Radiation resistant coating, radiation resistant coating layer and method for producing the same

Abstract

The application discloses an anti-radiation coating, an anti-radiation coating layer and a preparation method thereof, and belongs to the technical field of coatings. The anti-radiation coating comprises the following components in parts by mass: 25-40 parts of a benzene propylene emulsion, 8-15 parts of talcum powder, 5-12 parts of a cosolvent, 4-12 parts of silica sol, 4-9 parts of magnetic silicon dioxide microspheres containing a silicon alcohol group, 3-7 parts of modified barite powder, 2-5 parts of zirconium sol, 1-4 parts of expanded graphite, 0.2-1 part of hydroxypropyl methyl cellulose, 0.1-1 part of amino-modified polysiloxane, 0.1-0.6 parts of alcohol ester twelve and 5-18 parts of deionized water. The coating has excellent anti-radiation performance, can reduce the penetration of rays, weaken electromagnetic waves, and can isolate radiation to a certain extent, absorb radiation waves, and has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of coating technology, in particular to an anti-radiation coating, an anti-radiation coating layer and a preparation method thereof. BACKGROUND

[0002] With the development of electronic communication technology and the explosive growth of Internet data traffic, carrier leakage is very common in optical communication, and there is currently no good anti-radiation coating. Anti-radiation coating is a new type of building material with broad application prospects, and it is of great significance to develop a coating with excellent anti-radiation effect. SUMMARY

[0003] The present application aims to overcome the deficiencies in the prior art and provide an anti-radiation coating, an anti-radiation coating layer and a preparation method thereof. The anti-radiation coating has excellent anti-radiation performance.

[0004] To achieve the above-mentioned purpose, the technical solution adopted by the present application is as follows:

[0005] An anti-radiation coating comprises the following components by mass: 25-40 parts of a styrene-acrylic emulsion, 8-15 parts of talcum powder, 5-12 parts of a cosolvent, 4-12 parts of a silica sol, 4-9 parts of magnetic silica microspheres containing a silicon alcohol group, 3-7 parts of modified barite powder, 2-5 parts of a zirconium sol, 1-4 parts of expanded graphite, 0.2-1 part of hydroxypropyl methyl cellulose, 0.1-1 part of amino-modified polysiloxane, 0.1-0.6 part of alcohol ester twelve, and 5-18 parts of deionized water.

[0006] The present application combines the above-mentioned various raw materials in a specific ratio to obtain a coating with excellent anti-radiation performance. The coating can reduce the penetration of radiation, weaken electromagnetic waves, and to some extent, isolate and absorb radiation waves, thus having a wide application prospect.

[0007] As a preferred embodiment of the present application, the anti-radiation coating comprises the following components by mass: 30-40 parts of a styrene-acrylic emulsion, 10-15 parts of talcum powder, 8-12 parts of a cosolvent, 6-12 parts of a silica sol, 5-9 parts of magnetic silica microspheres containing a silicon alcohol group, 4-7 parts of modified barite powder, 2-3 parts of a zirconium sol, 1-3 parts of expanded graphite, 0.2-0.8 parts of hydroxypropyl methyl cellulose, 0.1-0.8 parts of amino-modified polysiloxane, 0.1-0.5 parts of alcohol ester twelve, and 10-18 parts of deionized water.

[0008] As a preferred embodiment of the present invention, the radiation-resistant coating comprises the following components by weight: 35 parts styrene-acrylic emulsion, 12 parts talc, 10 parts cosolvent, 8 parts silica sol, 8 parts silanol-containing magnetic silica microspheres, 6 parts modified barite powder, 2.7 parts zirconium sol, 2 parts expanded graphite, 0.6 parts hydroxypropyl methylcellulose, 0.5 parts amino-modified polysiloxane, 0.2 parts alcohol ester dodecahydrate, and 15 parts deionized water. When these ingredients are combined in this specific ratio, the radiation-resistant performance is optimal.

[0009] As a preferred embodiment of the present invention, the particle size of the magnetic silica microspheres containing silanol groups is 0.1 to 5 μm.

[0010] As a preferred embodiment of the present invention, the cosolvent includes at least one of ethyl acetate, butyl acetate, propylene glycol methyl ether, propylene glycol butyl ether, ethylene glycol methyl ether, and N-methyl pyrrolidone.

[0011] As a preferred embodiment of the present invention, the preparation method of the modified barite powder is:

[0012] Grind the barite to 200-1000 mesh to obtain barite powder;

[0013] Concentrated sulfuric acid, concentrated nitric acid and deionized water are prepared into a modification liquid in a mass ratio of 1:(0.5-2):(12-20), heavy metal powder is added to the modification liquid, ultrasonically treated, filtered and dried to obtain pretreated heavy metal powder;

[0014] The pretreated heavy metal powder is subjected to plasma modification treatment and dried to obtain modified barite powder.

