Construction of high electrical contact match and its application in a wing of a load-bearing de-icing integrated composite material

Abstract

The application provides a high electric contact matching construction and application thereof in a bearing deicing integrated composite wing, relates to the technical field of aircraft electric heating anti / deicing, and comprises the following steps: applying a nanocarbon material to a fiber cloth formed by conductive fibers, and compounding the nanocarbon material with a water-soluble resin to obtain the electric heating material; wherein the nanocarbon material comprises carbon nanotubes, graphene oxide and carbon powder. The fiber cloth formed by the conductive fibers is used as a toughening phase and a main conductive phase of the material, plays a role of a reinforcing body for bearing and a main conductive body with low resistivity, the nanocarbon material is used as a conductive and heat-conductive reinforcing phase, the carbon nanotubes are one-dimensional conductive and heat-conductive reinforcing phases, the graphene oxide is two-dimensional conductive and heat-conductive reinforcing phases, and the nanocarbon material is applied to the fiber cloth, so that the material can achieve a more uniform heating and heat-conducting effect.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of aircraft electrothermal anti-icing / de-icing technology, in particular to a high electrical contact matching construction and its application in a load-bearing de-icing integrated composite wing. BACKGROUND

[0002] Accumulative icing of aircraft refers to the phenomenon of ice layer gathering on some parts of the aircraft body surface. It is mainly formed by supercooled water droplets in the cloud or supercooled rain in the precipitation colliding with the aircraft body, and can also be formed by water vapor directly subliming on the aircraft body surface. Prolonged flight of the aircraft in the cloud can easily lead to icing. Accumulative icing of the aircraft can seriously affect flight safety. When the aircraft aerodynamic surface appears accumulative icing, it has a great impact on the aerodynamics. Wind tunnel tests show that when the wing leading edge has half-inch thick accumulative icing, the lift is reduced by 50% and the drag is increased by 60%. The speed of accumulative icing is very fast, and in the case of severe icing, the thickness of accumulative icing within 5 minutes can reach 2-3 inches. The most serious icing condition usually occurs when flying outside the cloud and encountering rain at icing temperature.

[0003] There are four current methods for aircraft anti-icing and de-icing: chemical solution anti-icing, gas heating anti-icing, mechanical de-icing, and electrothermal anti-icing. 1. Chemical solution de-icing is to spray anti-freezing liquid to the icing surface of the aircraft for anti-icing and de-icing. Anti-freezing liquid is a chemical liquid with very low freezing point, which lowers the freezing point of water and melts the formed ice layer. In general, when the aircraft is icing on the ground, de-icing is carried out by spraying with a de-icing vehicle. Ground spraying of chemical reagents not only pollutes the environment, but also can only be implemented on the ground, which has certain limitations. 2. Gas heating anti-icing is to introduce hot gas source into the parts that need to be anti-iced, such as wing and tail leading edge, to prevent icing. Engine bleed air de-icing increases the load of the engine. 3. Mechanical de-icing refers to installing a layer of inflatable rubber tube with air bag on the wing leading edge. The tube with air bag is attached to the wing during normal operation, and after icing, the tube with air bag is inflated and deflated periodically to break the ice layer on the surface, which is blown away by the airflow. The air bag de-icing easily destroys the air dynamic shape and increases the resistance, and is not thorough. 4. Electrothermal anti-icing is to embed strip-shaped, filament-shaped or film-shaped heating elements into the structure of the parts of the aircraft prone to icing, and to prevent and remove ice by heating. Electrothermal anti-icing and de-icing have the functions of anti-icing and de-icing, low energy consumption, good de-icing effect and easy control, and has become an important development trend of anti-icing and de-icing system. Electrothermal anti-icing and de-icing technology installs electrothermal devices inside the outer skin, and transmits heat from the inside to the outside after being heated by electricity, to make the ice layer attached to the surface of the aircraft body produce "detachment".

[0004] The physical mechanism of the aircraft electric heating anti / ice system is the Joule heat effect of the electric heating element material in the energized state, and the core element is the electric heating element. The electric heating element materials commonly used in the published patents 201720077351.1 and 201720078408.X are mostly metal alloys, thermosensitive ceramics and conductive fibers. The metal electric heating element has a difference in expansion coefficient with the insulation layer and other body structures and a high interfacial thermal resistance, which is easy to produce high thermal stress and structural thermal mismatch; the thermosensitive ceramic has high brittleness and poor processing performance, which is difficult to meet the requirements of the aviation material on impact resistance and fatigue resistance; the conductive fiber has good flexibility, but its uniformity is difficult to control, and local overheating is easy to occur to affect temperature control.

