CN113845817B - Preparation method of double-component functional filler composite coating for space high-energy proton radiation protection - Google Patents
Preparation method of double-component functional filler composite coating for space high-energy proton radiation protection Download PDFInfo
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- CN113845817B CN113845817B CN202111139045.3A CN202111139045A CN113845817B CN 113845817 B CN113845817 B CN 113845817B CN 202111139045 A CN202111139045 A CN 202111139045A CN 113845817 B CN113845817 B CN 113845817B
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
The invention discloses a preparation method of a double-component functional filler composite coating for space high-energy proton radiation protection, belonging to the technical field of functional material preparation. The invention solves the problem that the existing shielding material can not effectively shield space high-energy proton radiation such as neutrons, gamma rays and the like at the same time. According to the invention, rare earth metal oxide and a high-Z metal material are compounded through a ball milling process to form a core-shell structure, and then the composite particles are compounded with a resin matrix to prepare the radiation-proof coating. After the core-shell structure composite particles prepared by the invention are dispersed in a resin matrix, a multilayer alternating structure of different materials can be formed on a microstructure, so that the alternate penetration of rays in the materials is realized, the materials have better space high-energy proton radiation protection capability, and meanwhile, the preparation process of the multilayer alternating materials is simplified.
Description
Technical Field
The invention relates to a preparation method of a double-component functional filler composite coating for space high-energy proton radiation protection, belonging to the technical field of functional material preparation.
Background
When the spacecraft flies in outer space, the spacecraft is always in a severe space environment because the spacecraft is not protected by the atmosphere of the earth. Under a plurality of space environment factors, high-intensity irradiation is always a key factor influencing the working performance and the service life of the spacecraft. The space irradiation can be classified into heavy ions, alpha particles, protons, electrons, neutrons, X rays, gamma rays, and the like according to the types of particles, and the damage of different types of particles to space equipment is different in principle, so that if a spacecraft is to be well protected, materials need to be designed for the different types of particles to protect the spacecraft.
In a complex radiation environment, a single-element shielding material can only shield one type of ray, so that the capability of shielding two or more rays by one material cannot be achieved. It is known from the interaction mechanism of rays and substances that gamma ray shielding needs to be done by high-Z materials, while neutron shielding needs to be done by low-Z materials or other materials with very high neutron shielding cross section. However, if the high Z and low Z are combined, the low Z material will hardly work for gamma radiation, and only the high Z material can protect it. For neutron protection, however, low Z may have limited effectiveness. Therefore, it is necessary to provide a radiation composite material capable of effectively shielding spatially high-energy protons such as neutrons and gamma rays.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a preparation method of a double-component functional filler composite coating for space high-energy proton radiation protection.
The technical scheme of the invention is as follows:
the preparation method of the double-component functional filler composite coating for space high-energy proton radiation protection comprises the following steps:
step 1, preparing composite powder;
mixing rare earth metal oxide and a high-Z metal material, and then carrying out ball milling treatment to obtain composite powder;
step 2, preparing a composite coating;
and (3) mixing the composite 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 a composite coating.
Further limiting, the rare earth metal oxide is one or two of gadolinium oxide, erbium oxide, samarium oxide and cerium oxide which are mixed according to any proportion; the high-Z metal material is one or more of a tungsten simple substance, a tantalum simple substance and a bismuth simple substance which are mixed according to any proportion.
Further limiting, the ratio of balls to materials in the ball milling treatment process in the step 1 is 2:1, 4:1, 6:1 or 8: 1.
Further limiting, the mass ratio of the rare earth metal oxide to the high-Z metal material in the ball milling treatment process in the step 1 is 1:1, 2:1, 3:1, 4:1 or 5: 1.
Further limiting, the ball milling treatment conditions in the step 1 are as follows: and carrying out ball milling under normal pressure or introducing protective gas, wherein the rotating speed is 200-1000 rpm, and the ball milling time is 12-48 h.
Further limited, the shielding gas is Ar or N2。
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 10-50% of the total mass of the composite powder and the resin.