[0015] The surface of the modified barite powder contains abundant hydroxyl groups. Under stirring at a specific temperature, it can undergo a dehydration reaction with the silanol groups in the magnetic silica microspheres containing silanol groups. The generated ether and silicon-oxygen bonds more effectively improve the radiation protection performance. The combination of the two is more effective than the single modified barite powder or the magnetic silica microspheres containing silanol groups. That is, the two have a synergistic effect in radiation protection.

[0016] As a preferred embodiment of the present invention, the plasma modification treatment is carried out in a plasma cleaning machine of a plasma device, wherein the treatment time of the plasma cleaning machine is 10 to 40 minutes, the power is 150 to 300 W, and the air flow rate is 200 to 500 ml / min.

[0017] The present invention also provides a method for preparing a radiation-resistant coating, comprising the following steps:

[0018] Add silanol-containing magnetic silica microspheres, silica sol, modified barite powder, cosolvent, and deionized water into a reactor, heat to 75-95°C, and stir at 200-600 rpm for 12-24 hours;

[0019] The temperature was lowered to 35-45° C., styrene-acrylic emulsion, talc, zirconium sol, expanded graphite, hydroxypropyl methylcellulose, amino-modified polysiloxane and alcohol ester twelve were added, and the mixture was stirred at 400-1000 rpm to obtain an anti-radiation coating.

[0020] The present invention also provides an anti-radiation coating, comprising an upper layer, a middle layer, and a lower layer from top to bottom, wherein the upper layer is formed by using the anti-radiation coating described above.

[0021] As a preferred embodiment of the present invention, the middle layer is silicon dioxide and the lower layer is calcium fluoride;

[0022] The thickness of the upper layer is 100 to 500 nm; the thickness of the middle layer is 50 to 200 nm.

[0023] The beneficial effects of the present invention are: (1) the coating of the present invention has excellent radiation protection performance, the coating can reduce radiation penetration, weaken electromagnetic waves, and can isolate radiation to a certain extent, absorb radiation waves, and has broad application prospects; (2) the surface of the modified barite powder contains rich hydroxyl groups, which can undergo a dehydration reaction with the silanol groups in the magnetic silica microspheres containing silanol groups under stirring at a specific temperature, and the generated ether and silicon-oxygen bonds more effectively improve the radiation protection performance. The combination of the two is better than the single modified barite powder or the magnetic silica microspheres containing silanol groups, that is, the two have a synergistic effect in radiation protection. DETAILED DESCRIPTION

[0024] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0025] There is no particular limitation on the specific dispersing and stirring treatment methods.

[0026] In the present invention, unless otherwise stated, all parts are parts by mass.

[0027] The reagents or instruments used in the present invention, if the manufacturer is not indicated, are all conventional products that can be obtained commercially. The raw materials used in the examples and comparative examples of the present invention are as follows:

[0028] The styrene-acrylic emulsion is purchased from the Budrich Group, and the trade name is RS-998A.

[0029] The silica sol is purchased from Guangdong Kejing Technology Co., Ltd., and the trade name is HS-515.

[0030] The zirconium sol is purchased from Beijing Dekedaojin Technology Co., Ltd., and the trade name is DK-ZrO2-SL.

[0031] Silicon alcohol group-containing magnetic silica microspheres-1 are purchased from Karamay Reagent, and the item number is 211011092533, and the particle size is 4-5 μm.

[0032] Silicon alcohol group-containing magnetic silica microspheres-2 are purchased from Karamay Reagent, and the item number is 211011092516, and the particle size is 3-4 μm.

[0033] Silicon alcohol group-containing magnetic silica microspheres-3 are purchased from Karamay Reagent, and the item number is 211011092331, and the particle size is 0.1-1 μm.

[0034] The amino-modified polysiloxane is purchased from Guangzhou Longkai Chemical Co., Ltd., and the model number is LK-536.

[0035] The plasma treatment machine is a plasma vacuum plasma cleaning machine, which is a conventional commercially available product.

[0036] Example 1

[0037] An anti-radiation coating, comprising the following components by mass fraction: 35 parts of styrene-acrylic emulsion, 12 parts of talc, 10 parts of butyl acetate, 8 parts of silica sol, 8 parts of silicon alcohol group-containing magnetic silica microspheres-1, 6 parts of modified barite powder, 2.7 parts of zirconium sol, 2 parts of expanded graphite, 0.6 parts of hydroxypropyl methyl cellulose, 0.5 parts of amino-modified polysiloxane, 0.2 parts of alcohol ester twelve, and 15 parts of deionized water.

