Preparation method, material and application of flexible polymer-based super-hydrophobic coating material for tritium protection

Abstract

The present application discloses a preparation method, material and application of a flexible polymer-based super-hydrophobic coating material for tritium protection, belonging to the technical field of tritium protection materials; the super-hydrophobic coating on the surface of the flexible polymer is composed of functional nanoparticles, an adhesive and a dispersion; the coating material utilizes functional nanoparticles and an adhesive with hydrophobic properties, which are sprayed on the surface of a polymer substrate by a spraying method, and a super-hydrophobic coating is obtained after thermal curing; the super-hydrophobic properties of the prepared coating are still maintained under a stretched state and chemical corrosion conditions, and has important application value in the field of tritium protection.

Description

Technical Field

[0001] The present invention relates to the technical field of tritium protection materials, and in particular to a preparation method, material and application of a flexible polymer-based super-hydrophobic coating material for tritium protection. Background Art

[0002] In recent years, tritium protection equipment in the field of nuclear technology has a relevant demand for super-hydrophobic (water contact angle on the material surface is greater than 150°) technology. Tritium will exchange with hydrogen isotopes and easily exist in a water-containing environment. And the contact of organisms with tritiated water will cause tritium to enter the human body and cause internal irradiation, causing radiation hazards to organisms. Therefore, in the process of tritium protection, protection against tritiated water is the first line of defense. Therefore, the research on super-hydrophobic coatings for tritium protection equipment is urgently needed. The research on super-hydrophobic coatings of flexible polymer-based composite materials mainly focuses on the following aspects: 1. Material selection; 2. Coating structure design; 3. Surface modification technology.

[0003] At present, some studies have tried to select materials with good hydrophobic properties as the substrate or functional material of the coating to enhance the hydrophobicity of the composite material. Through the structural design of the hydrophobic coating, a micrometer or nanometer scale concave-convex structure is formed to improve the overall hydrophobicity of the material. Or the surface is treated by chemical modification technology to improve the hydrophobicity of the coating. However, the flexible composite materials used in tritium-related scenes will be subjected to tensile deformation during use. During the tensile deformation (strain greater than 350%), the super-hydrophobic coating structure is easily damaged, which eventually leads to the loss of super-hydrophobic properties (SuX, Li H, Lai X, et al. ACS Applied Materials & Interfaces, 2018, 10 (12): 10587-10597). Some scholars have used the spraying method to coat SiO 2 Add it to the ethanol solution and spray it evenly on the shrink film with a spray gun. Then mix a certain amount of PDMS and curing agent and pour it into the SiO 2 On a film, after curing, it is peeled off to obtain a composite material with super-hydrophobic properties with certain tensile properties; but this method is complicated and can only maintain super-hydrophobic properties under a change of 0-100%, and there are still limitations in tensile resistance (Xue CH, Tian QQ, Jia ST, et al. RSC Advances, 2020, 10 (33): 19466-19473). Super-hydrophobic coatings are easily damaged when used in acidic, alkaline, high humidity or salt environments. Once tritium invades this environment, super-hydrophobic coatings are required to have chemical corrosion resistance. Therefore, it is a difficult problem to prepare a flexible polymer-based super-hydrophobic coating material for tritium protection that is resistant to deformation and chemical corrosion. Summary of the invention

[0004] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a method for preparing and applying a flexible polymer-based super-hydrophobic coating material for tritium protection, aiming to solve the problems of weak deformation resistance and chemical corrosion resistance of super-hydrophobic coatings prepared by existing spraying technology.

