CN111647336A - Nano rare earth radiation-proof composite coating and preparation method thereof - Google Patents
Nano rare earth radiation-proof composite coating and preparation method thereof Download PDFInfo
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a nano rare earth radiation-proof composite coating and a preparation method thereof. Firstly, putting cerium oxide, iron oxide, ferroboron, tin oxide, cerium aluminum oxide and electrolytic nickel into a vacuum induction electromagnetic oven, and heating and melting; carrying out vacuum gas atomization treatment on the molten liquid to obtain alloy powder; then mixing alloy powder, epoxy resin, hydroxyl acrylic resin, ethylene-tetrafluoroethylene copolymer, graphene, nano magnesium powder, an antioxidant, nano aluminum powder, a coupling agent, a dispersing agent and a defoaming agent, dispersing, and filtering impurities to obtain a mixed solution; and finally, adding an epoxy curing agent into the mixed solution, stirring and mixing uniformly at room temperature, and standing to obtain the nano rare earth radiation-proof composite coating. The composite coating adopts the nano rare earth alloy and the nano metal as anti-radiation materials, can effectively absorb X rays and gamma rays, does not contain lead, and is environment-friendly and nontoxic; the preparation process is simple, can be prepared at room temperature, and is suitable for industrial popularization and application.
Description
Technical Field
The invention particularly relates to a nano rare earth radiation-proof composite coating and a preparation method thereof.
Background
Along with the development of science and technology, electronic devices are gradually applied to various industries, and have some worried aspects while bringing great convenience to human beings, wherein the most widely concerned is the problem that electromagnetic radiation affects human health. Ubiquitous electromagnetic radiation has become the fourth environmental pollution source in the world, which is mainly generated by several artificially manufactured systems, such as: electronic equipment, electrical devices, and the like. The harm of electromagnetic radiation is great. Firstly, the harm to human body. The major hazard of electromagnetic radiation to the human body is the cause of dysfunction of the central and autonomic nervous systems. The clinical symptoms comprise dizziness, hypodynamia, sleep disorder, hypomnesis, emotional instability, hyperhidrosis, alopecia, emaciation and the like. Secondly, the interference to communication and television can be caused, which leads to the out-of-control event of the airplane, medical accidents, fire accidents and the like.
Due to the radiation hazard, the radiation-proof composite powder is smeared on electronic equipment or walls in hospitals, factories, scientific research places and other places so as to reduce the hazard of radioactive rays as much as possible. The radiation-proof composite powder can absorb electromagnetic wave energy projected on the surface of the radiation-proof composite powder, and can be converted into heat energy through material loss, so that the interference of clutter on self equipment is reduced, the damage of electromagnetic radiation on surrounding equipment and personnel is effectively prevented, in addition, the radiation-proof composite powder can be coated on complex curved surfaces, tiny corners and the like, a coating film is accurately and firmly formed, and the requirements of industrial, scientific and medical equipment are met. It is known that the conventional radiation protection materials have the following disadvantages in application: firstly, the protection effect is poor; secondly, the painting layer is thick, airtight and poor in durability; and thirdly, a large amount of lead is added into some protective coatings, so that the protective coatings are toxic, lead content in the air is increased, scattered rays are caused, and the influence on human health is great. Therefore, the problem of preventing and controlling the electromagnetic radiation pollution also becomes an important difficult point and a hot point problem in the field of environmental protection.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a nano rare earth radiation-proof composite coating and a preparation method thereof.
