A heated de-icing graphene glass fiber cloth and its preparation method

Abstract

This invention relates to the field of graphene composite materials technology, and more particularly to a heated de-icing graphene glass fiber cloth and its preparation method. The heated de-icing graphene glass fiber cloth involves treating glass fibers with low-temperature plasma; depositing graphene on the surface of the plasma-treated glass fibers in a first mixed gas via chemical vapor deposition; then treating with water vapor at 700-800℃ to obtain graphene glass fibers; weaving the graphene glass fibers to obtain a fiber fabric; and depositing graphene on the surface of the fiber fabric in a second mixed gas via chemical vapor deposition to obtain the graphene glass fiber cloth. The fiber cloth obtained by this invention not only has a significantly reduced density and lighter weight per unit area, but also a high electrothermal heating rate and effectively improved electrothermal conversion efficiency, achieving a balance between flexibility, electrothermal stability, and mechanical strength in the graphene glass fiber cloth.

Description

Technical Field

[0001] This invention relates to the field of graphene composite materials technology, and in particular to a heated de-icing graphene glass fiber cloth and its preparation method. Background Technology

[0002] Graphene, a two-dimensional carbon material, is considered an ideal candidate for next-generation flexible electric heating materials due to its ultra-high thermal conductivity, excellent electrothermal conversion efficiency, and low resistivity. However, pure graphene films have low mechanical strength and are difficult to self-support, necessitating the use of composite structures for practical applications.

[0003] Super graphene materials are emerging members of the graphene composite material family. By performing high-temperature chemical deposition on traditional engineering materials, continuous graphene layers are formed, avoiding the challenging peeling-transfer process and solving the problem of non-self-support in ultrathin graphene films.

[0004] Glass fiber, with its lightweight, high strength, and high temperature resistance, is an ideal substrate material. By coating the surface of glass fiber with a graphene layer through chemical vapor deposition (CVD), graphene glass fiber cloth with high conductivity, flexibility, and mechanical strength can be prepared.

[0005] Although graphene-coated glass fiber cloth theoretically holds great promise for applications, current processes suffer from insufficient interfacial bonding strength between the graphene film and glass fiber. Under repeated bending or mechanical stress, it is prone to cracking or peeling, leading to breakage of the conductive network and a significant decline in electrical performance. Furthermore, deformation of the fiber cloth disrupts the continuity of the graphene layer, causing localized increases in resistance and triggering hotspot effects. This not only reduces heating efficiency but may also lead to thermal stress damage to the substrate due to uneven temperature distribution.

[0006] De-icing technology is crucial for transportation, power facilities, and aviation safety under extreme weather conditions. In recent years, electric heating de-icing technology has gained increasing attention due to its advantages such as strong controllability and fast response speed. However, existing commercial electric heating materials (such as nickel-chromium alloys and copper foil) generally suffer from defects such as poor flexibility, high density, and low thermal efficiency, making it difficult to meet the de-icing requirements of complex curved surfaces or dynamic environments. Especially in dynamic de-icing scenarios (such as wind turbine blade or wing de-icing), the fiber cloth needs to withstand periodic deformation. Existing materials are difficult to restore their initial electrothermal properties after deformation, and the heating stability cannot meet the continuous de-icing requirements.

[0007] The current graphene glass fiber cloth suffers from deficiencies in flexibility, deformation resistance, and electrothermal stability, making it difficult to balance efficient heating and long-term reliability in dynamic de-icing scenarios. This has become a pressing technical problem that needs to be solved. Summary of the Invention

[0008] The purpose of this invention is to address the shortcomings of existing technologies by proposing a heated de-icing graphene glass fiber cloth and its preparation method.

[0009] A graphene glass fiber cloth for heating and de-icing, which is prepared by the following method:

[0010] Step 1: Perform low-temperature plasma treatment on the glass fiber;

[0011] Step 2: Graphene is deposited on the surface of the glass fiber after low-temperature plasma treatment by chemical vapor deposition in the first mixed gas; then, it is treated with water vapor at a temperature of 700-800℃ to obtain graphene glass fiber; the first mixed gas includes hydrogen and methane, the flow ratio of hydrogen to methane is 1:10-100, and the hydrogen flow rate is 10-30 sccm;

[0012] Step 3: The graphene glass fiber is woven into a fiber fabric, and graphene is deposited on the surface of the fiber fabric in a second mixed gas by chemical vapor deposition to obtain graphene glass fiber cloth; the second mixed gas is a mixture of hydrogen, methane and ethanol preheated to 100-150℃, the flow ratio of hydrogen, methane and ethanol is 1:10-100:0.1-0.5, and the hydrogen flow rate is 10-30 sccm.