Further limiting, the thickness of the composite coating obtained in the step 2 is 100 um-1 cm.
Further, in the step 2, the resin is any one of epoxy resin, cyanate ester, polyurethane or high density polyethylene.
Further limiting, the slurry coating mode in the step 2 is a spraying method, a blade method or a spin coating method.
Further limiting, in the step 2, drying is carried out for 6-8 hours at the temperature of 30-100 ℃.
The invention has the following beneficial effects: according to the invention, rare earth metal oxide and a high-Z metal material are compounded through a ball milling process to form a core-shell structure, and then the composite particles are compounded with a resin matrix to prepare the radiation-proof coating. Has the following advantages:
(1) the rare earth material and the high-Z material are subjected to ball milling compounding by adopting a ball milling technology, the method is simple, and the size of the composite particles can be effectively controlled by adjusting ball milling parameters to form a core-shell structure;
(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 gamma ray and neutron shielding capability, and meanwhile, the preparation process of the multilayer alternate materials is simplified;
(3) according to the invention, the rare earth material and the traditional high-Z metal material are compounded, so that the capability of the composite material in shielding gamma rays and neutrons is greatly improved, and the materials provided by the method enrich the types of radiation shielding materials.
Drawings
FIG. 1 is an SEM photograph of a gadolinium oxide/W composite coating.
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 are not intended to 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:
firstly, preparing composite powder
Mixing gadolinium oxide and tungsten simple substance in a mass ratio of 1:1, pouring the mixture into a ball milling tank, enabling the ball-material ratio in the ball milling tank to be 2:1, putting the ball milling tank into a ball mill, ball-milling for 12 hours at a rotating speed of 200rpm under a normal pressure condition, taking out ball materials after ball milling is finished, and separating the ball materials to obtain composite powder with a core-shell structure;
second, composite powder
And mixing the obtained composite powder with epoxy resin, wherein the mass fraction of the composite powder is 10%, fully grinding and mixing the composite powder by using a three-roll grinder, the grinding time is 10min, after grinding is finished, coating the mixed slurry on the surface of an object to be protected by adopting a spraying mode to form a coating with the thickness of 100um, placing the coating in a vacuum drying oven, and drying for 6h at the temperature of 30 ℃ to obtain the composite coating.
The microstructure of the obtained composite coating is represented, and as can be seen from a scanning electron microscope image in fig. 1, the dispersibility of the powder in a resin matrix is good, the thickness of the coating after film formation is uniform, particles are not agglomerated in a large area, and neutron and gamma ray shielding can be well realized.
Example 2:
firstly, preparing composite powder
Mixing erbium oxide and tantalum simple substance in a mass ratio of 2:1, pouring the mixture into a ball milling tank, wherein the ball-material ratio in the ball milling tank is 2:1, putting the ball milling tank into a ball mill, ball-milling for 24 hours at a rotating speed of 200rpm under the protection of Ar, taking out ball materials after ball milling is finished, and separating the ball materials to obtain composite powder with a core-shell structure;
two, composite powder
And mixing the obtained composite powder with epoxy resin, wherein the mass fraction of the composite powder is 30%, fully grinding and mixing the composite powder by using a three-roll grinder, the grinding time is 10min, coating the mixed slurry on the surface of a protected object by adopting a blade coating mode after grinding is finished to form a coating with the thickness of 500um, placing the coating in a vacuum drying oven, and drying the coating for 8 hours at the temperature of 50 ℃ to obtain the composite coating.
Example 3:
firstly, preparing composite powder
Mixing cerium oxide and bismuth in a mass ratio of 5:1, pouring the mixture into a ball milling tank, enabling the ball-material ratio in the ball milling tank to be 2:1, putting the ball milling tank into a ball mill, ball-milling for 24 hours at a rotating speed of 400rpm under the protection of Ar, taking out ball materials after ball milling is finished, and separating the ball materials to obtain composite powder with a core-shell structure;
second, composite powder
And mixing the obtained composite powder with epoxy resin, wherein the mass fraction of the composite powder is 30%, fully grinding and mixing the composite powder by using a three-roll grinder, the grinding time is 10min, coating the mixed slurry on the surface of a protected object by adopting a blade coating mode after grinding is finished to form a coating with the thickness of 500um, placing the coating in a vacuum drying oven, and drying the coating for 8 hours at the temperature of 50 ℃ to obtain the composite coating.
