A method, product, and application for growing MoS2 nanosheets on carbon fiber surface

Abstract

This invention belongs to the field of carbon fiber surface modification, specifically relating to a method, product, and application for growing MoS2 nanosheets on the surface of carbon fibers. The method includes the following steps: desizing carbon fibers to obtain desizing carbon fibers; activating the desizing carbon fibers to obtain activated carbon fibers; placing the activated carbon fibers in a precursor solution containing gelatin, molybdenum salt, and a sulfur source for hydrothermal in-situ growth of MoS2 nanosheets; and washing and drying the carbon fibers after MoS2 nanosheet growth. This invention increases the surface roughness of carbon fibers by growing MoS2 nanosheets in situ, improving surface wettability and activity, which is beneficial for resin wetting and the formation of mechanical interlocking with the resin, thereby enhancing the interfacial bonding between the carbon fibers and the resin.

Description

Technical Field

[0001] This invention belongs to the field of carbon fiber surface modification, specifically relating to a method, product, and application for growing MoS2 nanosheets on the surface of carbon fibers. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Carbon fiber reinforced resin matrix composites (CFRPs) are widely used in aerospace, transportation, and civilian fields due to their excellent mechanical properties and low density. In these composites, the carbon fiber reinforcement is the main load-bearing component, the resin matrix is ​​the medium for load transfer, and the interface ensures the continuous propagation of load between the reinforcement and the matrix. Therefore, the interface is often a key factor determining the mechanical properties of composites. Thus, surface modification of carbon fibers can improve the interfacial bonding and mechanical properties of composites.

[0004] In recent years, besides wet and dry modification of carbon fibers, "multi-scale" modification has increasingly attracted researchers' attention. This involves grafting nanomaterials onto the surface of carbon fibers to increase surface roughness and enhance surface activity, which is beneficial for resin wetting and the formation of mechanical interlocks with the resin. There are two main approaches to grafting nanomaterials onto carbon fiber surfaces: one is through impregnation coating, where carbon fibers are immersed in a nanomaterial suspension; the other is through in-situ growth of nanomaterials on the carbon fiber surface. Generally, nanomaterials grown in situ bond more firmly and are more uniformly distributed on the carbon fiber surface, hence the increasing interest in in-situ growth of nanomaterials on carbon fiber surfaces. However, growing nanomaterials such as carbon nanotubes on carbon fiber surfaces via chemical vapor deposition (CVD) is a complex process. After desizing and activating the carbon fibers, catalysis and CVD are required. The CVD process involves temperatures exceeding 600°C, which can damage the carbon fiber surface. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a method, product, and application for growing MoS2 nanosheets on the surface of carbon fibers. In-situ growth of MoS2 nanosheets increases the surface roughness of carbon fibers, improves surface wettability and activity, which facilitates resin impregnation and the formation of mechanical interlocking with the resin, thereby enhancing the interfacial bonding between the carbon fibers and the resin.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0007] In a first aspect, the present invention provides a method for growing MoS2 nanosheets on the surface of carbon fibers, comprising the following steps:

[0008] S1. Desizing carbon fiber to obtain desizing carbon fiber, and then activating the desizing carbon fiber to obtain activated carbon fiber;

[0009] S2. Activated carbon fibers are placed in a precursor solution containing gelatin, molybdenum salt, and sulfur source for hydrothermal in-situ growth of MoS2 nanosheets; the carbon fibers after growing MoS2 nanosheets are cleaned and dried.

[0010] Preferably, the desizing process specifically involves heating the carbon fiber to 400-500°C under a nitrogen atmosphere, holding it at that temperature for 1-2 hours, and then washing and drying the carbon fiber with deionized water after cooling it to room temperature.

[0011] Preferably, the activation specifically involves: placing the desized carbon fiber in a 30% (w / w) H2O2 solution and keeping it at 85-95°C for 1-2 hours; after keeping it at 85-95°C, washing the carbon fiber with deionized water and drying it.