[0005] Therefore, the present application is proposed. SUMMARY

[0006] One of the purposes of the present application is to provide a preparation method of high electric contact matching electric heating material for bearing ice removal integrated composite wing, to at least solve one of the technical problems existing in the prior art. The preparation method provided by the present application makes the material heat and conduct heat more uniformly by applying nano-carbon material to the fiber cloth.

[0007] The second purpose of the present application is to provide an electric heating material prepared by the preparation method of high electric contact matching electric heating material for bearing ice removal integrated composite wing.

[0008] The third purpose of the present application is to provide an application of the electric heating material in preparing an electric heating element.

[0009] In order to achieve the above purposes of the present application, the following technical solutions are adopted:

[0010] In the first aspect, the present application provides a preparation method of high electric contact matching electric heating material for bearing ice removal integrated composite wing, comprising the following steps:

[0011] The nano-carbon material is applied to the fiber cloth formed by the conductive fiber, and then the fiber cloth is clamped in the water-soluble resin, and the electrode is pasted and pressed to obtain the electric heating material;

[0012] The nano-carbon material includes carbon nanotubes, graphene oxide and carbon powder.

[0013] After the nano-carbon material is applied to the fiber cloth, the fiber cloth is sequentially subjected to reduction agent application and drying treatment before being clamped in the water-soluble resin.

[0014] Further, the carbon nanotubes include at least one of oxidized carbon nanotubes and carbon nanotube powder.

[0015] Preferably, the mass ratio of the oxidized carbon nanotube, the graphene oxide, the carbon nanotube powder and the carbon powder is 2:2:1:1-3:3:1:1;

[0016] Preferably, the diameter of the oxidized carbon nanotube is 10-20nm, the flake diameter of the graphene oxide is 1-3μm, the diameter of the carbon nanotube powder is 10-20nm, and the diameter of the carbon powder is 20-30nm;

[0017] Preferably, the step of applying the nanocarbon material to the fiber cloth formed by the conductive fiber comprises: dispersing the formula amount of the oxidized carbon nanotube, the graphene oxide, the carbon nanotube powder and the carbon powder in water respectively to obtain an oxidized carbon nanotube suspension, a graphene oxide suspension, a carbon nanotube powder suspension and a carbon powder suspension, and then applying the oxidized carbon nanotube suspension, the carbon nanotube powder suspension and the carbon powder suspension to the fiber cloth, and then applying the graphene oxide suspension to the fiber cloth;

[0018] Preferably, the concentration of the oxidized carbon nanotube suspension, the graphene oxide suspension, the carbon nanotube powder suspension and the carbon powder suspension is 0.5-0.7mg / mL.

[0019] Further, the oxidized carbon nanotube suspension, the graphene oxide suspension, the carbon nanotube powder suspension and the carbon powder suspension are applied to the fiber cloth by spraying;

[0020] Preferably, each suspension is sprayed uniformly for 5-10 times.

[0021] Further, the conductive fiber comprises carbon fiber;

[0022] Preferably, the carbon fiber cloth is obtained by weaving carbon fiber.

[0023] Further, the water-soluble resin comprises water-soluble alkyd resin;

[0024] Preferably, the electrode spacing is 70-75mm;

[0025] Preferably, the calendering temperature is 70-130℃, and the roll gap is 0.4-0.5mm.

[0026] Further, the reducing agent comprises ascorbic acid solution;

[0027] Preferably, the mass ratio of the solute in the reducing agent to the nanocarbon material is 0.1:1-5:1;

[0028] Preferably, the concentration of the reducing agent is 50-3500mg / L;

[0029] Preferably, the reducing agent is applied to the fiber cloth by spraying;

[0030] Preferably, the temperature of the drying treatment is 40-60℃, and the time is 20-24h.

[0031] Further, before applying the nanocarbon material to the fiber cloth, the fiber cloth is subjected to a desizing treatment.

[0032] Preferably, the desizing treatment employs Soxhlet extraction.

[0033] In a third aspect, the present application provides the use of the electrothermal material in the preparation of an electrothermal element.

[0034] Further, the electrothermal element is in a sheet structure.

[0035] Compared with the prior art, the present application has the following beneficial effects:

[0036] The present application provides a preparation method of a high-electricity-contact matching electrothermal material for a load-icing integrated composite wing, which uses a fiber cloth formed by conductive fibers as a toughening phase and a main conductive phase, plays the role of a reinforcing body for loading and a main conductive body with low resistivity, uses nanocarbon materials as a conductive and heat-conductive reinforcing phase, wherein carbon nanotubes are one-dimensional conductive and heat-conductive reinforcing phases, graphene oxide is two-dimensional conductive and heat-conductive reinforcing phases, and carbon powder is three-dimensional conductive and heat-conductive reinforcing phases, and the nanocarbon materials are applied to the fiber cloth, so that the material can achieve a more uniform heating and heat-conducting effect. BRIEF DESCRIPTION OF DRAWINGS

[0037] In order to more clearly illustrate the technical solutions in the specific embodiments or the prior art, the following will briefly introduce the drawings needed to be used in the specific embodiments or the prior art description. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0038] Figure 1 The flowchart of the preparation method of the high-electricity-contact matching electrothermal material for a load-icing integrated composite wing provided by the present application is shown in the figure.