[0005] Specifically, the technical solutions provided in this application are as follows:

[0006] First, the present application provides a method for preparing a flexible polymer-based super-hydrophobic coating material for tritium protection, comprising the following steps:

[0007] (1) Preparation of adhesive dispersion:

[0008] Add polybutadiene and benzoyl peroxide to the container containing the dispersion solution at room temperature, seal the container, and stir it magnetically for 20-30 minutes to obtain an adhesive dispersion for later use;

[0009] The above dispersion liquid can be selected from one or more of n-hexane, ethanol, and acetone;

[0010] (2) Preparation of hydrophobic spray slurry: adding the functional nanoparticles to the adhesive dispersion prepared in step (1) at room temperature, sealing the container again, magnetically stirring for 1-3 minutes, and then ultrasonicating for 20-30 minutes to obtain a flexible polymer-based super-hydrophobic coating material for tritium protection;

[0011] The size of the functional nanoparticles is 50-500nm, and the shape can be spherical, rod-shaped or flake-shaped; the material can be selected from one or more of silicon dioxide, aluminum oxide, montmorillonite and carbon black;

[0012] The materials added above, by weight, are: 1-2 parts of functional nanoparticles, 2-3 parts of polybutadiene, 0.2-0.3 parts of benzoyl peroxide, and 100 parts of dispersion liquid;

[0013] Furthermore, the mass ratio of polybutadiene to benzoyl peroxide is preferably 10:1.

[0014] Secondly, the present application also provides a flexible polymer-based super-hydrophobic coating material for tritium protection prepared according to the above method.

[0015] Third, the present application provides the application of the flexible polymer-based super-hydrophobic coating material for tritium protection prepared by the above method in the preparation of tritium protection material coating. Its application method is: 1) the flexible polymer-based super-hydrophobic coating material for tritium protection is drawn with a dropper, and the loaded coating material is atomized with 25psi pressurized air using a spray pen, and the pen tip is aligned with the vertical line of the center of the substrate surface, and the pen tip position is 10-15cm away from the center of the target substrate. It is evenly sprayed on the target substrate surface for 30-45s, and the tritium protection material coating controls the coating material thickness within the range of 10-20μm to form a tritium protection material coating; 2) the substrate spraying surface is placed up, heated and cured in an oven at 120°C for 1h, and placed in a sealed environment after being taken out, and cooled at room temperature for 1h; that is, a flexible material that can be used for tritium protection is obtained. The above-mentioned substrate can use conventional substrates in the art, such as rubber (preferably flexible rubber), fiber fabrics, polyurethane films, etc.

[0016] Furthermore, the above-mentioned substrate also includes a cleaning step before spraying, and the specific method is as follows: 1) immersing the substrate in ethanol for ultrasonic cleaning for 20-30 minutes, and the ultrasonic power is 50-100W; 2) rinsing the substrate after ultrasonic cleaning with deionized water 2-3 times; 3) placing the above-mentioned cleaned substrate in a 60°C oven to dry for 12 hours, taking it out and sealing it with plastic wrap, and letting it stand at room temperature for 1 hour.

[0017] The flexible polymer-based super-hydrophobic coating for tritium protection provided in this application uses adhesives and functional nanoparticles to form micro-pillars at the target surface, gradually forming a rough hierarchical structure, and finally achieving super-hydrophobic performance. The contact angle of the obtained super-hydrophobic coating can reach up to 162.37°, with excellent hydrophobic performance; and it has excellent tensile resistance. In the process of stretching from 0-800%, the contact angle can stably maintain super-hydrophobic properties (greater than 150°). At the same time, the coating also has excellent chemical corrosion resistance. After soaking in pH=1 HCl solution, pH=14 NaOH solution and 3.5wt% NaCl solution for 2-8h, the coating can still maintain super-hydrophobic properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The present invention is a schematic diagram of the process of preparing and applying a flexible polymer-based super-hydrophobic coating for tritium protection in an embodiment;

[0019] Figure 2 This is a contact angle measurement diagram of the super-hydrophobic coating of the composite material obtained in Example 1 under tension;

[0020] Figure 3 The SEM images of the surface (A) and cross section (B) of the super-hydrophobic coating obtained by the method of Example 2;

[0021] Figure 4These are contact angle measurement graphs of super-hydrophobic coatings after immersion in acid, alkali or salt of Example 1 (AC), Example 2 (DF) and Example 3 (GI). DETAILED DESCRIPTION

[0022] The present invention is further described below by way of examples. The chemical reagents used in the examples are all analytically pure, polybutadiene (PB, Mw=2000) was purchased from Tianjin Xiensi Biochemical Technology Co., Ltd., benzoyl peroxide (BPO) was purchased from Aladdin Biochemical Technology Co., Ltd., and spherical carbon black N550 (CB, particle size range 50-150 nm) was purchased from Tianjin Yihuachang New Materials Co., Ltd.