In order to achieve the purpose, the technical scheme provided by the invention is as follows: a preparation method of a nanometer rare earth radiation-proof composite coating comprises the following steps:
(1) weighing 1-5 parts by mass of cerium oxide, 24-40 parts by mass of ferric oxide, 2-6 parts by mass of ferroboron, 2-5 parts by mass of tin oxide, 3-6 parts by mass of cerium aluminum oxide and 2-5 parts by mass of electrolytic nickel, sequentially putting the materials into a vacuum induction electromagnetic furnace according to the principle that materials with high melting point and low melting point and containing easily burnt elements are added at last, and then heating to completely melt the materials; carrying out vacuum gas atomization treatment on the molten liquid, wherein the gas atomization pressure is 2-4MPa, then drying, and screening the alloy powder with the grain size of 1000-1500 meshes;
(2) weighing 5-10 parts by mass of alloy powder, 60-80 parts by mass of epoxy resin, 30-50 parts by mass of hydroxyl acrylic resin, 20-30 parts by mass of ethylene-tetrafluoroethylene copolymer, 10-15 parts by mass of graphene, 3-5 parts by mass of nano magnesium powder, 1-3 parts by mass of antioxidant, 3-5 parts by mass of nano aluminum powder, 3-5 parts by mass of coupling agent, 3-5 parts by mass of dispersing agent and 1-3 parts by mass of defoaming agent, mixing the above substances, dispersing for 0.5-1h under the conditions of 30-60 ℃ and 800-1500rpm, and filtering impurities in the mixture to obtain a mixed solution;
(3) adding an epoxy curing agent into the mixed solution, wherein the mass ratio of the mixed solution to the epoxy curing agent is 15-20: 1, stirring and mixing uniformly at room temperature, and standing for 10min to obtain the nano rare earth radiation-proof composite coating.
The antioxidant is at least one of antioxidant 168, antioxidant 1010, antioxidant 1076, antioxidant BHT and antioxidant 502A.
The coupling agent is at least one of polydimethylsiloxane, phenyltriethoxysilane, terephthalic acid metal salt, tetraethoxysilane and triethylvinylsilane.
The dispersing agent is at least one of organic silicon modified polyether DL400, BYK104S, dispersing agent 5040 and dispersing agent MF.
The specific surface area of the graphene is more than 15m2(ii) thin-layer graphene or single-layer graphene per gram.
The defoaming agent is at least one of an organic silicon defoaming agent, a polyether defoaming agent, a defoaming agent 110, a defoaming agent 106, DF1088 and DF 1052.
The invention also discloses the nano rare earth radiation-proof composite coating prepared by the preparation method.
Has the advantages that:
(1) the nanometer rare earth radiation-proof composite coating provided by the invention adopts nanometer rare earth and metal as anti-ray materials, so that the product density is high, the painting layer is thin, and the cracking and falling-off can be avoided; the metal and rare earth elements contained in the product can effectively absorb the radiant quantity with different energies and different wavelengths, and can effectively absorb X rays and gamma rays, thereby greatly reducing the emission of scattered rays and avoiding the secondary damage of scattered rays of workers or patients under the radiation of rays.
(2) The coating does not contain lead, so that the coating is environment-friendly and nontoxic, and has no influence on the bodies of workers; the preparation process is simple, can be prepared at room temperature, and is suitable for industrial popularization and application.
(3) The construction is convenient, the operation is simple, the viscosity is good, and the construction is easy.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs.
The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The sources of all raw materials are not particularly limited in the invention, and the raw materials can be commercially available or self-made. The antioxidant is one or more of antioxidant 168, antioxidant 1010, antioxidant 1076, antioxidant BHT and antioxidant 502A. The coupling agent is one or more of polydimethylsiloxane, phenyltriethoxysilane, terephthalic acid metal salt, ethyl orthosilicate and triethylvinylsilane. The dispersing agent is one or more of organosilicon modified polyether DL400, BYK104S, dispersing agent 5040 and dispersing agent MF. The graphene is thin-layer graphene or single-layer graphene with the specific surface area larger than 15m 2/g. The defoaming agent is one or more of an organic silicon defoaming agent, a polyether defoaming agent, a defoaming agent 110, a defoaming agent 106, DF1088 and DF1052, and is not particularly limited.
In order to further illustrate the present invention, the following describes in detail a nano rare earth radiation protection composite coating and a preparation method thereof provided by the present invention with reference to examples.