[0039] Figure 2 The electrode patch position diagram of Example 1 of the present application is shown in the figure.

[0040] Figure legend: 1-carbon fiber cloth; 2-copper electrode. DETAILED DESCRIPTION

[0041] Unless otherwise defined, scientific and technical terms used in connection with the present application shall have the meanings that are commonly understood by those of ordinary skill in the art. The meaning and scope of the terms should be clear; however, in the event of any latent ambiguity, definitions provided herein take precedent over any dictionary or extrinsic definition. In this application, the use of "or" means "and / or" unless stated otherwise. Furthermore, use of the term "including" as well as other forms such as "include", "includes" or "included" is not limiting.

[0042] The technical solutions of the present application will be clearly and completely described below in combination with the embodiments. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the scope of protection of the present application.

[0043] The present application provides a preparation method of high electrical contact matching electrothermal material for a wing of a load-carrying deicing integrated composite material, comprising the following steps:

[0044] A nanocarbon material is applied to a fiber cloth formed by conductive fibers, and then the fiber cloth is sandwiched in a water-soluble resin, and an electrode is attached and then pressed and rolled to obtain the electrothermal material.

[0045] The nanocarbon material comprises carbon nanotubes, graphene oxide and carbon powder.

[0046] After the nanocarbon material is applied to the fiber cloth, the fiber cloth is subjected to reduction agent application and drying treatment in sequence before being sandwiched in the water-soluble resin.

[0047] The preparation method of high electrical contact matching electrothermal material for a wing of a load-carrying deicing integrated composite material provided by the present application uses a fiber cloth formed by conductive fibers as a toughening phase and a main conductive phase, plays the role of a reinforcing body for carrying and a main conductive body with low resistivity, uses a nanocarbon material as a conductive and heat-conductive reinforcing phase, wherein carbon nanotubes are one-dimensional conductive and heat-conductive reinforcing phases, graphene oxide is two-dimensional conductive and heat-conductive reinforcing phases, and carbon powder is three-dimensional conductive and heat-conductive reinforcing phases. By applying the nanocarbon material to the fiber cloth, the material can achieve a more uniform heating and heat-conducting effect.

[0048] In some preferred embodiments, the carbon nanotubes comprise at least one of oxidized carbon nanotubes and carbon nanotube powder.

[0049] Preferably, the mass ratio of the oxidized carbon nanotubes, the graphene oxide, the carbon nanotube powder and the carbon powder is 2:2:1:1-3:3:1:1, for example, can be 2:2:1:1, 2.5:2.5:1:1, 3:3:1:1, etc.

[0050] Preferably, the diameter of the oxidized carbon nanotube is 10-20 nm, for example, it can be 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, etc.; the diameter of the graphene oxide sheet is 1-3 μm, for example, it can be 1 μm, 2 μm, 3 μm, etc.; the diameter of the carbon nanotube powder is 10-20 nm, for example, it can be 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, etc.; the diameter of the carbon powder is 20-30 nm, for example, it can be 20 nm, 21 nm, 22 nm, 23 nm, 24 nm, 25 nm, 26 nm, 27 nm, 28 nm, 29 nm, 30 nm, etc.

[0051] Preferably, the step of applying the nanocarbon material to the fiber cloth formed by the conductive fibers comprises: dispersing the formula amount of the oxidized carbon nanotube, the graphene oxide, the carbon nanotube powder and the carbon powder in water respectively to obtain an oxidized carbon nanotube suspension, a graphene oxide suspension, a carbon nanotube powder suspension and a carbon powder suspension, and then applying the oxidized carbon nanotube suspension, the carbon nanotube powder suspension and the carbon powder suspension to the fiber cloth, and then applying the graphene oxide suspension to the fiber cloth.

[0052] Preferably, the concentration of the oxidized carbon nanotube suspension, the graphene oxide suspension, the carbon nanotube powder suspension and the carbon powder suspension is 0.5-0.7 mg / mL, for example, it can be 0.5 mg / mL, 0.6 mg / mL, 0.7 mg / mL, etc.

