A radiation-resistant color-developing coating, its preparation method and application

Abstract

This invention provides a radiation-resistant color-developing coating, its preparation method, and its application. The coating is prepared from components including component A and component B, with the mass ratio of component A to component B being 10:1 to 7. Component A comprises polyether-modified epoxy resin, epoxy resin, and an accelerator; component B includes a Mannich base curing agent. The radiation-resistant color-developing coating provided by this invention, when applied to the surface of equipment or facilities, provides corrosion protection when the radiation dose is low, and its color changes with the dose when the radiation dose is high. The coating can also be used as a means of radiation detection.

Description

Technical Field

[0001] This invention relates to the field of special functional coatings technology, and more specifically, to a radiation-resistant color-developing coating, its preparation method, and its application. Background Technology

[0002] As radiation research deepens and radiation technology matures, it is widely applied in various fields such as medicine and nuclear power. Radiation dose has become one of the important factors that need to be monitored and controlled in these applications. During normal operation, nuclear facilities are effectively protected, releasing relatively low doses of gamma radiation into the environment. However, when a nuclear facility experiences a radiation leak due to unknown factors, high doses of gamma radiation can appear in the environment within a short period, sometimes exceeding 10. 6 Gy is sometimes not detected in a timely manner by staff relying on relevant monitoring devices.

[0003] Radiochromic films are a colorimetric technology for radiation dose detection, allowing the measurement of total radiation dose through color-changing properties. These films are functional films made from organic materials coated with dyes. When irradiated by high-energy particles or rays, the film displays a specific color, and the radiation dose is determined by the color change. Currently, the linear range of the dose response for radiochromic films is mostly between 10⁻¹⁰ and 10⁻¹⁰. 3 Between Gy, these radiochromic films are generally used in low-dose monitoring fields such as medical treatment and human irradiation. Typically, in radiomedical and scientific experiments, these radiochromic films need to be placed in advance or carried by the individual at the known location of radiation leakage to be tested, with each film corresponding to one detection point. However, when the radiation leakage is unknown, difficult to predict, and exceeds the dose range monitored by the radiochromic film, placing the film is not feasible. Furthermore, currently developed radiochromic films primarily focus on high sensitivity under low-dose radiation environments, and these films lack corrosion resistance.

[0004] Currently, different areas of nuclear power plants are coated with conventional radiation-resistant anti-corrosion coatings of different colors according to design requirements, and even different colors are used as special markings. These conventional radiation-resistant anti-corrosion coatings have little color difference and little color change under irradiation, and do not have color development function. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a radiation-resistant color-developing coating and its preparation method. When the coating is applied to the surface of equipment or facilities, it provides corrosion protection when the radiation dose is low, and changes in color with the dose when the radiation dose is high. The coating can also be used as a means of radiation detection.

[0006] Firstly, one of the objectives of this invention is to provide a radiation-resistant color-developing coating.

[0007] Specifically, the coating is made from components including component A and component B, with the mass ratio of component A to component B being 10:1 to 7. Component A consists of components including polyether-modified epoxy resin, epoxy resin, and accelerator; component B includes a Mannich base curing agent.

[0008] It is worth mentioning that traditional radiation-resistant coatings mostly use low-molecular-weight liquid epoxy as the film-forming resin and polyamines such as polyamides as curing agents. The coating contains low levels of chromophores (amines or phenols), resulting in minimal discoloration under gamma irradiation. 6 After a cumulative dose of gamma radiation (Gy), the color difference is mostly below 10. This invention uses a Mannich base curing agent rich in two chromophores and increases its dosage to enhance the color-changing effect. However, compared to polyamide curing agents, Mannich base curing agents result in a more brittle coating after curing with epoxy resin. Simply increasing its dosage can lead to cracking during the application of the coating film. This invention uses a polyether-modified epoxy resin, which is significantly different from conventional epoxy resins, utilizing the soft segment structure of the polyether to balance the drawbacks of excessive Mannich base curing agents. Furthermore, this invention introduces haloamines (primary or secondary amines) as color-enhancing agents to improve the color development of the coating under irradiation. The haloamines used in this invention contain active amines that can participate in the resin curing reaction, are not easily leached, and exhibit good stability.

[0009] Furthermore, in the above coating, component A also includes titanium dioxide, extender filler, coupling agent, dispersant, and solvent A. The weight parts of each component are as follows, based on a total weight of 100 parts by weight for component A:

[0010]

[0011]

[0012] Furthermore, the molecular weight of the polyether-modified epoxy resin is 4000 to 20000; preferably, the polyether-modified epoxy resin is prepared from components including polyether polyurethane prepolymer and epoxy resin.