[0012] Preferably, the precursor solution is a mixture of a solution containing gelatin and a solution containing molybdenum salt and a sulfur source, wherein the mass ratio of gelatin to molybdenum salt is 1 to 2:1.

[0013] More preferably, the mass fraction of gelatin in the gelatin-containing solution is 0.1% to 0.5%.

[0014] More preferably, the molybdenum salt includes sodium molybdate dihydrate, and the sulfur source includes cysteine; the mass fraction of the molybdenum salt in the solution containing the molybdenum salt and the sulfur source is 0.1%-0.3%, the mass fraction of the sulfur source is 0.2%-0.6%, and the mass ratio of the molybdenum salt to the sulfur source is 1:1.9-2.1.

[0015] Preferably, the mass ratio of activated carbon fiber to molybdenum salt is 33:4 to 33:12.

[0016] Preferably, the temperature for hydrothermal in-situ growth is 150–200℃, and the holding time is 10–14 hours.

[0017] In a second aspect, the present invention provides a carbon fiber with MoS2 nanosheets grown on its surface, obtained by the method described in the first aspect.

[0018] Thirdly, the present invention provides the application of carbon fibers with surface-grown MoS2 nanosheets as described in the second aspect in the fabrication of aerospace equipment, automotive and marine equipment, and civil infrastructure.

[0019] The beneficial effects achieved by one or more technical solutions of the present invention are as follows:

[0020] (1) The present invention provides a method for growing MoS2 nanosheets on the surface of carbon fiber. The MoS2 nanosheets are uniformly distributed on the surface of carbon fiber and present a layered structure with a large specific surface area. This can increase the surface roughness of carbon fiber and improve surface activity, which is beneficial to resin wetting and forming mechanical interlock with the resin, thereby improving the interfacial bonding between carbon fiber and resin.

[0021] (2) The present invention uses hydrothermal method to grow nanomaterials in situ. Compared with the impregnation coating method, the nanomaterials are more firmly bonded to the carbon fiber and the distribution is more uniform. Compared with the vapor deposition method, it does not damage the carbon fiber and preserves the original mechanical properties of the carbon fiber.

[0022] (3) The preparation method of the present invention is simple, easy to operate and low in cost. Attached Figure Description

[0023] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0024] Figure 1 The image shows a secondary electron scanning microscope image of carbon fiber obtained in Example 1 of the present invention, wherein (A) is carbon fiber on which MoS2 nanosheets are grown, and (B) is MoS2 nanosheets uniformly grown on the surface of carbon fiber.

[0025] Figure 2 The image shows a secondary electron scanning microscope image of carbon fiber obtained in Example 2 of the present invention. In the image, (A) is the carbon fiber on which MoS2 nanosheets are grown, and (B) is the MoS2 nanosheet uniformly grown on the surface of the carbon fiber.

[0026] Figure 3 The image shows a secondary electron scanning microscope image of the carbon fiber obtained in Example 3 of the present invention. In the image, (A) is the carbon fiber on which MoS2 nanosheets are grown, and (B) is the MoS2 nanosheet uniformly grown on the surface of the carbon fiber.

[0027] Figure 4 The image shows a secondary electron scanning microscope image of the carbon fiber obtained in Example 4 of the present invention. In this image, (A) is the carbon fiber on which MoS2 nanosheets are grown, and (B) is the MoS2 nanosheet uniformly grown on the surface of the carbon fiber.

[0028] Figure 5 High-resolution transmission electron microscope image of MoS2 nanosheets;

[0029] Figure 6 The bar chart shows the interlaminar shear strength of the carbon fiber reinforced polyether ether ketone composites prepared in Comparative Example 1, Examples 1, 2, 3, and 4. Detailed Implementation

[0030] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments and comparative examples.

[0031] Example 1

[0032] Step 1: Place the carbon fiber into a tube furnace and heat it to 450℃ for 1.5 hours in a nitrogen atmosphere to remove the sizing agent from the surface of the carbon fiber. After cooling to room temperature, take it out and wash it several times with deionized water. Then put it into an oven to dry and obtain desized carbon fiber.