[0053] In the present application, one-dimensional and two-dimensional conductive and heat-conductive reinforcing phases are introduced into the main conductive phase by spraying, carbon nanotubes are used as one-dimensional conductive and heat-conductive reinforcing phases, graphene oxide is used as two-dimensional conductive and heat-conductive reinforcing phases, and the conductive and heat-conductive reinforcing phases are filled into the fiber bundles by spraying, so that the thermal conductivity of the material is more uniform.

[0054] In the present application, the above carbon nanomaterials are introduced in batches, first, the nanoscale oxidized carbon nanotubes, carbon nanotube powder and carbon powder are introduced, which are used to fill the interstitial space of the fiber bundle, and then the micrometer-scale graphene oxide is introduced, which is used to fill the interstitial space between the fiber bundles.

[0055] In some preferred embodiments, the oxidized carbon nanotube suspension, the graphene oxide suspension, the carbon nanotube powder suspension and the carbon powder suspension are applied to the fiber cloth by spraying;

[0056] Preferably, each suspension is sprayed uniformly for 5-10 times.

[0057] In the present application, the carbon fiber cloth is uniformly sprayed by using an electric paint spraying gun, and the drying method is natural air drying, and the spraying operation is repeated after air drying, and the spraying times of each suspension are controlled to be 5-10 times, for example, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, etc.

[0058] In some preferred embodiments, the conductive fiber comprises carbon fiber;

[0059] Preferably, the carbon fiber cloth is obtained by weaving carbon fiber, and the size of the carbon fiber cloth is 100*60mm.

[0060] In the present application, the continuous fiber (specifically, carbon fiber) is used as the toughening phase and the main conductive item of the electric heating material.

[0061] In some preferred embodiments, the fiber cloth is desized before the nanocarbon material is applied to the fiber cloth;

[0062] In the present application, the desizing treatment is preferably performed by Soxhlet extraction method, and the surface of the carbon fiber on the market is coated with a sizing agent, and the carbon fiber cloth is desized by the Soxhlet extraction method to remove the sizing agent on the surface of the carbon fiber, thereby improving the conductivity.

[0063] In some preferred embodiments, before being compounded with the water-soluble resin, the preparation method further comprises: sequentially applying a reducing agent and drying treatment to the fiber cloth on which the nanocarbon material is deposited;

[0064] Preferably, the reducing agent is applied to the fiber cloth by spraying;

[0065] Preferably, the reducing agent comprises an ascorbic acid solution;

[0066] Preferably, the concentration of the reducing agent is 50-3500mg / L; for example, 50mg / L, 100mg / L, 500mg / L, 1000mg / L, 3000mg / L, 3500mg / L, etc.

[0067] Preferably, the mass ratio of the solute in the reducing agent to the nanocarbon material is 0.1:1-5:1, for example, 0.1:1, 1:1, 2:1, 3:1, 4:1, 5:1, etc.

[0068] Preferably, the temperature of the drying treatment is 40-60℃, for example, 40℃, 50℃, 60℃, etc.

[0069] In the present application, in order to obtain better conductivity, the carbon fiber cloth deposited with oxidized carbon nanomaterial is reduced by a reducing agent, the oxidized carbon nanotube and graphene oxide are reduced by the reducing agent, and the reduced oxidized carbon nanomaterial is obtained, wherein the reducing agent is ascorbic acid which is green and harmless.

[0070] In some preferred embodiments, the water-soluble resin comprises a self-drying water-soluble alkyd resin;

[0071] Preferably, the electrode spacing is 70-75 mm, for example, it can be 70 mm, 71 mm, 72 mm, 73 mm, 74 mm, 75 mm, etc.; the electrode is preferably a copper electrode;

[0072] Preferably, the pressing temperature is 70-130 DEG C, for example, it can be 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 115 DEG C, 120 DEG C, 130 DEG C, etc.; the roll gap is 0.4-0.5 mm, for example, it can be 0.4 mm, 0.5 mm, etc.

[0073] In the present application, the water-soluble resin is used for packaging, the electric heating sheet obtained after the reduction step is clamped in the alkyd resin sheet, and the copper electrode is pressed and rolled after being attached. The electric heating material is prepared by using a dry pre-impregnated material method, and the electric heating material is a continuous fiber reinforced conductive resin-based composite pre-impregnated material.

[0074] The second aspect of the present application provides an electric heating material prepared by a method for preparing a high electric contact matching electric heating material for a bearing / de-icing integrated composite wing.

[0075] The third aspect of the present application provides an application of the electric heating material in preparing an electric heating element, and the electric heating element is a sheet layer structure.

