layer on the outer surface of the rare earth metal oxide nano particles by adopting a vapor deposition method to obtain core-shell structure powder; the operation process of the gas phase deposition in the step 1 is as follows: the method comprises the following steps of (1) carrying out contact reaction on rare earth metal oxide nanoparticles and reaction gas at the temperature of 550-750 ℃, wherein the reaction time is 30-120 min, and depositing and coating a BN or BC film on the surfaces of the rare earth metal oxide nanoparticles;
wherein the residence time of the reaction gas is 0.15-0.35 s, the reaction pressure is 3.5-5.5 kpa, and the diluent gas is inert gas with the purity of 99.999% or hydrogen with the purity of 99.999%;
the reaction gas consists of BX3、N2、H2And NH3The gas flow rate is respectively as follows: BX3Is 15 v/ml.min-1、N2Is 105v/ml min-1、H2Is 15 v/ml.min-1And NH3Is 65 v/ml.min-1Or BX3Is 20 v/ml.min-1、N2Is 100 v/ml.min-1、H2Is 20 v/ml.min-1And NH3Is 60 v/ml.min-1Or BX3Is 25 v/ml.min-1、N2Is 95 v/ml.min-1、H2Is 25 v/ml.min-1And NH3Is 55 v/ml.min-1；
The BX3Is boron chloride, boron bromide or boron iodide;
step 2, preparing a composite coating;
and (3) mixing the core-shell structure powder obtained in the step (1) with resin, grinding the mixture by using a three-roll grinder, coating the obtained slurry on the surface of the protected object after grinding, and drying the coated object to form the composite coating.
2. The method for preparing the boron-based material modified rare earth oxide space n-gamma mixed field radiation shielding composite coating according to claim 1, wherein the rare earth metal oxide is one or two of gadolinium oxide and erbium oxide mixed according to any proportion, the average particle diameter of the rare earth metal oxide is 10-30 nm, and the thickness of the BN or BC film deposited on the outer surface of the rare earth metal oxide nano-particles is 30-50 nm.
3. The method for preparing the boron-based material modified rare earth oxide space n-gamma mixed field radiation shielding composite coating according to claim 1, wherein the grinding treatment time in the step 2 is 5-10 min.
4. The method for preparing the boron-based material modified rare earth oxide space n-gamma mixed field radiation shielding composite coating according to claim 1, wherein the addition amount of the composite powder in the step 2 is 10-80% of the total mass of the composite powder and the resin.
5. The method for preparing the boron-based material modified rare earth oxide space n-gamma mixed field radiation shielding composite coating according to claim 1, wherein the drying temperature in the step 2 is 30-80 ℃.
6. The method for preparing a boron-based material modified rare earth oxide space n-gamma mixed field radiation shielding composite coating according to claim 1, wherein the resin in the step 2 is epoxy resin, cyanate ester or polyurethane.
7. The method for preparing the boron-based material modified rare earth oxide space n-gamma mixed field radiation shielding composite coating according to claim 1, wherein the slurry coating mode in the step 2 is a spraying method, a spin coating method or a blade coating method.
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