[0033] Step 2: Place the desized carbon fiber obtained in Step 1 into a 30% (w / w) H2O2 solution and keep it at 90℃ for 1.5 hours. After taking it out, wash it several times with deionized water and dry it in an oven to obtain activated carbon fiber.

[0034] Step 3: Stir gelatin and deionized water in a 60°C water bath to obtain a homogeneous solution with a gelatin mass fraction of 0.19%.

[0035] Step 4: Stir sodium molybdate dihydrate, cysteine ​​and deionized water into a homogeneous solution. The mass fraction of sodium molybdate dihydrate is 0.10% and the mass fraction of cysteine ​​is 0.20%.

[0036] Step 5: Stir the homogeneous solutions obtained in Steps 3 and 4 at a mass ratio of gelatin to sodium molybdate dihydrate of 2:1 to obtain a homogeneous solution.

[0037] Step 6: The activated carbon fibers obtained in Step 2, with a mass ratio of activated carbon fibers to sodium molybdate dihydrate of 33:4, are placed into the solution obtained in Step 5. Then, the solution is transferred to a hydrothermal reactor and hydrothermally heated at 180°C for 12 hours to obtain carbon fibers with MoS2 nanosheets.

[0038] Step 7: After the reactor cools down, take out the carbon fiber obtained in Step 6, wash it several times with deionized water, and dry it in an oven to obtain carbon fiber with MoS2 nanosheets grown on it.

[0039] like Figure 1 As shown in (A), MoS2 nanosheets are uniformly grown on the surface of the carbon fiber, increasing the surface roughness of the carbon fiber. Figure 1 As shown in (B), MoS2 nanosheets form a plate-like stacked structure on the carbon fiber surface, possessing a large specific surface area. This improves the surface wettability and activity of the carbon fiber, which is beneficial for resin impregnation and forms a mechanical interlock with the resin. Figure 5 As shown, the MoS2 grown on the carbon fiber surface has a typical crystal structure, exposing the (100), (002), (103), and (110) crystal planes.

[0040] Example 2

[0041] Step 1: Place the carbon fiber into a tube furnace and heat it to 450℃ for 1.5 hours in a nitrogen atmosphere to remove the sizing agent from the surface of the carbon fiber. After cooling to room temperature, take it out and wash it several times with deionized water. Then put it into an oven to dry and obtain desized carbon fiber.

[0042] Step 2: Place the desized carbon fiber obtained in Step 1 into a 30% (w / w) H2O2 solution and keep it at 90℃ for 1.5 hours. After taking it out, wash it several times with deionized water and dry it in an oven to obtain activated carbon fiber.

[0043] Step 3: Stir gelatin and deionized water in a 60°C water bath to obtain a homogeneous solution with a gelatin mass fraction of 0.19%.

[0044] Step 4: Stir sodium molybdate dihydrate, cysteine ​​and deionized water into a homogeneous solution. The mass fraction of sodium molybdate dihydrate is 0.12% and the mass fraction of cysteine ​​is 0.24%.

[0045] Step 5: Stir the homogeneous solutions obtained in Steps 3 and 4 at a mass ratio of gelatin to sodium molybdate dihydrate of 2:1 to obtain a homogeneous solution.

[0046] Step 6: The activated carbon fibers obtained in Step 2, with a mass ratio of activated carbon fibers to sodium molybdate dihydrate of 33:5, are placed into the solution obtained in Step 5. Then, the solution is transferred to a hydrothermal reactor and hydrothermally heated at 180°C for 12 hours to obtain carbon fibers with MoS2 nanosheets.

[0047] Step 7: After the reactor cools down, take out the carbon fiber obtained in Step 6, wash it several times with deionized water, and dry it in an oven to obtain carbon fiber with MoS2 nanosheets grown on it.