[0076] The electric heating element in the present application is a high electric contact matching electric heating element for a bearing / de-icing integrated composite wing. Carbon fiber is used as a structural toughening phase and a main conductive phase, one-dimensional and two-dimensional conductive reinforcing phases are introduced, and water-soluble resin is used for bonding and packaging to form a sheet layer structure. The sheet layer structure is a single layer structure, the structural toughening phase and the main conductive phase of the sheet layer structure are carbon fiber cloth formed by weaving carbon fiber, which plays the role of a reinforcing body for bearing and a main conductive body with low resistivity. One-dimensional and two-dimensional conductive and thermal conductive reinforcing phases are introduced to the main conductive phase by spraying, and the pre-impregnated material is prepared by using water-soluble resin for bonding and packaging after spraying, which is convenient for cutting and preparing an integrated composite wing. Compared with the prior art, the product prepared by the present application has the advantages of lightweight, high bearing, single layer structure, etc., and the preparation method has a high-efficiency preparation mode of systematization and industrialization production, and is suitable for manufacturing electric heating elements for bearing / de-icing integrated composite wings of any size of aircraft.

[0077] Further, the application provides a preparation method of the high electrical contact matching electrothermal material for the wing of the integrated composite material bearing deicing, which specifically comprises the following steps: Figure 1 as shown, specifically comprising the following steps:

[0078] (1) carbon fiber cloth woven by carbon fibers is selected, the size of the carbon fiber cloth is 100*60mm, and the carbon fiber cloth is subjected to desizing treatment by Soxhlet extraction method, the specific operation of the extraction method is as follows: the cut carbon fiber cloth is wrapped with filter paper and defatted cotton, and then is loaded into an extraction tube of a Soxhlet extractor, 200mL of acetone is added into an extraction bottle, and extraction is carried out at 75-80℃ for 72h. After the reaction is completed, the carbon fiber cloth is taken out, washed with anhydrous ethanol and deionized water respectively, and then is placed in a 60℃ oven for drying and standby use;

[0079] (2) the formula amount of oxidized carbon nanotubes, graphene oxide, carbon nanotube powder and carbon powder is respectively dispersed in deionized water, and ultrasonic stirring is carried out to prepare oxidized carbon nanotube suspension, graphene oxide suspension, carbon nanotube powder suspension and carbon powder suspension with certain concentrations respectively, then the oxidized carbon nanotube suspension, carbon nanotube powder suspension and carbon powder suspension are applied to the fiber cloth, and then the graphene oxide suspension is applied to the fiber cloth.

[0080] (3) an electric paint spraying gun is used to uniformly spray the mixed solution of the oxidized carbon nanotube suspension, the carbon nanotube powder suspension and the carbon powder suspension on the surface of the carbon fiber cloth, and then the graphene oxide suspension is sprayed, and the drying mode is natural air drying, after air drying, the spraying operation is repeated, and the total spraying times are controlled to be 5-10 times;

[0081] (4) then the carbon fiber cloth with the introduced oxidized carbon nanomaterial is reduced by using a reducing agent, ascorbic acid is weighed and dissolved in deionized water, and is introduced into the carbon fiber cloth by spraying, and after two hours, the reduction is completed, the carbon fiber cloth is washed with deionized water, and is placed in a vacuum oven at 40-60℃ for 20-24h to obtain an electrothermal sheet;

[0082] (5) the electrothermal sheet obtained in step (4) is clamped between two coating papers containing alkyd resin, a copper electrode is attached, and then is placed into a double-roller rolling machine, and after the rolling is completed, a continuous fiber reinforced conductive resin-based composite material prepreg, i.e., an electrothermal material, is obtained.

[0083] The application is further described below by examples. Unless otherwise specified, the materials in the examples are prepared according to the existing method or directly purchased from the market.

[0084] Example 1

[0085] The embodiment provides a preparation method of the high electrical contact matching electrothermal material for the wing of the integrated composite material bearing deicing, which comprises the following steps:

[0086] (1) Select carbon fiber cloth woven with carbon fiber, the size of carbon fiber cloth is 100*60mm, adopt Soxhlet extraction method to carry out desizing treatment on carbon fiber cloth, the specific operation of Soxhlet extraction method is: take the cut carbon fiber cloth, wrap it with filter paper and defatted cotton, then put it into the extraction tube of Soxhlet extractor, add 200mL acetone into the extraction bottle, extract at 75-80℃ for 72h. After the reaction is completed, take out the carbon fiber cloth, clean it with anhydrous ethanol and deionized water respectively, then put it into the 60℃ oven for drying and standby;

[0087] (2) Take the mass ratio of 2.5:2.5:1:1 of oxidized carbon nanotube, graphene oxide, carbon nanotube powder and carbon powder, respectively, disperse the above formula amount of oxidized carbon nanotube, graphene oxide, carbon nanotube powder and carbon powder in deionized water, and prepare a certain concentration of oxidized carbon nanotube suspension, graphene oxide suspension, carbon nanotube powder suspension and carbon powder suspension by ultrasonic stirring, the concentration of oxidized carbon nanotube suspension, graphene oxide suspension, carbon nanotube powder suspension and carbon powder suspension is 0.6mg / mL;