[0013] Furthermore, the epoxy resin has a molecular weight of 400 to 3000; preferably it is a bisphenol A type epoxy resin; more preferably it is one or a combination of E-51 epoxy resin, E-44 epoxy resin, E-20 epoxy resin, and E-12 epoxy resin.

[0014] Furthermore, the filler material is selected from silicate fillers; preferably from one or a combination of calcium carbonate, talc, mica powder, and silica fume.

[0015] Furthermore, the accelerator is selected from halogenated compounds having active hydrogen atoms of primary and / or secondary amines; preferably from one or a combination of dibromo-p-phenylenediamine and dichloro-p-phenylenediamine.

[0016] Furthermore, the coupling agent is selected from siloxanes having an epoxy functional group. It can be selected from conventional coupling agents with epoxy functional groups in the art, such as one or a combination of KH560 and Z-6040.

[0017] Furthermore, the dispersant is selected from one or a combination of BYK-P104S, BYK-110, Disponer928, and FX9086.

[0018] Further, solvent A is selected from one or a combination of benzene, alcohol, ketone, and ester solvents; preferably from one or a combination of xylene, n-butanol, and cyclohexanone; more preferably from a mixture of xylene, n-butanol, and cyclohexanone; wherein the mass ratio of xylene, n-butanol, and cyclohexanone is 1:0.2 to 1:0.2 to 1.

[0019] Furthermore, in the above coating, component B also includes solvent B; solvent B is selected from one or a combination of benzene, alcohol, ketone, and ester solvents; preferably from one or a combination of xylene and n-butanol.

[0020] Furthermore, taking 100 parts by weight of component B as the total weight, the parts by weight of each component are as follows:

[0021] 30-98 parts by weight of Mannich alkaline curing agent;

[0022] Solvent B: 3-70 parts by weight.

[0023] The Mannich base curing agent is selected from amine curing agents containing phenolic hydroxyl groups and primary or secondary amines; preferably, it is selected from one or a combination of Mannich base T31, Mannich base NX-2009, NX-2015, NX-5607, and LITE2001.

[0024] Secondly, another objective of this invention is to provide a method for preparing a radiation-resistant color-developing coating, which is one of the objectives of this invention.

[0025] Specifically, the method includes: mixing the raw material components in component A to form a slurry, mixing the raw material components in component B to form a solution, and then mixing component A and component B to obtain a radiation-resistant color-developing coating.

[0026] More specifically, the method includes the following steps:

[0027] Step 1: Add the polyether-modified epoxy resin, epoxy resin, coupling agent, dispersant, and solvent A to a mixing container according to the prescribed dosage. Stir at 500–1500 r / min for 10–60 min until homogeneous. Then add titanium dioxide, extender filler, and accelerator. Disperse the mixture using high-speed stirring or a sand mill until the fineness is less than 50 micrometers. Filter through an 80–120 mesh screen, measure and package to obtain the slurry of component A.

[0028] Step 2: Add Mannich base curing agent and solvent B to the stirring container according to the formula dosage, stir at 300-800 r / min for 10-30 min until uniform, filter through an 80-120 mesh screen, measure and package to obtain component B solution;

[0029] Step 3: Mix the solutions prepared in Step 1 and Step 2 evenly according to the weight ratio to obtain the radiation-resistant color-developing coating.

[0030] Finally, a third objective of the present invention is to provide an application of the radiation-resistant color-developing coating, which is one of the objectives of the present invention.

[0031] Specifically, the application method is as follows: the radiation-resistant color-developing coating obtained by mixing component A and component B is applied to the surface of an object by brushing, spraying, or rolling to obtain a coating.

[0032] The coating provided by this invention can display different colors as the cumulative dose of gamma radiation accumulates.

[0033] The coating provided by the present invention is in 10 4 After a cumulative dose of gamma radiation (Gy), the color difference is mostly around 10 or less, meaning that the appearance color remains stable under normal operating conditions of nuclear facilities; however, when the cumulative gamma radiation dose reaches 10... 5 At the Gy level, the color difference reaches 25, and the color change becomes more obvious. Furthermore, the color gradually deepens with increasing dose, reaching a point where the cumulative gamma radiation dose reaches 10. 7 At the Gy level, the color difference reaches 70, serving as a strong warning. The coating of this invention has a significant color-changing effect, providing workers with a strong visual impact and serving as an instant warning and reminder, thus acting as an effective auxiliary means for radiation detection.