Example 1
(1) Weighing 3 parts by mass of cerium oxide, 32 parts by mass of ferric oxide, 4 parts by mass of ferroboron, 4 parts by mass of tin oxide, 4 parts by mass of cerium aluminum oxide and 3 parts by mass of electrolytic nickel, sequentially putting the materials into a vacuum induction electromagnetic furnace according to the principle that materials with high melting point, low melting point and easy-to-burn elements are added at last, and then heating to completely melt the materials; carrying out vacuum gas atomization treatment on the molten liquid, wherein the gas atomization pressure is 3MPa, then drying, and screening alloy powder with the particle size of 1200 meshes;
(2) weighing 7 parts by mass of alloy powder, 70 parts by mass of epoxy resin, 40 parts by mass of hydroxy acrylic resin, 25 parts by mass of ethylene-tetrafluoroethylene copolymer, 13 parts by mass of graphene, 4 parts by mass of nano magnesium powder, 2 parts by mass of antioxidant, 4 parts by mass of nano aluminum powder, 4 parts by mass of coupling agent, 4 parts by mass of dispersing agent and 2 parts by mass of defoaming agent, mixing the above substances, dispersing for 1h at the conditions of 40 ℃ and 1200rpm, and filtering impurities from the mixture to obtain a mixed solution;
(3) adding an epoxy curing agent into the mixed solution, wherein the mass ratio of the mixed solution to the epoxy curing agent is 18: 1, stirring and mixing uniformly at room temperature, and standing for 10min to obtain the nano rare earth radiation-proof composite coating.
Example 2
(1) Weighing 1 part by mass of cerium oxide, 24 parts by mass of ferric oxide, 2 parts by mass of ferroboron, 2 parts by mass of tin oxide, 3 parts by mass of cerium aluminum oxide and 2 parts by mass of electrolytic nickel, sequentially putting the materials into a vacuum induction electromagnetic furnace according to the principle that materials with high melting point, low melting point and easy-to-burn elements are added at last, and then heating to completely melt the materials; carrying out vacuum gas atomization treatment on the molten liquid, wherein the gas atomization pressure is 2MPa, then drying, and screening alloy powder with the particle size of 1000 meshes;
(2) weighing 5 parts by mass of alloy powder, 60 parts by mass of epoxy resin, 30 parts by mass of hydroxy acrylic resin, 20 parts by mass of ethylene-tetrafluoroethylene copolymer, 10 parts by mass of graphene, 3 parts by mass of nano magnesium powder, 1 part by mass of antioxidant, 3 parts by mass of nano aluminum powder, 3 parts by mass of coupling agent, 3 parts by mass of dispersing agent and 1 part by mass of defoaming agent, mixing the above substances, dispersing for 0.5h at the conditions of 30 ℃ and 800rpm, and filtering impurities from the mixture to obtain a mixed solution;
(3) adding an epoxy curing agent into the mixed solution, wherein the mass ratio of the mixed solution to the epoxy curing agent is 15: 1, stirring and mixing uniformly at room temperature, and standing for 10min to obtain the nano rare earth radiation-proof composite coating.
Example 3
(1) Weighing 2 parts by mass of cerium oxide, 30 parts by mass of ferric oxide, 3 parts by mass of ferroboron, 3 parts by mass of tin oxide, 4 parts by mass of cerite and 3 parts by mass of electrolytic nickel, sequentially putting the materials into a vacuum induction electromagnetic oven according to the principle that materials with high melting point, low melting point and easy-to-burn elements are added at last, and then heating to completely melt the materials; carrying out vacuum gas atomization treatment on the molten liquid, wherein the gas atomization pressure is 2MPa, then drying, and screening alloy powder with the particle size of 1000 meshes;
(2) weighing 6 parts by mass of alloy powder, 65 parts by mass of epoxy resin, 35 parts by mass of hydroxy acrylic resin, 24 parts by mass of ethylene-tetrafluoroethylene copolymer, 12 parts by mass of graphene, 3 parts by mass of nano magnesium powder, 1 part by mass of antioxidant, 3 parts by mass of nano aluminum powder, 3 parts by mass of coupling agent, 3 parts by mass of dispersing agent and 1 part by mass of defoaming agent, mixing the above substances, dispersing for 0.5h at the conditions of 35 ℃ and 900rpm, and filtering impurities from the mixture to obtain a mixed solution;
(3) adding an epoxy curing agent into the mixed solution, wherein the mass ratio of the mixed solution to the epoxy curing agent is 16: 1, stirring and mixing uniformly at room temperature, and standing for 10min to obtain the nano rare earth radiation-proof composite coating.