[0023] Example 1 Preparation and application of super hydrophobic coating material

[0024] Figure 1 The following is a schematic diagram of the process of preparing and applying a flexible polymer-based super-hydrophobic coating for tritium protection in an embodiment, and the specific steps are as follows:

[0025] (1) Preparation of adhesive dispersion solution

[0026] 2 g of polybutadiene and 0.2 g of benzoyl peroxide were added to 100 g of n-hexane at room temperature, the container of the mixed solution was sealed, and magnetic stirring was performed for 30 min (1000 rpm) at a speed of 1000 r / min to obtain an adhesive dispersion.

[0027] (2) Preparation of hydrophobic spray slurry

[0028] 2 g of carbon black was added to the binder dispersion solution at room temperature, the container was sealed, magnetic stirring was performed for 1 min, and then ultrasonication was performed for 30 min at an ultrasonic power of 450 W to obtain a spray slurry.

[0029] (3) Spraying

[0030] A 30mm*60mm*1mm substrate (butyl rubber film) that had been cleaned in advance was fixed on a glass plate, 20mL of spray slurry was taken with a dropper, and the loaded spray slurry was atomized with 25psi pressurized air using an airbrush (purchased from Ningbo Fenghua Tiandi Airbrush Manufacturing Co., Ltd., TD-180). The pen tip was aligned with the center vertical line of the substrate surface, and the pen tip was positioned 10cm away from the center of the target substrate. The target substrate surface was evenly sprayed for 30s to form a tritium protective material coating, and the coating thickness was controlled at about 15μm (ensure that it is within the range of 10-20 microns).

[0031] The above cleaning refers to: 1) immersing the substrate in ethanol for ultrasonic cleaning for 20 minutes, with an ultrasonic power of 450W; 2) rinsing the substrate after ultrasonic cleaning with deionized water twice; 3) placing the substrate after the above cleaning in a 60°C oven to dry for 12 hours, taking it out and sealing it with plastic wrap, leaving it at room temperature for 1 hour before spraying the slurry.

[0032] (4) Heating and curing

[0033] The sample was placed in a culture dish with the sprayed surface facing upward, and the sample and the culture dish were placed in an oven at 120° C. for heating and curing for 1 hour. After being taken out, the sample was sealed with plastic wrap and allowed to stand at room temperature for 1 hour to obtain a composite material 1 having a hydrophobic coating with tritium protection.

[0034] According to the GB / T 30447-2013 standard, the water contact angle of the hydrophobic coating for tritium protection on the surface of the composite material 1 obtained in this embodiment reached 162.37°, reaching the super hydrophobic (150°) standard, using a JC2000D2 contact angle meter produced by Shanghai Zhongchen Digital Technology Equipment Co., Ltd.

[0035] like Figure 2 As shown, the hydrophobic coating always maintains superhydrophobic properties during the tensile deformation process of 0-800%.

[0036] The hydrophobic coating prepared in this embodiment was tested for chemical stability resistance (for the detection method, see the document "Dai Xiaogang. Preparation of super-hydrophobic silica and application research of its coating [D]. Beijing University of Chemical Technology, 2022". DOI: 10.26939 / d.cnki.gbhgu.2022.002133). After immersion in pH = 1 HCl solution, pH = 14 NaOH solution and 3.5wt% NaCl solution for 8 hours, the hydrophobic coating in this embodiment can still maintain its super-hydrophobic properties.

[0037] Example 2 Preparation and application of super hydrophobic coating material

[0038] The preparation method is as follows:

[0039] (1) Preparation of adhesive dispersion solution

[0040] 2.67 g of polybutadiene and 0.27 g of benzoyl peroxide were added to 100 g of n-hexane at room temperature to obtain a mixed solution I. The container containing the mixed solution I was sealed and magnetically stirred for 30 min at a speed of 1000 r / min to obtain an adhesive dispersion.