[0013] Preferably, in step 1, the low-temperature plasma treatment time is 1-3 min, the low-temperature plasma treatment power is 80-120 W, and the pressure during the low-temperature plasma treatment is 80-120 Pa.

[0014] The present invention uses plasma etching to etch glass fibers, which can effectively increase the surface roughness and active sites of the fibers, thereby improving the initial bonding force of the subsequent first deposition of graphene.

[0015] Preferably, in step 1, during the low-temperature plasma treatment process, the working gas includes argon and oxygen, with a volume ratio of argon to oxygen of 3-6:1.

[0016] Preferably, the specific operation of step 2 is as follows: using glass fiber treated with low-temperature plasma as a substrate, place it in a CVD furnace, evacuate the furnace, and then introduce argon gas for washing. The temperature is raised to 1100-1150℃, and argon gas is continued to be introduced to make the pressure in the CVD furnace reach the standard atmospheric pressure. Then, the first mixed gas is introduced for 1-2 hours, and then the introduction of the first mixed gas is stopped. Argon gas is introduced, and the temperature is lowered to 700-800℃. Then, water vapor at a temperature of 700-800℃ is introduced for treatment for 5-10 minutes, and the temperature is allowed to drop naturally to room temperature. Argon gas is continuously introduced during the natural cooling process.

[0017] This invention introduces water vapor etching after the initial deposition. The hydroxyl radicals generated by the high-temperature water vapor selectively remove residual amorphous carbon impurities on the substrate surface and disordered carbon at the edges of the graphene, clearing more active sites on the substrate surface and defect sites at the edges of the graphene. This provides a stronger chemical bonding basis for the subsequent secondary deposition of graphene, significantly improving the interfacial bonding strength between graphene and the glass fiber matrix. This makes the graphene layer less prone to peeling off due to interfacial debonding when the material is repeatedly bent, thus maintaining the continuity of the conductive network.

[0018] More preferably, after evacuation, argon gas is introduced for washing, with an argon gas flow rate of 50-150 sccm.

[0019] More preferably, after heating to 1100-1150℃, argon gas is continuously introduced at a flow rate of 400-500 sccm.

[0020] More preferably, the water vapor flow rate is 5-15 sccm.

[0021] Preferably, in step 3, the warp and weft density of the fiber fabric is 12×12 threads / cm. 2 The fineness of the yarn used in the fiber fabric is 30-35 tex, and the thickness of the fiber fabric is 0.05-0.08 mm.

[0022] The above-mentioned method for preparing heated and de-iced graphene glass fiber cloth includes the following steps: feeding the fiber blank into a CVD furnace, evacuating it, and then purging it with argon gas for 4-10 minutes, raising the temperature to 1000-1120℃, continuing to purge with argon gas to make the pressure in the CVD furnace at standard atmospheric pressure, purging with a second mixed gas for 10-30 minutes, stopping the purge with the second mixed gas, purging with argon gas, and allowing it to cool naturally to room temperature.

[0023] Preferably, after heating to 1000-1120℃, argon gas is continuously introduced at a flow rate of 400-500 sccm.

[0024] Preferably, during the process of heating to 1000-1120℃, the heating rate is 5-10℃ / min.

[0025] Beneficial effects:

[0026] This invention utilizes the decomposition of ethanol in the second mixed gas at high temperature to generate hydroxyl radicals and small molecule hydrocarbon species. The hydroxyl radicals have a strong selective oxidation ability on disordered carbon, which can preferentially attack the disordered carbon at the edges or grain boundaries of graphene, causing it to be oxidized and removed and regrown into an ordered graphene lattice structure, reducing the defect density of graphene, improving carrier mobility, and making the resistivity distribution more uniform. At the same time, during the secondary deposition process, the small molecule hydrocarbon species decomposed from ethanol and methane synergistically regulate the carbon source supply rate, inhibiting the excessive growth of polycrystalline graphene and further optimizing the electrothermal conversion efficiency.

[0027] This invention uses a fiber prefabricated fabric as a mechanical framework to support the graphene layer and disperse external stress. The two-layer graphene deposition effectively combines and maintains the continuity of the conductive network. When bent, the graphene layer and the fiber prefabricated fabric are allowed to deform together, dispersing local stress to a larger area and avoiding stress concentration at a single location. The synergistic effect enables the material to maintain the integrity of the graphene layer under dynamic loads (such as the periodic vibration of wind turbine blades), reducing crack propagation caused by repeated deformation, thereby ensuring the long-term stability of heating performance.