[0038] The preparation method of the modified barite powder is as follows:

[0039] Grind the barite to 800 mesh to obtain barite powder;

[0040] Prepare a modification liquid by mixing concentrated sulfuric acid, concentrated nitric acid and deionized water in a mass ratio of 1:1:18, add the heavy metal powder to the modification liquid (wherein the solid-liquid ratio of the heavy metal powder to the modification liquid is 1 g:8 ml), and treat with ultrasonic waves at 600 W for 30 min, filter, and dry to obtain the pretreated heavy metal powder;

[0041] The pretreated heavy metal powder was added into a plasma cleaning machine for plasma modification treatment, wherein the treatment time of the plasma cleaning machine was 30 minutes, the power was 200W, and the air flow rate was 300 ml / min. The powder was taken out and dried to obtain modified barite powder.

[0042] The preparation method of the radiation-resistant coating comprises the following steps:

[0043] Add silanol-containing magnetic silica microspheres-1, silica sol, modified barite powder, cosolvent, and deionized water into a reactor, heat to 90°C, and stir at 500 rpm for 20 h;

[0044] The temperature was lowered to 40° C., and styrene acrylic emulsion, talc, zirconium sol, expanded graphite, hydroxypropyl methylcellulose, amino-modified polysiloxane, and alcohol ester twelve were added and stirred at 800 rpm to obtain an anti-radiation coating.

[0045] Example 2

[0046] An anti-radiation coating comprises the following components in parts by mass: 28 parts of styrene-acrylic emulsion, 15 parts of talc, 12 parts of butyl acetate, 10 parts of silica sol, 4 parts of silanol-containing magnetic silica microspheres-2, 7 parts of modified barite powder, 3 parts of zirconium sol, 2 parts of expanded graphite, 0.6 parts of hydroxypropyl methylcellulose, 0.5 parts of amino-modified polysiloxane, 0.4 parts of alcohol ester dodecahydrate, and 17.5 parts of deionized water.

[0047] The preparation method of the modified barite powder is:

[0048] Grind the barite to 200 mesh to obtain barite powder;

[0049] Concentrated sulfuric acid, concentrated nitric acid and deionized water were prepared into a modification solution in a mass ratio of 1:0.5:18.5, heavy metal powder was added to the modification solution (wherein the solid-liquid ratio of heavy metal powder to modification solution was 1 g:8 ml), ultrasonically treated at 500 W for 35 min, filtered and dried to obtain pretreated heavy metal powder;

[0050] The pretreated heavy metal powder was added into a plasma cleaning machine for plasma modification treatment, wherein the treatment time of the plasma cleaning machine was 40 minutes, the power was 150W, and the air flow rate was 200 ml / min. The powder was taken out and dried to obtain modified barite powder.

[0051] The preparation method of the radiation-resistant coating comprises the following steps:

[0052] Add silanol-containing magnetic silica microspheres-2, silica sol, modified barite powder, cosolvent, and deionized water into a reactor, heat to 90°C, and stir at 500 rpm for 20 h;

[0053] The temperature was lowered to 40° C., and styrene acrylic emulsion, talc, zirconium sol, expanded graphite, hydroxypropyl methylcellulose, amino-modified polysiloxane, and alcohol ester twelve were added and stirred at 800 rpm to obtain an anti-radiation coating.

[0054] Example 3

[0055] An anti-radiation coating comprises the following components in parts by mass: 40 parts of styrene-acrylic emulsion, 8 parts of talc, 8 parts of butyl acetate, 6 parts of silica sol, 9 parts of silanol-containing magnetic silica microspheres-3, 3 parts of modified barite powder, 5 parts of zirconium sol, 4 parts of expanded graphite, 1 part of hydroxypropyl methylcellulose, 0.1 part of amino-modified polysiloxane, 0.1 part of alcohol ester dodecahydrate, and 15.8 parts of deionized water.

[0056] The preparation method of the modified barite powder is:

[0057] Grind the barite to 1000 mesh to obtain barite powder;

[0058] Concentrated sulfuric acid, concentrated nitric acid and deionized water were prepared into a modification solution in a mass ratio of 1:2:17, heavy metal powder was added to the modification solution (wherein the solid-liquid ratio of heavy metal powder to modification solution was 1 g:8 ml), ultrasonically treated at 400 W for 40 min, filtered and dried to obtain pretreated heavy metal powder;

[0059] The pretreated heavy metal powder was added into a plasma cleaning machine for plasma modification treatment, wherein the treatment time of the plasma cleaning machine was 20 minutes, the power was 300W, and the air flow rate was 400ml / min. The powder was taken out and dried to obtain modified barite powder.