[0041] (2) Preparation of hydrophobic spray slurry

[0042] 1.33 g of carbon black was added to the binder dispersion solution prepared in step (1) at room temperature to obtain a mixed solution II. The container of the mixed solution II was sealed, magnetically stirred for 1 min, and then ultrasonicated for 30 min (450 W) to obtain a spray slurry.

[0043] (3) Spraying

[0044] Fix the pre-cleaned 30mm*60mm*1mm butyl rubber film on a glass plate, use a dropper to absorb 20mL of spray slurry, and use the TD-180 model airbrush produced by Ningbo Fenghua Tiandi Airbrush Manufacturing Co., Ltd. to atomize the loaded spray slurry with 25psi pressurized air. Align the pen tip with the center vertical line of the substrate surface, and position the pen tip 10cm away from the center of the target substrate. Evenly spray it on the target substrate surface for 30s to form a tritium protective material coating, and control the coating thickness to about 15μm.

[0045] The above cleaning refers to: 1) immersing the substrate in ethanol for ultrasonic cleaning for 20 minutes, with an ultrasonic power of 80W; 2) rinsing the substrate after ultrasonic cleaning with deionized water twice; 3) placing the substrate after the above cleaning in a 60°C oven to dry for 12 hours, taking it out and sealing it with plastic wrap, leaving it at room temperature for 1 hour before spraying the slurry.

[0046] (4) Heating and curing

[0047] The sample was placed in a culture dish with the sprayed surface facing upward, and the sample and the culture dish were placed in an oven at 120°C for heating and curing for 1 hour. After being taken out, the sample was sealed with plastic wrap and allowed to stand at room temperature for 1 hour to obtain a composite material 2 having a tritium-protected hydrophobic coating.

[0048] After testing (the testing method is the same as that in Example 1), the water contact angle of the hydrophobic coating for tritium protection on the surface of the composite material 2 obtained in this example reaches 161.84°, reaching the super-hydrophobic standard; during the tensile deformation process of 0-800%, the hydrophobic coating always maintains the super-hydrophobic property; and after being immersed in a pH = 1 HCl solution, a pH = 14 NaOH solution, and a 3.5wt% NaCl solution for 8 hours, the hydrophobic coating can still maintain the super-hydrophobic property.

[0049] Example 3 Preparation and application of super hydrophobic coating material

[0050] (1) Preparation of adhesive dispersion solution

[0051] 3 g of polybutadiene and 0.3 g of benzoyl peroxide were added to 100 g of n-hexane at room temperature to obtain a mixed solution. The container of the mixed solution was sealed and magnetically stirred for 30 min at a speed of 1000 r / min to obtain an adhesive dispersion.

[0052] (2) Preparation of hydrophobic spray slurry

[0053] 1 g of carbon black was added to the binder dispersion solution at room temperature, the container was sealed again, magnetic stirring was performed for 1 min, and then ultrasonication was performed for 30 min with the ultrasonic power set to 450 W to obtain a spray slurry.

[0054] (3) Spraying

[0055] Fix the pre-cleaned 30mm*60mm*1mm butyl rubber on a glass plate, use a dropper to absorb 20mL of spray slurry, and use the TD-180 model airbrush produced by Ningbo Fenghua Tiandi Airbrush Manufacturing Co., Ltd. to atomize the loaded spray slurry with 25psi pressurized air. The pen tip is aligned with the vertical line of the center of the substrate surface. The pen tip is positioned 10cm away from the center of the target substrate and evenly sprayed on the target substrate surface for 30s to form a tritium protective material coating with a coating thickness controlled at about 15μm.

[0056] The above cleaning refers to: 1) immersing the substrate in ethanol for ultrasonic cleaning for 20 minutes, with an ultrasonic power of 450W; 2) rinsing the substrate after ultrasonic cleaning with deionized water twice; 3) placing the substrate after the above cleaning in a 60°C oven to dry for 12 hours, taking it out and sealing it with plastic wrap, leaving it at room temperature for 1 hour before spraying the slurry.

