A stainless steel mesh-based super-amphiphobic material, a preparation method and application thereof

Abstract

The application belongs to the technical field of composite materials, and specifically discloses a super-amphiphobic material based on a stainless steel mesh, a preparation method and application thereof, the preparation method comprising the following steps: firstly, uniformly loading copper oxide nanoclusters CuO-NCs on the surface of a stainless steel mesh SSM to obtain an intermediate product CuO-NCs@SSM; and secondly, uniformly loading MSFG on the surface of the intermediate product CuO-NCs@SSM, so as to obtain the super-amphiphobic material MSFG@CuO-NCs@SSM based on the stainless steel mesh. Compared with the super-amphiphobic materials on the market, the super-amphiphobic material has the advantages of simple preparation process, low preparation cost, high material durability, and a static contact angle of up to 155°, and lays a foundation for further expanding the self-cleaning performance of the material.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of composite materials, and particularly relates to a super-amphiphobic material based on a stainless steel mesh and a preparation method and application thereof. BACKGROUND

[0002] With the rapid development of industry, metals and alloys have great application potential in pipeline transportation, shipbuilding, communication electronics, self-cleaning, etc. However, the metal surface is very active and is easily contaminated and corroded. Therefore, how to explore a method to make metal materials more stable has become a hot research topic. The protection methods of metals mainly include electrochemical protection method, corrosion inhibitor protection method and surface coating method. At present, the surface coating method mainly forms a super-amphiphobic coating on the metal surface in situ to achieve the protection effect. However, most super-amphiphobic coatings have problems such as complex preparation process, high preparation cost and secondary pollution, which are difficult to mass-produce. From the perspective of practical application, it is of great significance to develop a simple and low-cost super-amphiphobic material.

[0003] In recent years, super-amphiphobic materials based on metal mesh have attracted much attention due to their high mechanical strength, easy availability and long durability. The preparation of super-amphiphobic metal mesh mainly involves surface modification by changing the micro-geometric structure. However, most methods are usually completed under harsh conditions, such as expensive equipment or devices, complex synthesis steps, toxic reagents or by-products, etc. Therefore, the present application proposes a method for preparing super-amphiphobic materials based on stainless steel mesh with simple preparation process, high durability and low cost to be applied in daily life and industrial production. SUMMARY

[0004] In order to solve the above problems, the primary purpose of the present application is to provide a super-amphiphobic material based on a stainless steel mesh and a preparation method and application thereof.

[0005] The specific technical scheme of the present application includes:

[0006] The present application provides a preparation method of a super-amphiphobic material based on a stainless steel mesh, comprising the following steps:

[0007] (1) Preparation of the reaction solution, dissolve copper acetylacetonate in ethanol solution to obtain solution A, add bis[3-(trimethoxysilyl)]propylbutylamine to anhydrous ethanol and stir to obtain solution B, add perfluorooctanoic acid to anhydrous ethanol and stir to obtain solution C, slowly add solution B dropwise to solution C and stir to obtain mixture D;

[0008] (2) Preparation of intermediate product, clean stainless steel mesh (hereinafter referred to as SSM) is immersed in solution A for treatment, and then taken out and ignited in air, and the operation is repeated to uniformly load copper oxide nanoclusters (hereinafter referred to as CuO-NCs) on the surface of the stainless steel mesh, and after cleaning and drying, the intermediate product (hereinafter referred to as CuO-NCs@SSM) is obtained and reserved;

[0009] (3) Surface modification treatment, the intermediate product is added into solution D, and is placed at room temperature for more than 24 hours, and after cleaning and drying, the intermediate product CuO-NCs@SSM is uniformly loaded with chemically branched fluorinated silane groups (hereinafter referred to as MSFG), and the stainless steel mesh-based super-amphiphobic composite material (hereinafter referred to as MSFG@CuO-NCs@SSM) is obtained.

[0010] As a further optimization scheme of the present application, the stainless steel mesh is sequentially cleaned with ethanol and deionized water, and then placed in an oven at 80 DEG C for drying for 5 hours, and taken out for reservation.

[0011] As a further optimization scheme of the present application, the method for uniformly loading copper oxide nanoclusters on the surface of the stainless steel mesh is specifically as follows: the clean stainless steel mesh is immersed in solution A for 5 seconds, and then taken out and ignited in air, and after burning, it is immersed in solution A again for 5 seconds, and then taken out and ignited in air again. This process is repeated for 20 times.