[0028] Compared to rigid materials such as nickel-chromium alloys, the fiber cloth obtained by this invention not only has a significantly lower density and lighter weight per unit area, making it suitable for lightweight applications, but also has a high electric heating rate and effectively improved electrothermal conversion efficiency. This achieves a balance between flexibility, electrothermal stability, and mechanical strength in the graphene glass fiber cloth, providing a reliable solution for dynamic de-icing in extreme environments. Attached Figure Description

[0029] Figure 1 The graph shows a comparison of the stable values ​​of the electric heating temperature of the fiber fabrics obtained in Examples 1-5, the graphene glass fiber fabric obtained in Example 5, and the graphene glass fiber fabrics obtained in Comparative Examples 1-3.

[0030] Figure 2 The graph shows a comparison of the electro-thermal radiation conversion efficiency of the fiber fabrics obtained in Examples 1-5, the graphene glass fiber fabric obtained in Example 5, and the graphene glass fiber fabrics obtained in Comparative Examples 1-3.

[0031] Figure 3 The graph shows the comparison of the stable values ​​of the electric heating temperature and the decay rate of the stable values ​​of the electric heating temperature after 1000 hours of flight for the graphene glass fiber cloths obtained in Examples 1-5 and Comparative Examples 1-3. Detailed Implementation

[0032] The present invention will be further explained below with reference to specific embodiments.

[0033] Example 1

[0034] A method for preparing a heated de-icing graphene glass fiber cloth includes the following steps:

[0035] (1) The glass fiber was etched in a low-temperature plasma modification device for 1 min, with a power of 80 W and a pressure of 80 Pa. The working gas was obtained by mixing argon and oxygen in a volume ratio of 3:1. The glass fiber was then dried at 80 °C for 10 min to obtain pretreated glass fiber.

[0036] (2) The pretreated glass fiber was placed in a CVD furnace as a substrate. After evacuation, argon gas with a flow rate of 50 sccm was introduced to wash the furnace. The temperature was raised to 1100℃. Argon gas with a flow rate of 400 sccm was introduced to make the pressure in the CVD furnace the standard atmospheric pressure. The first mixed gas (composed of hydrogen gas with a flow rate of 10 sccm and methane gas with a flow rate of 100 sccm) was introduced for 1 hour. The first mixed gas was then stopped. Argon gas was then introduced and the temperature was lowered to 700℃. Water vapor at a temperature of 700℃ was introduced for 5 minutes with a water vapor flow rate of 5 sccm. The temperature was allowed to drop naturally to room temperature. Argon gas was continuously introduced during the natural cooling process to obtain graphene glass fiber.

[0037] (3) Graphene glass fibers are woven into a fiber fabric (plain weave) with a warp and weft density of 12×12 threads / cm. 2 The yarn fineness is 32 tex, and the fiber cloth thickness is 0.05 mm. After ultrasonically cleaning the fiber cloth with deionized water, it is dried with high-purity nitrogen and sent into the CVD furnace. After evacuation, argon gas with a flow rate of 300 sccm is introduced to purge for 4 minutes. The temperature is increased to 1000℃ at a rate of 5℃ / min. Argon gas with a flow rate of 400 sccm is continued to be introduced to maintain the pressure in the CVD furnace at standard atmospheric pressure. A second mixed gas (composed of hydrogen with a flow rate of 10 sccm, methane with a flow rate of 100 sccm, and ethanol with a flow rate of 1 sccm) preheated to 100℃ is introduced for 10 minutes. The introduction of the second mixed gas is stopped, argon gas is introduced, and the temperature is allowed to drop naturally to room temperature.

[0038] Example 2

[0039] A method for preparing a heated de-icing graphene glass fiber cloth includes the following steps:

[0040] (1) The glass fiber was etched in a low-temperature plasma modification device for 3 minutes. The power was set to 120W and the pressure to 120Pa. The working gas was obtained by mixing argon and oxygen in a volume ratio of 6:1. The glass fiber was then dried at 100℃ for 20 minutes to obtain pretreated glass fiber.

[0041] (2) The pretreated glass fiber is placed in a CVD furnace as a substrate. After evacuation, argon gas with a flow rate of 150 sccm is introduced for washing. The temperature is raised to 1150℃. Argon gas with a flow rate of 500 sccm is introduced to make the pressure in the CVD furnace the standard atmospheric pressure. The first mixed gas (composed of hydrogen with a flow rate of 30 sccm and methane with a flow rate of 3000 sccm) is introduced for 1-2 hours. The first mixed gas is then stopped. Argon gas is then introduced, and the temperature is lowered to 800℃. Water vapor at 800℃ is introduced for 10 minutes with a flow rate of 15 sccm. The temperature is then allowed to drop naturally to room temperature. Argon gas is continuously introduced during the natural cooling process to obtain graphene glass fiber.