[0057] (4) Heating and curing

[0058] The sample was placed in a culture dish with the sprayed surface facing upward, and the sample and the culture dish were placed in an oven at 120°C for heating and curing for 1 hour. After being taken out, the sample was sealed with plastic wrap and allowed to stand at room temperature for 1 hour to obtain a composite material 3 having a tritium-protected hydrophobic coating.

[0059] After testing (the testing method is the same as that in Example 1), the water contact angle of the hydrophobic coating for tritium protection obtained in this example reaches 156.57°, reaching the super-hydrophobic standard; during the tensile deformation process of 0-800%, the hydrophobic coating always maintains super-hydrophobic properties; and after being immersed in a pH = 1 HCl solution, a pH = 14 NaOH solution, and a 3.5wt% NaCl solution for 8 hours, the hydrophobic coating of the composite material 3 can still maintain super-hydrophobic properties.

[0060] Table 1 shows the contact angle variation data of the super-hydrophobic coating of composite materials 1-3 under tension (tensile deformation 0-800%).

[0061] Table 1 Data changes of contact angle under tensile state

[0062]

[0063] Figure 2 The contact angle measurement result of the super-hydrophobic coating of the composite material obtained in Example 1 under tension.

[0064] Figure 3 The SEM images of the surface (A) and cross-section (B) of the super-hydrophobic coating obtained by the method of Example 2 show that during the tensile deformation of 0-800%, the hydrophobic coating obtained in this example always maintains a super-hydrophobic property (contact angle greater than 150°), which is derived from the rough micro-column structure formed on the surface of the material.

[0065] Figure 4 These are contact angle measurement graphs of super-hydrophobic coatings after immersion in acid, alkali or salt of Example 1 (AC), Example 2 (DF) and Example 3 (GI).

[0066] The above test results show that the super-hydrophobic properties (contact angle greater than 150°) of the super-hydrophobic coatings obtained in all embodiments are not affected after chemical corrosion.

Claims

1. A method for preparing a flexible polymer-based super-hydrophobic coating material for tritium protection, It is characterized in that The specific steps are as follows: 1) Add polybutadiene and benzoyl peroxide to the dispersion solution, seal, stir, and obtain an adhesive dispersion for later use; The above-mentioned dispersion solution includes one or more of n-hexane, ethanol, and acetone; The mass ratio of the added polybutadiene to benzoyl peroxide is 10:1; 2) adding the functional nanoparticles into the adhesive dispersion, sealing, stirring, and ultrasonic treatment to obtain the flexible polymer-based super-hydrophobic coating material for tritium protection; The functional nanoparticles are one or more of silicon dioxide, aluminum oxide, montmorillonite, and carbon black; In parts by mass, the added functional nanoparticles account for 1-2 parts, the polybutadiene accounts for 2-3 parts, the benzoyl peroxide accounts for 0.2-0.3 parts, and the dispersion solution accounts for 100 parts.

2. The method for preparing a flexible polymer-based super-hydrophobic coating material for tritium protection according to claim 1, It is characterized in that The size of the functional nanoparticles is 50-500 nm.

3. A flexible polymer-based super-hydrophobic coating material for tritium protection obtained according to the preparation method of claim 1 or 2.

4. Use of the flexible polymer-based super-hydrophobic coating material for tritium protection obtained by the preparation method of claim 1 or 2 in the preparation of tritium protection material coating.

5. The use according to claim 4, It is characterized in that The application refers to: 1) loading the flexible polymer-based super-hydrophobic coating material for tritium protection into a spray gun, atomizing it, and then evenly spraying it on the surface of the target substrate to form a tritium protection material coating; 2) curing the substrate at 120° C. for 1 hour, and then cooling it in a closed environment to obtain a flexible material that can be used for tritium protection.

6. The use according to claim 5, It is characterized in that The substrate includes at least one of flexible rubber, fiber fabric, and polyurethane film.

7. The use according to claim 6, It is characterized in that The tritium protection material coating has a thickness of 10-20 μm.

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