Example 4
(1) Weighing 4 parts by mass of cerium oxide, 35 parts by mass of ferric oxide, 5 parts by mass of ferroboron, 4 parts by mass of tin oxide, 5 parts by mass of cerium aluminum oxide and 4 parts by mass of electrolytic nickel, sequentially putting the materials into a vacuum induction electromagnetic oven according to the principle that materials with high melting point, low melting point and easy-to-burn elements are added at last, and then heating to completely melt the materials; carrying out vacuum gas atomization treatment on the molten liquid, wherein the gas atomization pressure is 3MPa, then drying, and screening alloy powder with the particle size of 1200 meshes;
(2) weighing 8 parts by mass of alloy powder, 75 parts by mass of epoxy resin, 45 parts by mass of hydroxyl acrylic resin, 28 parts by mass of ethylene-tetrafluoroethylene copolymer, 14 parts by mass of graphene, 5 parts by mass of nano magnesium powder, 3 parts by mass of antioxidant, 5 parts by mass of nano aluminum powder, 5 parts by mass of coupling agent, 5 parts by mass of dispersing agent and 3 parts by mass of defoaming agent, mixing the above substances, dispersing for 1h at the conditions of 50 ℃ and 1200rpm, and filtering impurities from the mixture to obtain a mixed solution;
(3) adding an epoxy curing agent into the mixed solution, wherein the mass ratio of the mixed solution to the epoxy curing agent is 18: 1, stirring and mixing uniformly at room temperature, and standing for 10min to obtain the nano rare earth radiation-proof composite coating.
Example 5
(1) Weighing 5 parts by mass of cerium oxide, 40 parts by mass of ferric oxide, 6 parts by mass of ferroboron, 5 parts by mass of tin oxide, 6 parts by mass of cerium aluminum oxide and 5 parts by mass of electrolytic nickel, sequentially putting the materials into a vacuum induction electromagnetic oven according to the principle that materials with high melting point, low melting point and easy-to-burn elements are added at last, and then heating to completely melt the materials; carrying out vacuum gas atomization treatment on the molten liquid, wherein the gas atomization pressure is 4MPa, then drying, and screening alloy powder with the grain size of 1500 meshes;
(2) weighing 10 parts by mass of alloy powder, 80 parts by mass of epoxy resin, 50 parts by mass of hydroxy acrylic resin, 30 parts by mass of ethylene-tetrafluoroethylene copolymer, 15 parts by mass of graphene, 5 parts by mass of nano magnesium powder, 3 parts by mass of antioxidant, 5 parts by mass of nano aluminum powder, 5 parts by mass of coupling agent, 5 parts by mass of dispersing agent and 3 parts by mass of defoaming agent, mixing the above substances, dispersing for 1h at the conditions of 60 ℃ and 1500rpm, and filtering impurities from the mixture to obtain a mixed solution;
(3) adding an epoxy curing agent into the mixed solution, wherein the mass ratio of the mixed solution to the epoxy curing agent is 20: 1, stirring and mixing uniformly at room temperature, and standing for 10min to obtain the nano rare earth radiation-proof composite coating.
Example 6
The nano rare earth radiation-proof composite coating obtained in the embodiment 1-5 is respectively coated on a square iron plate with the thickness of 3mm and the coating thickness of 2mm, wherein the square iron plate is 50cm x 50 cm. The properties of the composite coatings obtained in the above examples were measured and are shown in table 1.