[0060] The preparation method of the radiation-resistant coating comprises the following steps:

[0061] Add silanol-containing magnetic silica microspheres-3, silica sol, modified barite powder, cosolvent, and deionized water into a reactor, heat to 90°C, and stir at 500 rpm for 20 h;

[0062] The temperature was lowered to 40° C., and styrene acrylic emulsion, talc, zirconium sol, expanded graphite, hydroxypropyl methylcellulose, amino-modified polysiloxane, and alcohol ester twelve were added and stirred at 800 rpm to obtain an anti-radiation coating.

[0063] Example 4

[0064] An anti-radiation coating comprises an upper layer, a middle layer, and a lower layer from top to bottom, wherein the upper layer is formed by using the anti-radiation coating described in Example 1.

[0065] The middle layer is silicon dioxide, and the lower layer is calcium fluoride; the thickness of the upper layer is 385 nm; the thickness of the middle layer is 115 nm, and the thickness of the lower layer is 500 nm.

[0066] Comparative Example 1

[0067] The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 does not contain the silanol-containing magnetic silica microspheres-1, and uses an equal amount of modified barite powder, and all other conditions are the same.

[0068] In this comparative example, the anti-radiation coating includes the following components in parts by mass: 35 parts of styrene acrylic emulsion, 12 parts of talc, 10 parts of butyl acetate, 8 parts of silica sol, 14 parts of modified barite powder, 2.7 parts of zirconium sol, 2 parts of expanded graphite, 0.6 parts of hydroxypropyl methylcellulose, 0.5 parts of amino-modified polysiloxane, 0.2 parts of alcohol ester dodecahydrate, and 15 parts of deionized water.

[0069] Comparative Example 2

[0070] The difference between Comparative Example 2 and Example 1 is that Comparative Example 2 does not contain the silanol-containing magnetic silica microspheres-1, and uses an equal amount of modified barite powder, and all other conditions are the same.

[0071] In this comparative example, the anti-radiation coating includes the following components in parts by mass: 35 parts of styrene-acrylic emulsion, 12 parts of talc, 10 parts of butyl acetate, 8 parts of silica sol, 14 parts of silanol-containing magnetic silica microspheres-1, 2.7 parts of zirconium sol, 2 parts of expanded graphite, 0.6 parts of hydroxypropyl methylcellulose, 0.5 parts of amino-modified polysiloxane, 0.2 parts of alcohol ester dodecahydrate, and 15 parts of deionized water.

[0072] Comparative Example 3

[0073] The difference between Comparative Example 3 and Example 1 is that Comparative Example 3 uses barite powder instead of modified barite powder, and the other contents are the same.

[0074] The preparation method of the barite powder is: grinding barite to 800 mesh to obtain the barite powder.

[0075] Comparative Example 4

[0076] The difference between Comparative Example 4 and Example 1 is that Comparative Example 4 uses amino-containing magnetic silica microspheres-4 to replace silanol-containing magnetic silica microspheres-1, and all other conditions are the same.

[0077] The amino-containing magnetic silica microspheres-4 in this comparative example were purchased from Clamar Reagent, item number: 211008155408, with a particle size of 4-5 μm.

[0078] Test Case

[0079] The radiation-resistant coatings of Examples 1 to 3 and Comparative Examples 1 to 4 were tested according to NB / T 20133.3-2012, wherein the radiation dose was 3.6 Gy / s. When the radiation dose reached 2.592*10 6 After 10 days of irradiation, the coating was inspected and rated according to GB / T 1766. Thereafter, the coating was continuously irradiated at a dose of 3.6 Gy / s, and the coating was observed every other day until discoloration, gloss loss, chalking, blistering, cracking, or rusting as specified in GB / T 1766 appeared. The time was counted, and the test results are shown in Table 1.

[0080] Table 1

[0081]

[0082] It can be seen from Table 1 that the radiation-proof coating of the present invention has excellent radiation-proof performance.

[0083] Comparing Examples 1 to 3, it can be seen that different raw material ratios can affect the radiation protection performance to a certain extent, among which Example 1 is the best implementation method and has the best radiation protection performance.

[0084] By comparing Example 1 with Comparative Examples 1 to 2, it can be seen that the modified barite powder of the present invention and the magnetic silica microspheres containing silanol groups have a synergistic effect in radiation protection, and the combined use of the two can significantly improve the radiation protection performance.