[0048] like Figure 2 As shown in (A), MoS2 nanosheets are uniformly grown on the surface of the carbon fiber, increasing the surface roughness of the carbon fiber. Figure 2 As shown in (B), MoS2 nanosheets form a sheet-like stacked structure on the surface of carbon fibers, which has a large specific surface area, can improve the surface wettability and activity of carbon fibers, which is beneficial to resin impregnation and can form a mechanical interlock with the resin.

[0049] Example 3

[0050] Step 1: Place the carbon fiber into a tube furnace and heat it to 450℃ for 1.5 hours in a nitrogen atmosphere to remove the sizing agent from the surface of the carbon fiber. After cooling to room temperature, take it out and wash it several times with deionized water. Then put it into an oven to dry and obtain desized carbon fiber.

[0051] Step 2: Place the desized carbon fiber obtained in Step 1 into a 30% (w / w) H2O2 solution and keep it at 90℃ for 1.5 hours. After taking it out, wash it several times with deionized water and dry it in an oven to obtain activated carbon fiber.

[0052] Step 3: Stir gelatin and deionized water in a 60°C water bath to obtain a homogeneous solution with a gelatin mass fraction of 0.19%.

[0053] Step 4: Stir sodium molybdate dihydrate, cysteine ​​and deionized water into a homogeneous solution. The mass fraction of sodium molybdate dihydrate is 0.14% and the mass fraction of cysteine ​​is 0.28%.

[0054] Step 5: Stir the homogeneous solutions obtained in Steps 3 and 4 at a mass ratio of gelatin to sodium molybdate dihydrate of 2:1 to obtain a homogeneous solution.

[0055] Step 6: The activated carbon fibers obtained in Step 2, with a mass ratio of activated carbon fibers to sodium molybdate dihydrate of 33:6, are placed into the solution obtained in Step 5. Then, the solution is transferred to a hydrothermal reactor and hydrothermally heated at 180°C for 12 hours to obtain carbon fibers with MoS2 nanosheets.

[0056] Step 7: After the reactor cools down, take out the carbon fiber obtained in Step 6, wash it several times with deionized water, and dry it in an oven to obtain carbon fiber with MoS2 nanosheets grown on it.

[0057] like Figure 3 As shown in (A), MoS2 nanosheets are uniformly grown on the surface of the carbon fiber, increasing the surface roughness of the carbon fiber. Figure 3 As shown in (B), MoS2 nanosheets form a sheet-like stacked structure on the surface of carbon fibers, which has a large specific surface area, can improve the surface wettability and activity of carbon fibers, which is beneficial to resin impregnation and can form a mechanical interlock with the resin.

[0058] Example 4

[0059] Step 1: Place the carbon fiber into a tube furnace and heat it to 450℃ for 1.5 hours in a nitrogen atmosphere to remove the sizing agent from the surface of the carbon fiber. After cooling to room temperature, take it out and wash it several times with deionized water. Then put it into an oven to dry and obtain desized carbon fiber.

[0060] Step 2: Place the desized carbon fiber obtained in Step 1 into a 30% (w / w) H2O2 solution and keep it at 90℃ for 1.5 hours. After taking it out, wash it several times with deionized water and dry it in an oven to obtain activated carbon fiber.

[0061] Step 3: Stir gelatin and deionized water in a 60°C water bath to obtain a homogeneous solution with a gelatin mass fraction of 0.19%.

[0062] Step 4: Stir sodium molybdate dihydrate, cysteine ​​and deionized water into a homogeneous solution. The mass fraction of sodium molybdate dihydrate is 0.16% and the mass fraction of cysteine ​​is 0.32%.

[0063] Step 5: Stir the homogeneous solutions obtained in Steps 3 and 4 at a mass ratio of gelatin to sodium molybdate dihydrate of 2:1 to obtain a homogeneous solution.