Comparative example 1:
preparation of high Z composite coatings
Mixing tungsten simple substance powder with epoxy resin in advance, wherein the mass fraction of the powder is 10%, fully grinding and mixing the powder by using a three-roll grinder, the grinding time is 10min, after grinding is finished, coating the mixed slurry on the surface of a protected object by adopting a spraying mode to form a coating with the thickness of 100um, placing the coating in a vacuum drying oven, and drying for 6h at the temperature of 30 ℃ to obtain the composite coating.
Comparative example 2:
preparation of rare earth composite coating
Mixing gadolinium oxide with epoxy resin, wherein the mass fraction of powder is 10%, fully grinding and mixing by using a three-roll grinder, the grinding time is 10min, after grinding is finished, coating the mixed slurry on the surface of a protected object by adopting a spraying mode to form a coating with the thickness of 100um, placing the coating in a vacuum drying oven, and drying for 6h at the temperature of 30 ℃ to obtain the composite coating.
The composite coating was subjected to performance testing, and the results were 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 shows that the linear attenuation coefficient of the modified composite coating is obviously higher than that of the unmodified coating material, and the modified composite coating is241The Am source energy is attenuated to one tenth of the original energy and only needs 0.0.187cm, and the radiation of the high-energy protons in the space can be effectively resisted.
Claims (7)
1. The preparation method of the double-component functional filler composite coating for space high-energy proton radiation protection is characterized by comprising the following steps of:
step 1, preparing composite powder;
mixing rare earth metal oxide and a high-Z metal material, and then carrying out ball milling treatment to obtain composite powder;
the ball-material ratio in the ball milling treatment process in the step 1 is 2:1, 4:1, 6:1 or 8: 1;
the mass ratio of the rare earth metal oxide to the high-Z metal material in the ball milling treatment process in the step 1 is 1:1, 2:1, 3:1, 4:1 or 5: 1;
the ball milling treatment conditions in the step 1 are as follows: carrying out ball milling at normal pressure or introducing protective gas for ball milling at the rotating speed of 200-1000 rpm for 12-48 h;
step 2, preparing a composite coating;
and (3) mixing the composite 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 a composite coating.
2. The preparation method of the two-component functional filler composite coating for the high-energy proton radiation protection in the space according to claim 1, wherein the rare earth metal oxide is one or two of gadolinium oxide, erbium oxide, samarium oxide and cerium oxide mixed according to any proportion; the high-Z metal material is one or more of a tungsten simple substance, a tantalum simple substance and a bismuth simple substance which are mixed according to any proportion.
3. The preparation method of the two-component functional filler composite coating for space high-energy proton radiation protection according to claim 1, wherein the grinding treatment time in the step 2 is 5-10 min.
4. The preparation method of the two-component functional filler composite coating for space high-energy proton radiation protection according to claim 1, wherein the amount of the composite powder added in the step 2 is 10-50% of the total mass of the composite powder and the resin.
5. The method for preparing the dual-component functional filler composite coating for protecting space high-energy proton radiation according to claim 1, wherein the thickness of the composite coating obtained in the step 2 is 100 μm to 1 cm.
6. The method for preparing the two-component functional filler composite coating for protecting space high-energy proton radiation according to claim 1, wherein the resin in the step 2 is any one of epoxy resin, cyanate ester, polyurethane or high-density polyethylene.
7. The method for preparing the two-component functional filler composite coating for protecting space high-energy proton radiation according to claim 1, wherein the slurry coating manner in the step 2 is a spraying method, a blade coating method or a spin coating method.
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