[0034] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0035] 1. The coating provided by this invention can change color with the accumulation of dosage, and can also have the functions of conventional anti-corrosion protection, accident detection, and warning reminder.

[0036] 2. The coating of the present invention is applied to the surface of equipment and facilities under irradiation environment. When the nuclear facility is in normal use and the radiation dose is low, the coating can provide good anti-corrosion protection, and the coating color changes little, which can ensure the stability of appearance.

[0037] 3. The coating provided by this invention can provide corrosion protection for equipment when the radiation dose is low, and the coating can change color with the dose when the radiation dose is high, especially when receiving high doses (greater than 10). 5 After being irradiated with gamma rays, Gy exhibits different levels of color change with increasing dose. It can be used in environments with potential high-dose nuclear radiation leaks. The coating can be used to assist in radiation detection, determine the occurrence of accidents, or provide warnings.

[0038] 4. The radiation-resistant color-developing coating provided by this invention achieves unexpected results by adding an excess of Mannich base curing agent, an appropriate amount of reactive accelerator, and polyether-modified epoxy resin. The coating is effective at 10... 4 After a cumulative dose of gamma radiation (Gy), the color difference is mostly below 10, meaning that under long-term normal operation of nuclear facilities, the color change is small, the appearance is stable, the decorative effect is good, and the coating has a good anti-corrosion protection effect; when the cumulative dose of gamma radiation reaches 10... 5 At the Gy level, the color difference can reach 25, with noticeable color changes. The color gradually deepens with increasing dose, reaching a maximum when the cumulative gamma radiation dose reaches 10. 7 After reaching the Gy level, the color difference reaches 70, and the color contrasts greatly with the original color, which can serve as a good warning. Attached Figure Description

[0039] Figure 1 The diagram shows a comparison of color changes of the coating under different doses of irradiation and different color differences. Detailed Implementation

[0040] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0041] In the following examples and comparative examples, all raw materials were commercially available. Specifically, the polyether-modified epoxy resin was purchased from Idico Japan; E-51 and E-44 epoxy resins were purchased from Nantong Xingchen Synthetic Materials Co., Ltd.; E-20 and E-12 epoxy resins were purchased from Nanya Epoxy Resin (Kunshan) Co., Ltd.; dibromo-p-phenylenediamine and dichloro-p-phenylenediamine were purchased from Hubei Guangao Biotechnology Co., Ltd.; Mannich base T31 was purchased from Tianjin Chengli Chemical Co., Ltd.; and Mannich base NX-2009 was purchased from Cardlä Specialty Chemicals Co., Ltd.

[0042] The test methods used in the following embodiments are as follows:

[0043] Impact strength (Kg.cm) test: GB / T1732-2020 Test Method for Impact Resistance of Coating Film was adopted;

[0044] Adhesion (with primer): The adhesion was determined using the pull-off method of paints and varnishes as specified in GB / T 5210-2006.

[0045] Neutral salt spray resistance test (with primer): GB / T1771-2007 Test method for neutral salt spray resistance of paints and varnishes; the total dry film thickness was 140μm and the test time was 1000h. The paint film did not blister or crack.

[0046] Radiation resistance test: The test was conducted according to the test method for the effect of gamma-ray irradiation on coating systems, as specified in NB / T20133.3-2012.

[0047] Example 1

[0048] This embodiment illustrates the preparation of radiation-resistant color-developing coatings, wherein the raw material components and amounts of components A and B are shown in Table 1:

[0049] Table 1:

[0050] Component A Dosage (parts by weight) Polyether modified epoxy resin 5 E-44 epoxy resin 30 Titanium dioxide 30 talcum powder 10 dibromo-p-phenylenediamine 2 KH560 2 BYK-110 3 xylene 10 n-Butanol 5 Cyclohexanone 3 total 100 Component B Dosage (parts by weight) Mannich base T31 80 xylene 15 n-Butanol 5 total 100

[0051] The following describes the preparation method for component A:

[0052] Add the polyether-modified epoxy resin (molecular weight 12000), E-44 epoxy resin (molecular weight approximately 450), KH560, BYK-110 and solvent to the above dosage into a stirring container, and stir at 800 r / min for 30 min until homogeneous; then add titanium dioxide, talc and dibromo-p-phenylenediamine, and grind with a sand mill until the fineness is less than 50 microns, pass through a 100-mesh filter, and meter and package to obtain component A slurry.