[0042] (3) Graphene glass fibers are woven into a fiber fabric (plain weave) with a warp and weft density of 12×12 threads / cm. 2 The yarn fineness is 32 tex, and the fiber cloth thickness is 0.08 mm. After ultrasonically cleaning the fiber cloth with deionized water, it is dried with high-purity nitrogen and sent into the CVD furnace. After evacuation, argon gas with a flow rate of 400 sccm is introduced to purge for 10 min. The temperature is increased to 1120℃ at a rate of 10℃ / min. Argon gas with a flow rate of 500 sccm is continued to be introduced to maintain the pressure in the CVD furnace at standard atmospheric pressure. A second mixed gas (composed of hydrogen with a flow rate of 30 sccm, methane with a flow rate of 3000 sccm, and ethanol with a flow rate of 15 sccm) preheated to 150℃ is introduced for 30 min. The introduction of the second mixed gas is stopped, argon gas is introduced, and the temperature is allowed to drop naturally to room temperature.

[0043] Example 3

[0044] A method for preparing a heated de-icing graphene glass fiber cloth includes the following steps:

[0045] (1) The glass fiber was etched in a low-temperature plasma modification device for 2 minutes. The power was set to 90W and the pressure to 110Pa. The working gas was obtained by mixing argon and oxygen in a volume ratio of 4:1. Then it was dried at 95℃ for 12 minutes to obtain pretreated glass fiber.

[0046] (2) The pretreated glass fiber was placed in a CVD furnace as a substrate. After evacuation, argon gas with a flow rate of 120 sccm was introduced to wash the furnace. The temperature was raised to 1110℃. Argon gas with a flow rate of 480 sccm was introduced to make the pressure in the CVD furnace the standard atmospheric pressure. The first mixed gas (composed of hydrogen gas with a flow rate of 15 sccm and methane gas with a flow rate of 1500 sccm) was introduced for 80 min. The first mixed gas was then stopped. Argon gas was then introduced and the temperature was lowered to 780℃. Water vapor at a temperature of 720℃ was introduced for 9 min at a flow rate of 8 sccm. The temperature was allowed to drop naturally to room temperature. Argon gas was continuously introduced during the natural cooling process to obtain graphene glass fiber.

[0047] (3) Graphene glass fibers are woven into a fiber fabric (plain weave) with a warp and weft density of 12×12 threads / cm. 2The yarn fineness is 32 tex, and the fiber cloth thickness is 0.06±0.01 mm. After ultrasonically cleaning the fiber cloth with deionized water, it is dried with high-purity nitrogen and sent into the CVD furnace. After vacuuming, argon gas at a flow rate of 370 sccm is introduced to purge for 6 minutes. The temperature is raised to 1020℃ at a rate of 9℃ / min. Argon gas at a flow rate of 480 sccm is continued to maintain the pressure in the CVD furnace at standard atmospheric pressure. A second mixed gas (composed of hydrogen at a flow rate of 25 sccm, methane at a flow rate of 500 sccm, and ethanol at a flow rate of 10 sccm) preheated to 110℃ is introduced for 15 minutes. The second mixed gas is then stopped, and argon gas is introduced. The furnace is allowed to cool naturally to room temperature.

[0048] Example 4

[0049] A method for preparing a heated de-icing graphene glass fiber cloth includes the following steps:

[0050] (1) The glass fiber was etched in a low-temperature plasma modification device for 2 minutes. The power was set to 110W and the pressure to 90Pa. The working gas was obtained by mixing argon and oxygen in a volume ratio of 5:1. The glass fiber was then dried at 85℃ for 18 minutes to obtain pretreated glass fiber.

[0051] (2) The pretreated glass fiber was placed in a CVD furnace as a substrate. After evacuation, argon gas with a flow rate of 80 sccm was introduced to wash the furnace. The temperature was raised to 1130℃. Argon gas with a flow rate of 420 sccm was introduced to make the pressure in the CVD furnace the standard atmospheric pressure. The first mixed gas (composed of hydrogen with a flow rate of 25 sccm and methane with a flow rate of 500 sccm) was introduced for 100 min. The first mixed gas was then stopped. Argon gas was then introduced and the temperature was lowered to 720℃. Water vapor at a temperature of 780℃ was introduced for 7 min at a flow rate of 12 sccm. The temperature was allowed to drop naturally to room temperature. Argon gas was continuously introduced during the natural cooling process to obtain graphene glass fiber.