[0012] As a further optimization scheme of the present application, the step (1) is specifically as follows: 2-6 g of copper acetylacetonate is added into 100 mL of ethanol solution, and stirred at a magnetic stirring speed of 300 r / min for 1 hour to make it fully dissolved, and solution A is obtained. 100 μL of bis[3-(trimethoxysilyl)]propylbutylamine is added into 15 mL of anhydrous ethanol, and stirred for 0.5 hour to obtain solution B. 0.5-2 g of perfluorooctanoic acid is placed into 15 mL of anhydrous ethanol, and stirred to obtain solution C, and solution B is slowly added dropwise into solution C, and stirred for 0.5 hour to obtain mixed solution D.

[0013] As a further optimization scheme of the present application, the drying process of the steps (2) and (3) is drying in an oven at 80 DEG C for 3 hours.

[0014] The present application also provides a stainless steel mesh-based super-amphiphobic material prepared by any of the above preparation methods, and the material has super-amphiphobicity.

[0015] The present application also provides an application of the stainless steel mesh-based super-hydrophobic composite material as described above in material self-cleaning.

[0016] In summary, the present application has the following beneficial effects:

[0017] Compared with the super-amphiphobic material on the market, the preparation process is simple, the preparation cost is low, the material durability is high, the static contact angle is as high as 155 degrees, and the foundation is laid for further expanding the self-cleaning performance of the material. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 FESEM images of SSM, CuO-NCs@SSM and MSFG@CuO-NCs@SSM (Note: Fig. a, d is SSM, Fig. b, e is CuO-NCs@SSM, Fig. c, f is MSFG@CuO-NCs@SSM);

[0019] Figure 2 TEM image of CuO-NCs;

[0020] Figure 3 XPS image of MSFG@CuO-NCs@SSM;

[0021] Figure 4 XRD image of SSM, CuO-NCs@SSM and MSFG@CuO-NCs@SSM;

[0022] Figure 5 Direct performance test of MSFG@CuO-NCs@SSM in different solvents;

[0023] Figure 6 Self-cleaning performance determination of TiO2, glycerol and mud water on MSFG@CuO-NCs@SSM (Note: Fig. a-c corresponds to TiO2, glycerol and mud water, respectively);

[0024] Figure 7 Static contact angle test of MSFG@CuO-NCs@SSM for different solvents;

[0025] Figure 8 Durability evaluation of MSFG@CuO-NCs@SSM at different temperatures;

[0026] Figure 9 Durability evaluation of MSFG@CuO-NCs@SSM at different pH values. DETAILED DESCRIPTION

[0027] The following detailed description of the application will be further described in conjunction with the accompanying drawings, and it is necessary to point out here that the following detailed description is only used to further illustrate the application, and cannot be understood as limiting the scope of protection of the application, and those skilled in the art can make some non-essential improvements and adjustments to the application according to the above application content.

[0028] I. Material

[0029] The methods used in this example are conventional methods known to those skilled in the art, and the reagents and the like materials are commercially available products unless otherwise specified.

[0030] II. Method

[0031] The stainless steel mesh SSM was cleaned with ethanol and deionized water respectively, and then placed in an oven at 80°C for drying for 5h, and taken out for standby use;

[0032] 2g of copper acetylacetonate was added to 100mL of ethanol solution, and stirred at a magnetic stirring speed of 300r / min for 1h to make it fully dissolved, to obtain solution A. 100μL of bis[3-(trimethoxysilyl)]propylamine (BTMEPA) was added to 15mL of anhydrous ethanol, and stirred for 0.5h to obtain solution B. 0.5g of perfluorooctanoic acid (PFOA) was placed in 15mL of anhydrous ethanol, and stirred to obtain solution C. Solution B was slowly added dropwise to solution C, and stirred for 0.5h to obtain mixture D.

[0033] A certain amount of clean SSM was immersed in solution A for 5s, and then taken out to ignite in air. After burning out, it was immersed in solution A again for 5s, and then taken out to ignite in air again. This process was repeated for 20 times to prepare copper oxide nanoclusters CuO-NCs uniformly loaded on the surface of SSM, which was named as CuO-NCs@SSM. After being cleaned with deionized water, CuO-NCs@SSM was placed in an oven at 80°C for drying for 3h, and then taken out for standby use;

[0034] CuO-NCs@SSM was added to solution D, and left to stand at room temperature for 24h to prepare uniform loading of MSFG on the surface of CuO-NCs@SSM, which was named as MSFG@CuO-NCs@SSM. Subsequently, MSFG@CuO-NCs@SSM was cleaned with deionized water, and then placed in an oven at 80°C for drying for 3h to obtain the super-amphiphobic SSM composite material.