[0053] The following describes the preparation method for component B:

[0054] Add Mannich base T31, xylene, and n-butanol to the stirring container according to the above dosage, stir at 300 r / min for 10 min until uniform, pass through a 100-mesh filter, measure and package to obtain curing agent component B.

[0055] Mix the above components A and B at a weight ratio of 10:3 and set aside for later use.

[0056] Example 2

[0057] This embodiment illustrates the preparation of radiation-resistant color-developing coatings, wherein the raw material components and amounts of components A and B are shown in Table 2:

[0058] Table 2

[0059] Component A Dosage (parts by weight) Polyether modified epoxy resin 3 E-20 epoxy resin 27 Titanium dioxide 30 Silica powder 15 dichloro-p-phenylenediamine 3 Z-6040 2 FX9086 2 xylene 10 n-Butanol 5 Cyclohexanone 3 total 100 Component B Dosage (parts by weight) Mannich base NX-2009 40 xylene 40 n-Butanol 20 total 100

[0060] The following describes the preparation method for component A:

[0061] Add the polyether-modified epoxy resin (molecular weight approximately 8000), E-20 epoxy resin (molecular weight approximately 900), Z-6040, FX9086 and solvent to the stirring container according to the above dosage. Stir at 1200 r / min for 20 min until homogeneous. Then add titanium dioxide, silica powder and dichloro-p-phenylenediamine. Grind the mixture in a sand mill until the fineness is less than 50 microns. Pass the mixture through a 100-mesh filter, measure and package it to obtain component A slurry.

[0062] The following describes the preparation method for component B:

[0063] Add Mannich base NX-2009, xylene, and n-butanol to the stirring container according to the above dosage. Stir at 500 r / min for 30 min until homogeneous. Pass through a 100-mesh filter, measure and package to obtain curing agent component B.

[0064] Mix the above components A and B at a weight ratio of 10:4 and set aside for later use.

[0065] Comparative Example 1

[0066] This comparative example illustrates the preparation of radiation-resistant color-developing coatings. The raw material components and amounts of components A and B are shown in Table 3.

[0067] Table 3:

[0068] Component A Dosage (parts by weight) Polyether modified epoxy resin 3 E-20 epoxy resin 27 Titanium dioxide 35 Silica powder 10 Z-6040 2 FX9086 2 xylene 13 Butanol 5 Cyclohexanone 3 total 100 Component B Dosage (parts by weight) NX-2009 40 xylene 40 n-Butanol 20 total 100

[0069] The preparation method of this comparative coating is the same as that of Example 2.

[0070] Comparative Example 2

[0071] This comparative example illustrates the preparation of radiation-resistant color-developing coatings. The raw material components and amounts of components A and B are shown in Table 4.

[0072] Table 4:

[0073]

[0074]

[0075] The preparation method of this comparative coating is the same as that of Example 2.

[0076] Comparative Example 3

[0077] This comparative example illustrates the preparation of radiation-resistant color-developing coatings. The raw material components and amounts of components A and B are shown in Table 5.

[0078] Table 5:

[0079] Component A Dosage (parts by weight) Polyether modified epoxy resin 3 E-20 epoxy resin 27 Titanium dioxide 30 Silica powder 15 dichloro-p-phenylenediamine 3 Z-6040 2 FX9086 2 xylene 10 n-Butanol 5 Cyclohexanone 3 total 100 Component B Dosage (parts by weight) SY-115 polyamide 55 xylene 30 Butanol 15 total 100

[0080] The preparation method of this comparative coating is the same as that of Example 2.

[0081] The coatings prepared in the above embodiments and comparative proportions were subjected to performance tests. The substrate used in the test was a 150×75×3mm hot-rolled sandblasted steel plate. The coating was applied by air spraying and the film thickness was 50μm. With the addition of a 90μm special primer, a total film thickness of 140μm was obtained. The test results are shown in Table 6.

[0082] Table 6:

[0083]

[0084] As shown in Table 6, the coatings provided in Examples 1-2 all have good impact resistance, neutral salt spray resistance, and anti-corrosion protection performance, and their adhesion is far higher than the technical requirement of 3MPa for nuclear-grade radiation-resistant coatings.

[0085] Furthermore, a comparison between Comparative Example 1 and Example 2 shows that Comparative Example 1 did not add a color development promoter, and its color did not change under low-dose irradiation, while the color change was not obvious under high-dose irradiation.