[0052] (3) Graphene glass fibers are woven into a fiber fabric (plain weave) with a warp and weft density of 12×12 threads / cm. 2 The yarn fineness is 32 tex, and the fiber cloth thickness is 0.06±0.01 mm. After ultrasonically cleaning the fiber cloth with deionized water, it is dried with high-purity nitrogen and sent into the CVD furnace. After vacuuming, argon gas with a flow rate of 330 sccm is introduced to purge for 8 minutes. The temperature is raised to 1100℃ at a rate of 7℃ / min. Argon gas with a flow rate of 420 sccm is continued to be introduced to maintain the pressure in the CVD furnace at standard atmospheric pressure. A second mixed gas (composed of hydrogen with a flow rate of 15 sccm, methane with a flow rate of 1200 sccm, and ethanol with a flow rate of 3 sccm) preheated to 130℃ is introduced for 25 minutes. The introduction of the second mixed gas is stopped, argon gas is introduced, and the temperature is allowed to drop naturally to room temperature.

[0053] Example 5

[0054] A method for preparing a heated de-icing graphene glass fiber cloth includes the following steps:

[0055] (1) The glass fiber was etched in a low-temperature plasma modification device for 2 minutes. The power was set to 100W and the pressure to 100Pa. The working gas was obtained by mixing argon and oxygen in a volume ratio of 4.5:1. The glass fiber was then dried at 90℃ for 15 minutes to obtain pretreated glass fiber.

[0056] (2) The pretreated glass fiber was placed in a CVD furnace as a substrate. After evacuation, argon gas with a flow rate of 100 sccm was introduced to wash the furnace. The temperature was raised to 1120℃. Argon gas with a flow rate of 450 sccm was introduced to make the pressure in the CVD furnace the standard atmospheric pressure. The first mixed gas (composed of hydrogen with a flow rate of 20 sccm and methane with a flow rate of 1000 sccm) was introduced for 90 min. The first mixed gas was then stopped. Argon gas was then introduced and the temperature was lowered to 750℃. Water vapor at a temperature of 750℃ was introduced for 8 min at a flow rate of 10 sccm. The temperature was allowed to drop naturally to room temperature. Argon gas was continuously introduced during the natural cooling process to obtain graphene glass fiber.

[0057] (3) Graphene glass fibers are woven into a fiber fabric (plain weave) with a warp and weft density of 12×12 threads / cm. 2 The yarn fineness is 32 tex, and the fiber cloth thickness is 0.06±0.01 mm. After ultrasonically cleaning the fiber cloth with deionized water, it is dried with high-purity nitrogen and sent into the CVD furnace. After vacuuming, argon gas at a flow rate of 350 sccm is introduced to purge for 7 minutes. The temperature is increased to 1060℃ at a rate of 8℃ / min. Argon gas at a flow rate of 450 sccm is continued to be introduced to maintain the pressure in the CVD furnace at standard atmospheric pressure. A second mixed gas (composed of hydrogen at a flow rate of 20 sccm, methane at a flow rate of 1000 sccm, and ethanol at a flow rate of 6 sccm) preheated to 120℃ is introduced for 20 minutes. The second mixed gas is then stopped, and argon gas is introduced. The furnace is allowed to cool naturally to room temperature.

[0058] Comparative Example 1

[0059] A method for preparing a heated de-icing graphene glass fiber cloth includes the following steps:

[0060] (1) Glass fiber is used as a substrate and placed in a CVD furnace. After evacuation, argon gas with a flow rate of 100 sccm is introduced for washing. The temperature is raised to 1120℃. Argon gas with a flow rate of 450 sccm is introduced to make the pressure in the CVD furnace the standard atmospheric pressure. The first mixed gas (composed of hydrogen with a flow rate of 20 sccm and methane with a flow rate of 1000 sccm) is introduced for 90 min. The first mixed gas is then stopped. Argon gas is then introduced and the temperature is lowered to 750℃. Water vapor at a temperature of 750℃ is introduced for 8 min with a water vapor flow rate of 10 sccm. The temperature is then allowed to drop naturally to room temperature. Argon gas is continuously introduced during the natural cooling process to obtain graphene glass fiber.

[0061] (2) Graphene glass fibers are woven into a fiber fabric (plain weave) with a warp and weft density of 12×12 threads / cm. 2 The yarn fineness is 32 tex, and the fiber cloth thickness is 0.06±0.01 mm. After ultrasonically cleaning the fiber cloth with deionized water, it is dried with high-purity nitrogen and sent into the CVD furnace. After vacuuming, argon gas at a flow rate of 350 sccm is introduced to purge for 7 minutes. The temperature is increased to 1060℃ at a rate of 8℃ / min. Argon gas at a flow rate of 450 sccm is continued to be introduced to maintain the pressure in the CVD furnace at standard atmospheric pressure. A second mixed gas (composed of hydrogen at a flow rate of 20 sccm, methane at a flow rate of 1000 sccm, and ethanol at a flow rate of 6 sccm) preheated to 120℃ is introduced for 20 minutes. The second mixed gas is then stopped, and argon gas is introduced. The furnace is allowed to cool naturally to room temperature.