[0064] Step 6: The activated carbon fibers obtained in Step 2, with a mass ratio of activated carbon fibers to sodium molybdate dihydrate of 33:7, are placed into the solution obtained in Step 5. Then, the solution is transferred to a hydrothermal reactor and hydrothermally heated at 180°C for 12 hours to obtain carbon fibers with MoS2 nanosheets.

[0065] Step 7: After the reactor cools down, take out the carbon fiber obtained in Step 6, wash it several times with deionized water, and dry it in an oven to obtain carbon fiber with MoS2 nanosheets grown on it.

[0066] like Figure 4 As shown in (A), MoS2 nanosheets are uniformly grown on the surface of the carbon fiber, increasing the surface roughness of the carbon fiber. Figure 4 As shown in (B), MoS2 nanosheets form a sheet-like stacked structure on the surface of carbon fibers, which has a large specific surface area, can improve the surface wettability and activity of carbon fibers, which is beneficial to resin impregnation and can form a mechanical interlock with the resin.

[0067] Compare with Example 1

[0068] Carbon fibers are placed in a tube furnace and heated to 450°C for 1.5 hours in a nitrogen atmosphere to remove the sizing agent from the surface of the carbon fibers. After cooling to room temperature, the carbon fibers are taken out, washed several times with deionized water, and then dried in an oven to obtain desized carbon fibers.

[0069] The desized carbon fibers obtained in Comparative Example 1 and the carbon fibers with MoS2 nanosheets grown in Examples 1-4 were respectively used to prepare carbon fiber reinforced polyetheretherketone (PEEK) composites. The interlaminar shear strength of the composites was tested, and the results are as follows: Figure 6 As shown, carbon fibers growing MoS2 nanosheets can effectively enhance the interlaminar shear strength of composite materials.

[0070] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for growing MoS2 nanosheets on the surface of carbon fibers, characterized in that, The method comprises the following steps: S1, desizing carbon fibers to obtain desized carbon fibers, and activating the desized carbon fibers to obtain activated carbon fibers; S2, placing the activated carbon fibers in a precursor solution containing gelatin, a molybdenum salt and a sulfur source to hydrothermally grow MoS2 nanosheets in situ, and cleaning and drying the carbon fibers after growing the MoS2 nanosheets; The precursor solution is obtained by mixing a solution containing gelatin and a solution containing a molybdenum salt and a sulfur source, and the mass ratio of gelatin to the molybdenum salt is 1-2:1; The activation specifically comprises placing the desized carbon fibers in a 30% H2O2 solution, and keeping the temperature at 85-95 ℃ for 1-2 h, and then washing and drying the carbon fibers with deionized water after keeping the temperature.

2. The method of claim 1, wherein, The desizing process specifically comprises heating the carbon fibers to 400-500 ℃ under a nitrogen atmosphere, keeping the temperature for 1-2 h, and then washing and drying the carbon fibers with deionized water after reducing the temperature to room temperature.

3. The method of claim 1, wherein, The mass fraction of gelatin in the solution containing gelatin is 0.1%-0.5%.

4. The method of claim 1, wherein, The molybdenum salt comprises sodium molybdate dihydrate, and the sulfur source comprises cysteine; the mass fraction of the molybdenum salt in the solution containing the molybdenum salt and the sulfur source is 0.1%-0.3%, the mass fraction of the sulfur source is 0.2%-0.6%, and the mass ratio of the molybdenum salt to the sulfur source is 1:1.9-2.

1.

5. The method of claim 1, wherein, The mass ratio of the activated carbon fibers to the molybdenum salt is 33:4-33:

12.

6. The method of claim 1, wherein, The temperature for hydrothermal in-situ growth is 150-200 ℃, and the keeping time is 10-14 h.

7. A carbon fiber having surface grown MoS2 nanosheets, characterized in that, The carbon fibers are obtained by the method according to any one of claims 1-6.

8. Use of the carbon fibers on which MoS2 nanosheets are grown on the surface in the preparation of aerospace equipment, automobiles, ships and civil infrastructure according to claim 7.

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