[0035] III. Verification process

[0036] 1. Physical properties of the super-amphiphobic material based on stainless steel mesh

[0037] The morphologies of SSM, CuO-NCs@SSM and MSFG@CuO-NCs@SSM were observed by Zeiss Gemini 500 FESEM, and the results are shown in Figure 1 The morphology of copper oxide nanoclusters CuO-NCs was observed by Tecnai G2 F20 TEM, and the results are shown in Figure 2

[0038] ​Result analysis: The surface morphologies of SSM, CuO-NCs@SSM, MSFG@CuO-NCs@SSM are shown in Figure 1 Fig. 1. Figure 1 As shown in (a, d), the clean SSM surface is relatively smooth, with a diameter of about 33 pm; by observing Figure 1 (b, e), the average diameter of CuO-NCs@SSM after in-situ flame treatment is 38.3 pm. According to the diameter difference between SSM and CuO-NCs@SSM, it is found that the thickness of CuO-NCs layer is about 5.3 pm. Then, the TEM image Figure 2 clearly confirms that CuO-NCs is composed of CuO nanoparticles. In addition, CuO-NCs not only provides a larger surface area for the loading of MSFG, but also effectively enhances the adhesion between MSFG and SSM. After modification, a dense self-assembled MSFG layer is coated on the surface of CuO-NCs@SSM, forming MSFG@CuO-NC@SSM Figure 1 c, f).

[0039] The composition and distribution of elements on the surface of MSFG@CuO-NCs@SSM were determined by ThermoFisher ESCALAB 250Xi XPS, and the results are shown in Figure 3 Fig. 4. First, the surface XPS results of SSM verify the presence of C (284.11 eV) and O (529.7 eV) elements. In addition, Si 2s peak is also detected on the surface of SSM. Second, the absence of Si 2s peak in the XPS results of CuO-NCs@SSM may be due to the plating of CuO-NCs on the surface of SSM, and Cu 2p is also detected on the surface, further proving the successful loading of CuO-NCs. Finally, Si 2p, Si 2s, N 1s and F1s peaks are also detected on the surface of MSFG@CuO-NCs@SSM. These XPS results further confirm the successful preparation of MSFG on the surface of CuO-NCs@SSM.

[0040] The crystal phase of SSM, CuO-NCs@SSM, MSFG@CuO-NCs@SSM was determined by Japanese Rigaku SmartLab SE, and the results are shown in Figure 4As shown in Figure 6, the XRD pattern of the sample has three characteristic peaks at 43.86°, 51.02° and 74.84°, which are distributed in the (111), (200) and (220) lattice planes of SSM, respectively. In addition, the diffraction pattern of CuO-NCs@SSM shows 11 characteristic peaks, which are respectively corresponding to the (110), (002), (200), (200), (-202), (020), (202), (-113), (022), (220), (113) and (311) lattice planes of CuO-NCs nanoparticles. This result further confirms the successful preparation of CuO-NCs on the surface of SSM. Due to the poor crystallinity of MSFG, no obvious characteristic diffraction peaks can be detected.

[0041] 2. Direct performance test of MSFG@CuO-NCs@SSM with different solvents

[0042] Water, diesel, glycerol, corn oil and liquid paraffin were respectively dropped on the surface of MSFG@CuO-NCs@SSM in equal amounts, and the state of water, diesel, glycerol, corn oil and liquid paraffin on the surface of MSFG@CuO-NCs@SSM was observed, and the results are shown in Figure 5 In order to ensure the accuracy of the experimental data, the static contact angle of each solvent on the surface of the composite material was tested multiple times.

[0043] Result analysis: As shown in Figure 7 It can be seen that the static contact angle of water, diesel, glycerol, corn oil and liquid paraffin on the surface of the composite material ranges from 148 to 155°, which has super-amphiphobic characteristics. This result shows that the joint action of CuO-NCs and MSFG can effectively enhance the hydrophobic and oleophobic properties of the surface of SSM.

[0044] 3. Self-cleaning performance determination of TiO2, glycerol and muddy water on MSFG@CuO-NCs@SSM

[0045] The test process is shown in Figure 6 TiO2powder was placed on the surface of the composite material, and water was added on the surface using a disposable dropper. After a period of time, it was found that the TiO2powder could all fall into the beaker along with the spherical water beads, making the surface of the composite material clean, as shown in Figure 6 In addition, the composite material was immersed in glycerol Figure 6 b) and dirty water Figure 6 c), respectively, and then taken out and wiped on a paper towel, but the surface did not stick to the dirty water and glycerol, further confirming that the super-amphiphobic performance of the composite material has self-cleaning properties.