TABLE 1 detection results of nano rare earth radiation-proof composite coating
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Surface hardness | 3H | 3H | 3H | 3H | 3H |
| Adhesion force | Level 1 | Level 1 | Level 1 | Level 1 | Level 1 |
| Acid resistance (hydrochloric acid, 7 d) | Without obvious change | Without obvious change | Without obvious change | Without obvious change | Without obvious change |
| Alkali resistance (sodium hydroxide, 7 d) | Without obvious change | Without obvious change | Without obvious change | Without obvious change | Without obvious change |
| X-ray shielding rate (60 kv) | 98.70% | 94.23% | 93.61% | 92.81% | 94.18% |
| Gamma ray shielding rate (123 kev) | 73.3% | 68.23% | 67.19% | 67.46% | 68.11% |
The data show that the invention technically solves the problem of shielding and protecting X rays by using a non-lead radiation protection material, the X ray absorption rate is higher than 92%, the gamma ray absorption rate is higher than 67%, and the radiation protection effect and the radiation absorption effect are obviously superior to those of the prior art. Meanwhile, the coating has good adhesive force, excellent corrosion resistance and long service life, and the production cost is much lower than that of the existing lead-containing radiation protection coating. Compared with the radiation protection coating containing lead or less lead, the material has the advantages that the main materials and the auxiliary materials do not contain lead, the material is non-toxic and environment-friendly, the problem of post-treatment is solved, the environmental protection and the health of users are facilitated, and the material belongs to a novel green shielding protection material.
Claims (7)
1. A preparation method of a nanometer rare earth radiation-proof composite coating is characterized by comprising the following steps:
(1) weighing 1-5 parts by mass of cerium oxide, 24-40 parts by mass of ferric oxide, 2-6 parts by mass of ferroboron, 2-5 parts by mass of tin oxide, 3-6 parts by mass of cerium aluminum oxide and 2-5 parts by mass of electrolytic nickel, sequentially putting the materials into a vacuum induction electromagnetic furnace according to the principle that materials with high melting point and low melting point and containing easily burnt elements are added at last, and then heating to completely melt the materials; carrying out vacuum gas atomization treatment on the molten liquid, wherein the gas atomization pressure is 2-4MPa, then drying, and screening the alloy powder with the grain size of 1000-1500 meshes;
(2) weighing 5-10 parts by mass of alloy powder, 60-80 parts by mass of epoxy resin, 30-50 parts by mass of hydroxyl acrylic resin, 20-30 parts by mass of ethylene-tetrafluoroethylene copolymer, 10-15 parts by mass of graphene, 3-5 parts by mass of nano magnesium powder, 1-3 parts by mass of antioxidant, 3-5 parts by mass of nano aluminum powder, 3-5 parts by mass of coupling agent, 3-5 parts by mass of dispersing agent and 1-3 parts by mass of defoaming agent, mixing the above substances, dispersing for 0.5-1h under the conditions of 30-60 ℃ and 800-1500rpm, and filtering impurities in the mixture to obtain a mixed solution;
(3) adding an epoxy curing agent into the mixed solution, wherein the mass ratio of the mixed solution to the epoxy curing agent is 15-20: 1, stirring and mixing uniformly at room temperature, and standing for 10min to obtain the nano rare earth radiation-proof composite coating.
2. The preparation method of the nano rare earth radiation-proof composite coating according to claim 1, characterized by comprising the following steps: the antioxidant is at least one of antioxidant 168, antioxidant 1010, antioxidant 1076, antioxidant BHT and antioxidant 502A.
3. The preparation method of the nano rare earth radiation-proof composite coating according to claim 1, characterized by comprising the following steps: the coupling agent is at least one of polydimethylsiloxane, phenyltriethoxysilane, terephthalic acid metal salt, tetraethoxysilane and triethylvinylsilane.
4. The preparation method of the nano rare earth radiation-proof composite coating according to claim 1, characterized by comprising the following steps: the dispersing agent is at least one of organic silicon modified polyether DL400, BYK104S, dispersing agent 5040 and dispersing agent MF.
5. The preparation method of the nano rare earth radiation-proof composite coating according to claim 1, characterized by comprising the following steps: the specific surface area of the graphene is more than 15m2(ii) thin-layer graphene or single-layer graphene per gram.
6. The preparation method of the nano rare earth radiation-proof composite coating according to claim 1, characterized by comprising the following steps: the defoaming agent is at least one of an organic silicon defoaming agent, a polyether defoaming agent, a defoaming agent 110, a defoaming agent 106, DF1088 and DF 1052.
7. The nano rare earth radiation protective composite coating prepared by the method of any one of claims 1 to 6.
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Application publication date: 20200911 |