[0062] Comparative Example 2

[0063] A method for preparing a heated de-icing graphene glass fiber cloth includes the following steps:

[0064] (1) The glass fiber was etched in a low-temperature plasma modification device for 2 minutes. The power was set to 100W and the pressure to 100Pa. The working gas was obtained by mixing argon and oxygen in a volume ratio of 4.5:1. The glass fiber was then dried at 90℃ for 15 minutes to obtain pretreated glass fiber.

[0065] (2) The pretreated glass fiber was placed in the CVD furnace as a substrate. After evacuation, argon gas with a flow rate of 100 sccm was introduced to wash the furnace. The temperature was raised to 1120℃. Argon gas with a flow rate of 450 sccm was introduced to make the pressure in the CVD furnace the standard atmospheric pressure. The first mixed gas (composed of hydrogen gas with a flow rate of 20 sccm and methane gas with a flow rate of 1000 sccm) was introduced for 90 min. The first mixed gas was then introduced. Argon gas was then introduced and the temperature was lowered to 750℃. The temperature was allowed to drop naturally to room temperature. Argon gas was continuously introduced during the natural cooling process to obtain graphene glass fiber.

[0066] (3) Graphene glass fibers are woven into a fiber fabric (plain weave) with a warp and weft density of 12×12 threads / cm. 2 The yarn fineness is 32 tex, and the fiber cloth thickness is 0.06±0.01 mm. After ultrasonically cleaning the fiber cloth with deionized water, it is dried with high-purity nitrogen and sent into the CVD furnace. After vacuuming, argon gas at a flow rate of 350 sccm is introduced to purge for 7 minutes. The temperature is increased to 1060℃ at a rate of 8℃ / min. Argon gas at a flow rate of 450 sccm is continued to be introduced to maintain the pressure in the CVD furnace at standard atmospheric pressure. A second mixed gas (composed of hydrogen at a flow rate of 20 sccm, methane at a flow rate of 1000 sccm, and ethanol at a flow rate of 6 sccm) preheated to 120℃ is introduced for 20 minutes. The second mixed gas is then stopped, and argon gas is introduced. The furnace is allowed to cool naturally to room temperature.

[0067] Comparative Example 3

[0068] A method for preparing a heated de-icing graphene glass fiber cloth includes the following steps:

[0069] (1) The glass fiber was etched in a low-temperature plasma modification device for 2 minutes. The power was set to 100W and the pressure to 100Pa. The working gas was obtained by mixing argon and oxygen in a volume ratio of 4.5:1. The glass fiber was then dried at 90℃ for 15 minutes to obtain pretreated glass fiber.

[0070] (2) The pretreated glass fiber was placed in a CVD furnace as a substrate. After evacuation, argon gas with a flow rate of 100 sccm was introduced to wash the furnace. The temperature was raised to 1120℃. Argon gas with a flow rate of 450 sccm was introduced to make the pressure in the CVD furnace the standard atmospheric pressure. The first mixed gas (composed of hydrogen with a flow rate of 20 sccm and methane with a flow rate of 1000 sccm) was introduced for 90 min. The first mixed gas was then stopped. Argon gas was then introduced and the temperature was lowered to 750℃. Water vapor at a temperature of 750℃ was introduced for 8 min at a flow rate of 10 sccm. The temperature was allowed to drop naturally to room temperature. Argon gas was continuously introduced during the natural cooling process to obtain graphene glass fiber.

[0071] (3) Graphene glass fibers are woven into a fiber fabric (plain weave) with a warp and weft density of 12×12 threads / cm. 2The yarn fineness is 32 tex, and the fiber cloth thickness is 0.06±0.01 mm. After ultrasonically cleaning the fiber cloth with deionized water, it is dried with high-purity nitrogen and sent into the CVD furnace. After vacuuming, argon gas with a flow rate of 350 sccm is introduced to purge for 7 minutes. The temperature is raised to 1060℃ at a rate of 8℃ / min. Argon gas with a flow rate of 450 sccm is continued to be introduced to maintain the pressure in the CVD furnace at standard atmospheric pressure. A first mixed gas (composed of hydrogen with a flow rate of 20 sccm and methane with a flow rate of 1000 sccm) preheated to 120℃ is introduced for 20 minutes. The second mixed gas is stopped, and argon gas is introduced. The temperature is lowered to 750℃. Water vapor at a temperature of 750℃ is introduced for 8 minutes at a flow rate of 10 sccm. The temperature is then allowed to drop naturally to room temperature. Argon gas is continuously introduced during the natural cooling process.