[0085] By comparing Example 1 with Comparative Example 3, it can be seen that the radiation protection performance can be effectively improved by modifying the barite.

[0086] By comparing Example 1 with Comparative Example 4, it can be seen that the magnetic silica microspheres containing silanol groups can more significantly improve the radiation protection performance compared with the magnetic silica microspheres with other functional groups.

[0087] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A radiation-resistant coating, characterized in that: The invention comprises the following components in parts by mass: 25 to 40 parts of styrene-acrylic emulsion, 8 to 15 parts of talc powder, 5 to 12 parts of cosolvent, 4 to 12 parts of silica sol, 4 to 9 parts of magnetic silica microspheres containing silanol groups, 3 to 7 parts of modified barite powder, 2 to 5 parts of zirconium sol, 1 to 4 parts of expanded graphite, 0.2 to 1 part of hydroxypropyl methylcellulose, 0.1 to 1 part of amino-modified polysiloxane, 0.1 to 0.6 parts of alcohol ester dodecahydrate, and 5 to 18 parts of deionized water; The preparation method of the modified barite powder is: Grind the barite to 200-1000 mesh to obtain barite powder; Concentrated sulfuric acid, concentrated nitric acid and deionized water are prepared into a modification solution in a mass ratio of 1: (0.5-2): (12-20), barite powder is added to the modification solution, ultrasonically treated, filtered and dried to obtain pretreated barite powder; The pretreated barite powder is subjected to plasma modification treatment and dried to obtain modified barite powder; The plasma modification treatment is carried out in a plasma cleaning machine of a plasma device, wherein the treatment time of the plasma cleaning machine is 10 to 40 minutes, the power is 150 to 300 W, and the air flow rate is 200 to 500 ml / min.

2. The radiation-resistant coating according to claim 1, characterized in that: The invention comprises the following components in parts by mass: 30 to 40 parts of styrene-acrylic emulsion, 10 to 15 parts of talc powder, 8 to 12 parts of cosolvent, 6 to 12 parts of silica sol, 5 to 9 parts of magnetic silica microspheres containing silanol groups, 4 to 7 parts of modified barite powder, 2 to 3 parts of zirconium sol, 1 to 3 parts of expanded graphite, 0.2 to 0.8 parts of hydroxypropyl methylcellulose, 0.1 to 0.8 parts of amino-modified polysiloxane, 0.1 to 0.5 parts of alcohol ester dodecanone, and 10 to 18 parts of deionized water.

3. The radiation-resistant coating according to claim 1, characterized in that: The invention comprises the following components in parts by mass: 35 parts of styrene-acrylic emulsion, 12 parts of talc, 10 parts of cosolvent, 8 parts of silica sol, 8 parts of magnetic silica microspheres containing silanol groups, 6 parts of modified barite powder, 2.7 parts of zirconium sol, 2 parts of expanded graphite, 0.6 parts of hydroxypropyl methylcellulose, 0.5 parts of amino-modified polysiloxane, 0.2 parts of alcohol ester dodecahydrate, and 15 parts of deionized water.

4. The radiation-resistant coating according to claim 1, characterized in that: The particle size of the magnetic silica microspheres containing silanol groups is 0.1 to 5 μm.

5. The radiation-resistant coating according to claim 1, characterized in that: The cosolvent includes at least one of ethyl acetate, butyl acetate, propylene glycol methyl ether, propylene glycol butyl ether, ethylene glycol methyl ether, and N-methyl pyrrolidone.

6. The method for preparing the radiation-resistant coating according to any one of claims 1 to 5, characterized in that: The following steps are involved: Add silanol-containing magnetic silica microspheres, silica sol, modified barite powder, cosolvent, and deionized water into a reactor, heat to 75-95°C, and stir at 200-600 rpm for 12-24 hours; The temperature was lowered to 35-45° C., styrene-acrylic emulsion, talc, zirconium sol, expanded graphite, hydroxypropyl methylcellulose, amino-modified polysiloxane and alcohol ester twelve were added, and the mixture was stirred at 400-1000 rpm to obtain an anti-radiation coating.

7. A radiation-resistant coating, characterized in that: The invention comprises an upper layer, a middle layer and a lower layer from top to bottom, wherein the upper layer is formed by using the anti-radiation coating according to any one of claims 1 to 5.

8. The radiation-resistant coating according to claim 7, characterized in that The middle layer is silicon dioxide and the lower layer is calcium fluoride; The thickness of the upper layer is 100 to 500 nm; the thickness of the middle layer is 50 to 200 nm.

Images