[0088] Among them, the diameter of the oxidized carbon nanotube is 15nm, the flake diameter of the graphene oxide is 2μm, the diameter of the carbon nanotube powder is 15nm, and the diameter of the carbon powder is 25nm;

[0089] (3) Adopt electric paint spraying gun to uniformly spray the mixed solution of oxidized carbon nanotube suspension, carbon nanotube powder suspension and carbon powder suspension on the surface of carbon fiber cloth, then spray graphene oxide suspension, after spraying, air dry for 24h, after air drying, repeat the spraying operation of oxidized carbon nanotube suspension, carbon nanotube powder suspension and carbon powder suspension and graphene oxide suspension, the total spraying times are controlled within 8 times;

[0090] (4) Then use reducing agent to reduce the carbon fiber cloth introduced with oxidized carbon nanomaterials, weigh ascorbic acid, dissolve it in deionized water, and introduce it into the carbon fiber cloth by spraying, after two hours, the reduction is completed, wash it with deionized water, and place it in a vacuum oven at 50℃ for 22h to obtain an electric heating sheet, wherein the mass ratio of ascorbic acid to the sum of the mass of the above oxidized carbon nanotube, graphene oxide, carbon nanotube powder and carbon powder is 3:1, and the concentration of reducing agent is 2000mg / L;

[0091] (5) Put the electric heating sheet obtained in step (4) between two coating papers containing self-drying alkyd resin, paste copper electrodes (electrode spacing is 73mm), then put it into a double roller mill (pressure rolling temperature is 100℃, roller gap is 0.45mm), after pressure rolling, a continuous fiber reinforced conductive resin matrix composite material prepreg, i.e. an electric heating material, is obtained;

[0092] Among them, the diameter of the oxidized carbon nanotube is 15nm, the flake diameter of the graphene oxide is 2μm, the diameter of the carbon nanotube powder is 15nm, and the diameter of the carbon powder is 25nm; Figure 2As shown, the copper electrode is arranged along the width direction of the carbon fiber cloth 1 (i.e. parallel to the 60mm side direction of the carbon fiber cloth 1), two copper electrodes 2 are arranged with a spacing of 73mm, and the two electrodes are centrally attached to the 100mm side of the carbon fiber cloth 1, the length of the copper electrode 2 is 80-85mm, and the width is 8-10mm.

[0093] Example 2

[0094] The embodiment provides a preparation method of high electrical contact matching electrothermal material for a wing of a deicing integrated composite material, and the method comprises the following steps:

[0095] (1) carbon fiber cloth woven by carbon fibers is selected, the size of the carbon fiber cloth is 100*60mm, and the carbon fiber cloth is subjected to desizing treatment by using a Soxhlet extraction method, the Soxhlet extraction method is specifically operated as follows: the cut carbon fiber cloth is wrapped with filter paper and defatted cotton, and then is loaded into an extraction tube of a Soxhlet extractor, 200mL of acetone is added into an extraction bottle, and extraction is performed at 75-80℃ for 72h. After the reaction is completed, the carbon fiber cloth is taken out, washed with anhydrous ethanol and deionized water respectively, and then is placed in a 60℃ oven for drying and standby;

[0096] (2) the mass ratio of the oxidized carbon nanotubes, the graphene oxide, the carbon nanotube powder and the carbon powder is 2:2:1:1, the oxidized carbon nanotubes, the graphene oxide, the carbon nanotube powder and the carbon powder are respectively dispersed in deionized water, and the oxidized carbon nanotube suspension, the graphene oxide suspension, the carbon nanotube powder suspension and the carbon powder suspension are respectively prepared by ultrasonic stirring to a certain concentration, and the concentration of the oxidized carbon nanotube suspension, the graphene oxide suspension, the carbon nanotube powder suspension and the carbon powder suspension is 0.7mg / mL;

[0097] The diameter of the oxidized carbon nanotubes is 10nm, the diameter of the graphene oxide sheet is 1μm, the diameter of the carbon nanotube powder is 10nm, and the diameter of the carbon powder is 30nm.

[0098] (3) the surface of the carbon fiber cloth is uniformly sprayed with a mixture of the oxidized carbon nanotube suspension, the carbon nanotube powder suspension and the carbon powder suspension by using an electric paint spraying gun, and then the graphene oxide suspension is sprayed, after the spraying is completed, the carbon fiber cloth is naturally air-dried for 24h, and after the air-drying, the spraying operation of the oxidized carbon nanotube suspension, the carbon nanotube powder suspension and the carbon powder suspension and the graphene oxide suspension is repeated, and the total spraying times are controlled to be 5 times.