[0072] The graphene glass fiber cloths obtained in Examples 1-5 and Comparative Examples 1-3 were cut to 10cm × 10cm. Copper foil conductive tape was used to tightly adhere the tape to the warp edges of the graphene glass fiber cloth, and one end of the tape was fixed to a copper wire with solder, connecting it to the two electrode posts of the power supply. After the sample with the circuit connected was fixed in a self-made iron frame fixture, an infrared thermal imager was vertically aligned with the sample surface, and the voltage and DC current were set for electrothermal analysis.

[0073] A 30V DC voltage was applied to the graphene glass fiber cloths obtained in Examples 1-5 and Comparative Examples 1-3, and the cloths were heated continuously for 3-5 seconds until the temperature stabilized. The stable temperature values ​​of each group were recorded.

[0074] like Figure 1 As shown, the graphene glass fiber cloth obtained in Examples 1-5 has a stable electric heating temperature of over 50°C, which is significantly better than that of Comparative Examples 1-3; while the graphene glass fiber cloth obtained in Example 5 has the highest stable electric heating temperature.

[0075] Referring to the thermal imaging measurement method in GB / T 7287-2008 "Test Method for Infrared Radiation Heaters", an infrared thermal imager was placed 50 cm away from the sample to measure the temperature of the graphene glass fiber cloth obtained in Examples 1-5 and the graphene glass fiber cloth obtained in Comparative Examples 1-3 under a DC voltage of 150V, and the electro-thermal radiation conversion efficiency was calculated.

[0076]

[0077] In the formula, η is the electro-thermal radiation conversion efficiency, in %; σ is the Stefan-Boltzmann constant, 5.67 × 10⁻⁶. -8 W / (m 2 ·K 4 S represents the sample area, in m². 2 ;T tT0 is the average radiant temperature in K; T0 is the ambient temperature in K; and P is the measured electrical power in W.

[0078] like Figure 2 As shown, the electro-thermal radiation conversion efficiency of the graphene glass fiber cloth obtained in Examples 1-5 is higher than 44.5%, which is significantly better than that of Comparative Examples 1-3; while the electro-thermal radiation conversion efficiency of the graphene glass fiber cloth obtained in Example 5 is the highest.

[0079] The graphene glass fiber cloths obtained in Examples 1-5 and Comparative Examples 1-3 were respectively attached to the surfaces of the four rotors of a quadcopter drone. The drone was launched and flight time was started. When the drone's flight time reached 1000 hours, the graphene glass fiber cloths on each rotor were removed, and a 28V DC voltage was applied for continuous heating for 3-5 seconds until the temperature stabilized. The stable temperature values ​​of each group of electric heating were recorded, and the decay rate of the stable temperature values ​​of electric heating was calculated.

[0080] The decay rate of the stable value of the electric heating temperature = (the stable value of the original electric heating temperature - the stable value of the electric heating temperature after 1000 hours of flight) ÷ the stable value of the original electric heating temperature × 100%.

[0081] The graphene-glass fiber cloth obtained in Comparative Example 1 could not withstand 1000 hours of flight. The remaining groups, such as... Figure 3 As shown, the graphene glass fiber cloth obtained in Example 5 still has the highest stable electric heating temperature value, and the lowest electric heating temperature stability decay rate, which is significantly better than the other groups.

[0082] The reason for the above results is that the present invention first performs plasma etching on the glass fiber, which can effectively increase the surface roughness and active sites of the fiber, and improve the initial bonding force of the first deposited graphene. After the first deposition, water vapor etching is introduced. The hydroxyl radicals generated by the high temperature water vapor selectively remove the residual amorphous carbon impurities on the substrate surface and the disordered carbon at the edge of the graphene, cleaning up more active sites on the substrate surface and defect sites at the edge of the graphene. This provides a stronger chemical bonding basis for the subsequent second deposition of graphene, significantly improving the interfacial bonding strength between graphene and the glass fiber matrix. This makes the graphene layer less likely to peel off due to interfacial debonding when the material is repeatedly bent, and the continuity of the conductive network is maintained. This invention utilizes the decomposition of ethanol in a second mixed gas at high temperature to generate hydroxyl radicals and small-molecule hydrocarbon species. The oxidative activity of hydroxyl radicals is significantly higher than that of hydrogen radicals generated by hydrogen decomposition, preferentially attacking disordered carbon at the edges or grain boundaries of graphene, promoting their oxidation and regeneration into an ordered lattice structure. This reduces the defect density of graphene, improves carrier mobility, and makes the resistivity distribution more uniform. Simultaneously, during the secondary deposition process, the small-molecule hydrocarbon species from ethanol decomposition synergistically regulate the carbon source supply rate with methane, inhibiting the overgrowth of polycrystalline graphene and further optimizing the electrothermal conversion efficiency. This invention uses a fiber fabric as a mechanical framework to support the graphene layer and disperse external stress. The two-deposited graphene layers effectively combine and maintain the continuity of the conductive network, allowing the graphene layer and fiber fabric to deform synergistically during bending, dispersing local stress over a larger area and avoiding stress concentration at a single location. This synergistic effect ensures that the material maintains the integrity of the graphene layer under dynamic loads (such as the periodic vibration of wind turbine blades), reducing crack propagation caused by repeated deformation, thereby ensuring the long-term stability of heating performance.