[0046] 4. Durability evaluation of MSFG@CuO-NCs@SSM at different temperatures

[0047] The MSFG@CuO-NCs@SSM material was placed in an oven at 25-200°C (25°C gradient) for 30 min, taken out and left to room temperature, and then the contact angle of water and oil on the surface of the composite material was measured using a contact angle meter, and the results are shown in Figure 8 It was found that the contact angle of water and glycerol on the MSFG@CuO-NCs@SSM was above 149° as the temperature increased. The results show that the material has good durability to temperature.

[0048] 5. Evaluation of the durability of MSFG@CuO-NCs@SSM to pH

[0049] An acid solution with pH = 1, 3, 5 was prepared by diluting concentrated hydrochloric acid with a mass concentration of 36.5%, and then 0.4 g of NaOH was dissolved in 100 mL of deionized water to obtain an alkaline solution with pH = 13, which was diluted to obtain solutions with pH = 9 and 11. The composite material was immersed in the above different pH solutions for 30 min, and then taken out and dried in an oven at 60°C for 1 h to measure the contact angle of water and oil on the surface of the treated material, and the results are shown in Figure 8 It was found that the composite material lost the superamphiphobic property under strong acid (pH = 1) and strong base (pH = 11, 13) conditions, and still maintained good wettability under other conditions, indicating that the composite material has good durability to pH.

[0050] The above examples only express several embodiments of the present application, and the description is more specific and detailed, but it should not be understood as limiting the scope of the patent of the present application. It should be noted that for ordinary skilled in the art, without departing from the concept of the present application, several improvements can be made, which are within the scope of protection of the present application.

Claims

1. A method for preparing a superhydrophobic and amphoteric material based on stainless steel mesh, characterized in that, Includes the following steps: (1) Preparation of reaction solution: Copper acetylacetonate is dissolved in ethanol solution to obtain solution A. Bis[3-(trimethoxysilyl)]propylbutamine is added to anhydrous ethanol and stirred to obtain solution B. Perfluorooctanoic acid is added to anhydrous ethanol and stirred to obtain solution C. Solution B is slowly added dropwise to solution C and stirred to obtain mixture D. (2) Preparation of intermediate product: The clean stainless steel mesh was immersed in solution A, then taken out and ignited in the air. The operation was repeated to uniformly load copper oxide nanoclusters on the surface of the stainless steel mesh. After cleaning and drying, the intermediate product was obtained and set aside for later use. (3) Surface modification treatment: the intermediate product is added to solution D, and the mixture is allowed to stand at room temperature. After cleaning and drying, the superhydrophobic material based on stainless steel mesh is obtained. The static contact angle of water, diesel, glycerin, corn oil and liquid paraffin on the surface of the superhydrophobic material is in the range of 148°~155°.

2. The method for preparing a superhydrophobic material based on stainless steel mesh according to claim 1, characterized in that, Step (2) further includes washing the stainless steel mesh with ethanol and deionized water in sequence, drying it in an oven at 80°C for 5 hours, and then taking it out for use.

3. The method for preparing a superhydrophobic material based on stainless steel mesh according to claim 1, characterized in that, The method for uniformly loading copper oxide nanoclusters onto the surface of a stainless steel mesh is as follows: immerse a clean stainless steel mesh in solution A for 5 seconds, then remove it and ignite it in the air. After it burns out, immerse it in solution A again for 5 seconds, remove it again and ignite it in the air. Repeat this process 20 times.

4. The method for preparing a superhydrophobic material based on stainless steel mesh according to claim 1, characterized in that, The specific steps (1) are as follows: 2-6g of copper acetylacetonate is added to 100mL of ethanol solution and stirred for 1h under magnetic stirring at 300r / min to fully dissolve it and obtain solution A. 100μL of bis[3-(trimethoxysilyl)]propylbutamine is added to 15mL of anhydrous ethanol and stirred for 0.5h to obtain solution B. 0.5-2g of perfluorooctanoic acid is added to 15mL of anhydrous ethanol and stirred to obtain solution C. Solution B is slowly added dropwise to solution C and stirred for 0.5h to obtain mixture D.

5. The method for preparing a superhydrophobic material based on stainless steel mesh according to claim 1, characterized in that, The drying process in steps (2) and (3) is to dry in an oven at 80°C for 3 hours.

6. A superhydrophobic material based on stainless steel mesh, characterized in that, It is prepared by any one of the preparation methods described in claims 1-5, and the superhydrophobic material has a static contact angle of 148° to 155° with water, diesel oil, glycerin, corn oil and liquid paraffin.

7. The application of the superhydrophobic material based on stainless steel mesh as described in claim 6 in material self-cleaning.

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