[0099] (4) After that, the carbon fiber cloth introduced with oxidized carbon nanomaterials is reduced with a reducing agent, ascorbic acid is weighed, dissolved in deionized water, introduced into the carbon fiber cloth in a spraying manner, and reduced after two hours. After washing with deionized water, it is placed in a vacuum oven at 40℃ for 24h to obtain an electrothermal sheet, wherein the mass ratio of ascorbic acid to the sum of the masses of the above-mentioned oxidized carbon nanotubes, graphene oxide, carbon nanotube powder and carbon powder is 0.1:1, and the concentration of the reducing agent is 50mg / L;

[0100] (5) The electrothermal sheet obtained in step (4) is sandwiched between two coated papers containing self-drying alkyd resin, copper electrodes (electrode spacing 70mm) are attached, and then placed in a double roller mill (pressure rolling temperature 70℃, roller gap 0.5mm). After pressure rolling, a continuous fiber reinforced conductive resin matrix composite prepreg, i.e. an electrothermal material, is obtained.

[0101] Wherein, the copper electrodes are arranged along the width direction of the carbon fiber cloth (i.e. parallel to the 60mm side direction of the carbon fiber cloth), and two copper electrodes are arranged with a spacing of 70mm, and the two electrodes are centrally attached to the 100mm side of the carbon fiber cloth. The length of the electrode is 80-85mm, and the width is 8-10mm.

[0102] Example 3

[0103] The present embodiment provides a method for preparing a high electrical contact matching electrothermal material for a wing of a bearing deicing integrated composite material, comprising the following steps:

[0104] (1) A carbon fiber cloth woven with carbon fibers is selected, and the size of the carbon fiber cloth is 100×60mm. The carbon fiber cloth is treated by Soxhlet extraction method. The specific operation of the Soxhlet extraction method is as follows: the cut carbon fiber cloth is wrapped with filter paper and defatted cotton, and then put into the extraction tube of the Soxhlet extractor. 200mL of acetone is added to the extraction bottle, and extraction is carried out at 75-80℃ for 72h. After the reaction is completed, the carbon fiber cloth is taken out, washed with anhydrous ethanol and deionized water, and then placed in a 60℃ oven for drying.

[0105] (2) Oxidized carbon nanotubes, graphene oxide, carbon nanotube powder and carbon powder with a mass ratio of 3:3:1:1 are weighed, and the above-mentioned formula amount of oxidized carbon nanotubes, graphene oxide, carbon nanotube powder and carbon powder are dispersed in deionized water respectively, and a certain concentration of oxidized carbon nanotube suspension, graphene oxide suspension, carbon nanotube powder suspension and carbon powder suspension are prepared by ultrasonic stirring. The concentration of the oxidized carbon nanotube suspension, graphene oxide suspension, carbon nanotube powder suspension and carbon powder suspension is 0.5mg / mL.

[0106] Wherein, the diameter of the oxidized carbon nanotube is 20nm, the diameter of the graphene oxide sheet is 3μm, the diameter of the carbon nanotube powder is 20nm, and the diameter of the carbon powder is 20nm.

[0107] (3) Adopting the electric paint spraying gun to uniformly spray the surface of the carbon fiber cloth with the particle size of 2 μm, and naturally air-drying for 24 h. After air-drying, the spraying operations of the above-mentioned oxidized carbon nanotube suspension, carbon nanotube powder suspension and carbon powder suspension and graphene oxide suspension are repeated, and the total spraying times are controlled to be 10 times;

[0108] (4) Then, the carbon fiber cloth introduced with the oxidized carbon nanomaterial is reduced by using a reducing agent. Ascorbic acid is weighed, dissolved in deionized water, and introduced into the carbon fiber cloth by spraying. After two hours, the reduction is completed. The carbon fiber cloth is washed with deionized water and placed in a vacuum oven at 60°C for 20 h to obtain an electrothermal sheet. The mass ratio of ascorbic acid to the sum of the masses of the above-mentioned oxidized carbon nanotube, graphene oxide, carbon nanotube powder and carbon powder is 5:1, and the concentration of the reducing agent is 3500 mg / L;

[0109] (5) The electrothermal sheet obtained in step (4) is sandwiched between two coating papers containing a self-drying alkyd resin, and copper electrodes (electrode spacing 75 mm) are attached. Then, the sandwiched structure is placed in a double-roller rolling machine (rolling temperature 130°C, roller gap 0.4 mm). After rolling, a continuous fiber-reinforced conductive resin-based composite material prepreg, i.e., an electrothermal material, is obtained.