[0086] Furthermore, a comparison between Comparative Example 2 and Example 2 shows that Comparative Example 2, without the addition of a flexible polyether-modified epoxy resin, can only pass the 30cm impact resistance test. The coating has poor impact resistance, poor flexibility, is brittle, and is easily broken.

[0087] Furthermore, a comparison between Comparative Example 3 and Example 2 shows that when polyamide resin curing agent SY-115 (which does not contain phenolic functional groups in its molecular structure) is added to the system of Comparative Example 3, the color development effect of the coating is not obvious.

[0088] Furthermore, through cooperation with Figure 1 As can be seen from the color comparison, the coatings provided in Examples 1 and 2 are resistant to radiation doses of 10. 4 Gy~1×10 7 At Gy, the coating exhibits distinct color changes, while the coatings provided in Comparative Examples 1 and 3 show no significant color changes. Therefore, the coating provided by this invention can meet the color warning requirements in scenarios involving high-dose radiation leaks in nuclear facilities.

[0089] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A radiation-resistant color-developing coating, prepared from components including component A and component B, wherein the mass ratio of component A to component B is 10:1 to 7; Component A consists of components including polyether-modified epoxy resin, epoxy resin, accelerator, titanium dioxide, extender filler, coupling agent, dispersant, and solvent A. Component B includes a Mannich base curing agent; Based on a total weight of 100 parts by weight for component A, the weight parts of each component are as follows: 3-30 parts by weight of polyether-modified epoxy resin; 10-50 parts by weight of epoxy resin; 10-40 parts by weight of titanium dioxide; 0-30 parts by weight of extender filler; Accelerator 1-10 parts by weight; 1-10 parts by weight of coupling agent; Dispersant 1-10 parts by weight; Solvent A: 10-40 parts by weight; The molecular weight of the polyether-modified epoxy resin is 4000 to 20000. The molecular weight of the epoxy resin is 400 to 3000; The promoter is selected from halogenated compounds having active hydrogen atoms of primary and / or secondary amines.

2. The radiation-resistant color-developing coating according to claim 1, characterized in that, The epoxy resin is selected from bisphenol A type epoxy resins; and / or, The bulk filler is selected from silicate fillers; and / or, The accelerator is selected from one or a combination of dibromo-p-phenylenediamine and dichloro-p-phenylenediamine; and / or, The coupling agent is selected from siloxanes having epoxy functional groups; and / or, The dispersant is selected from one or a combination of BYK-P104S, BYK-110, Disponer928, and FX9086; and / or, Solvent A is selected from one or a combination of benzene, alcohol, ketone, and ester solvents.

3. The radiation-resistant color-developing coating according to claim 2, characterized in that, The filler material is selected from one or a combination of calcium carbonate, talc, mica powder, and silica fume; and / or, Solvent A is selected from one or a combination of xylene, n-butanol, and cyclohexanone.

4. The radiation-resistant color-developing coating according to claim 1, characterized in that, Component B further includes solvent B; solvent B is selected from one or a combination of benzene, alcohol, ketone, and ester solvents.

5. The radiation-resistant color-developing coating according to claim 4, characterized in that, Solvent B is selected from one or a combination of xylene and n-butanol.

6. The radiation-resistant color-developing coating according to claim 4, characterized in that, Based on a total weight of 100 parts by weight for component B, the weight parts of each component are as follows: Mannich alkaline curing agent, 30-98 parts by weight; Solvent B3~70 parts by weight.

7. The radiation-resistant color-developing coating according to claim 1, characterized in that, The Mannich base curing agent is selected from amine curing agents containing phenolic hydroxyl groups and primary or secondary amines.

8. The radiation-resistant color-developing coating according to claim 7, characterized in that, The Mannice base curing agent is selected from one or a combination of Mannice base T31, Mannice base NX-2009, NX-2015, NX-5607, and LITE2001.

9. The method for preparing the radiation-resistant color-developing coating according to any one of claims 1 to 8, the method comprising: The raw material components in component A are mixed to form a slurry, and the raw material components in component B are mixed to form a solution. Then, components A and B are mixed to obtain the radiation-resistant color-developing coating.

10. The application of the radiation-resistant color-developing coating according to any one of claims 1 to 8, wherein the application method is as follows: the radiation-resistant color-developing coating into which component A and component B are mixed is applied to the surface of an object by brushing, spraying, or rolling to obtain a coating.

11. In the application of the radiation-resistant color-developing coating according to claim 10, the coating displays different colors as the cumulative dose of gamma radiation accumulates.

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