[0083] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A graphene glass fiber cloth for heating and de-icing, characterized in that, The graphene glass fiber cloth was prepared using the following method: Step 1: Perform low-temperature plasma treatment on the glass fiber; Step 2: Graphene is deposited on the surface of the glass fiber after low-temperature plasma treatment in the first mixed gas by chemical vapor deposition; then it is treated with water vapor at a temperature of 700-800℃ to obtain graphene glass fiber. Step 3: The graphene glass fiber is woven into a fiber fabric, and graphene is deposited on the surface of the fiber fabric in the second mixed gas by chemical vapor deposition to obtain graphene glass fiber cloth; The first mixed gas includes hydrogen and methane, with a flow rate ratio of hydrogen to methane of 1:10-100 and a hydrogen flow rate of 10-30 sccm. The second mixed gas is a mixture of hydrogen, methane, and ethanol preheated to 100-150°C, with a flow rate ratio of 1:10-100:0.1-0.5 for hydrogen, methane, and ethanol, and a hydrogen flow rate of 10-30 sccm.

2. The heated de-icing graphene glass fiber cloth according to claim 1, characterized in that, In step 1, the low-temperature plasma treatment time is 1-3 minutes, the low-temperature plasma treatment power is 80-120W, and the pressure during the low-temperature plasma treatment is 80-120Pa.

3. The heated de-icing graphene glass fiber cloth according to claim 1, characterized in that, In step 1, during the low-temperature plasma treatment process, the working gas includes argon and oxygen, with a volume ratio of argon to oxygen of 3-6:

1.

4. The heated de-icing graphene glass fiber cloth according to claim 1, characterized in that, The specific operation of step 2 is as follows: Using glass fiber treated with low-temperature plasma as a substrate, place it in a CVD furnace, evacuate the furnace, and then introduce argon gas for washing. Raise the temperature to 1100-1150℃, and continue to introduce argon gas to make the pressure in the CVD furnace reach the standard atmospheric pressure. Then, introduce the first mixed gas for 1-2 hours, and then stop introducing the first mixed gas. Introduce argon gas and cool down to 700-800℃. Then, introduce water vapor at a temperature of 700-800℃ for 5-10 minutes, and let it cool naturally to room temperature. During the natural cooling process, continue to introduce argon gas.

5. The heated de-icing graphene glass fiber cloth according to claim 4, characterized in that, After evacuation, argon gas is introduced for washing, with an argon gas flow rate of 50-150 sccm. After heating to 1100-1150℃, continue to introduce argon gas at a flow rate of 400-500 sccm.

6. The heated de-icing graphene glass fiber cloth according to claim 4, characterized in that, The steam flow rate is 5-15 sccm.

7. The heated de-icing graphene glass fiber cloth according to claim 1, characterized in that, In step 3, the warp and weft density of the fiber fabric is 12×12 threads / cm2, the fineness of the yarn used in the fiber fabric is 30-35tex, and the thickness of the fiber fabric is 0.05-0.08mm.

8. The heated de-icing graphene glass fiber cloth according to claim 1, characterized in that, The specific operation of step 3 is as follows: the graphene glass fiber is woven into a fiber fabric, the fiber fabric is fed into the CVD furnace, after vacuuming, argon gas is introduced to purge for 4-10 minutes, the temperature is raised to 1000-1120℃, argon gas is continued to be introduced to make the pressure in the CVD furnace the standard atmospheric pressure, the second mixed gas is introduced for 10-30 minutes, the introduction of the second mixed gas is stopped; argon gas is introduced and the temperature is allowed to drop naturally to room temperature.

9. The heated de-icing graphene glass fiber cloth according to claim 8, characterized in that, After heating to 1000-1120℃, continue to introduce argon gas at a flow rate of 400-500 sccm.

10. The heated de-icing graphene glass fiber cloth according to claim 8, characterized in that, During the process of heating to 1000-1120℃, the heating rate is 5-10℃ / min.

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