[0110] The copper electrodes are arranged along the width direction of the carbon fiber cloth (i.e., parallel to the 60 mm side direction of the carbon fiber cloth). Two copper electrodes are arranged with a spacing of 75 mm, and the two electrodes are centrally attached to the 100 mm side of the carbon fiber cloth. The length of the electrodes is 80-85 mm, and the width of the electrodes is 8-10 mm.

[0111] Example 4

[0112] The present embodiment provides a method for preparing a high electrical contact matching electrothermal material for a wing of a load-icing integrated composite material. The difference between the present embodiment and Example 1 is that the mass ratio of the oxidized carbon nanotube, graphene oxide, carbon nanotube powder and carbon powder is 1:1:1:1, and the remaining steps are consistent with those of Example 1.

[0113] Example 5

[0114] The present embodiment provides a method for preparing a high electrical contact matching electrothermal material for a wing of a load-icing integrated composite material. The difference between the present embodiment and Example 1 is that the mass ratio of the oxidized carbon nanotube, graphene oxide, carbon nanotube powder and carbon powder is 4:4:1:1, and the remaining steps are consistent with those of Example 1.

[0115] Example 6

[0116] The present embodiment provides a method for preparing a high electrical contact matching electrothermal material for a wing of a load-icing integrated composite material. The difference between the present embodiment and Example 1 is that:

[0117] In step (3), the graphene oxide suspension is sprayed first, and then the oxidized carbon nanotube suspension, the carbon nanotube powder suspension and the carbon powder suspension are sprayed; the remaining steps are consistent with those of Example 1.

[0118] Example 7

[0119] The present embodiment provides a method for preparing a high electrical contact matching electrothermal material for a wing of a deicing integrated composite material, which is different from Example 1 in that:

[0120] In step (2), the oxidized carbon nanotube suspension, the carbon nanotube powder suspension and the carbon powder suspension are sprayed onto the fiber cloth in sequence, and then the graphene oxide suspension is sprayed onto the fiber cloth;

[0121] The remaining steps are consistent with those of Example 1.

[0122] Application Examples 1-7

[0123] Application Examples 1-7 respectively use the electrothermal materials prepared by Examples 1-7 to prepare electrothermal elements.

[0124] Comparative Example 1

[0125] The present comparative example provides an electrothermal material, which is different from Example 1 in that: in step (2), graphene oxide and carbon powder with a mass ratio of 5:2 are weighed and dispersed in deionized water; the remaining steps are consistent with those of Example 1.

[0126] Comparative Example 2

[0127] The present comparative example provides an electrothermal material, which is different from Example 1 in that: in step (2), oxidized carbon nanotubes, carbon nanotube powder and carbon powder with a mass ratio of 5:1:1 are weighed and dispersed in deionized water; the remaining steps are consistent with those of Example 1.

[0128] Comparative Example 3

[0129] The present comparative example provides an electrothermal material, which is different from Example 1 in that: in step (2), oxidized carbon nanotubes, graphene oxide and carbon nanotube powder with a mass ratio of 2.5:2.5:2 are weighed and dispersed in deionized water; the remaining steps are consistent with those of Example 1.

[0130] Comparative Example 4

[0131] The present comparative example provides an electrothermal material, which is different from Example 1 in that: step (4) is not performed; the remaining steps are consistent with those of Example 1.

[0132] Comparative Application Examples 1-4

[0133] Comparative Application Examples 1-4 respectively use the electrothermal materials prepared by Comparative Examples 1-4 to prepare electrothermal elements.

[0134] Test Example

[0135] Test method:

[0136] The coated paper of the continuous fiber reinforced conductive resin matrix composite prepreg is torn, and is sandwiched between two glass fiber prepregs to obtain the continuous fiber reinforced conductive resin matrix composite by hot pressing. The hot pressing process parameters are 100-130℃, 2-3MPa, and 1h. The direct current power supply is turned on, and the voltage is adjusted to 100-120V. After reaching a stable state, the voltage and current are observed, and the electrical conductivity of the material can be calculated according to the size of the material. The voltage is adjusted so that the temperature of the material is maintained at 50-55℃, the surface temperature of the material is detected using an infrared thermal imager, a temperature distribution map is obtained, and the maximum surface temperature difference is calculated.

[0137] Test sample: The electrothermal elements prepared by the application examples 1-7 and the electrothermal elements prepared by the comparative application examples 1-4 are used as samples.

[0138] The test results are shown in Table 1.

[0139] Table 1

[0140]

[0141] From the data in Table 1, it can be seen that when the carbon nanomaterials in the embodiments of the present application are oxidized carbon nanotubes, graphene oxide, carbon nanotube powder and carbon powder, and the ratio is in the range of 2:2:1:1-3:3:1:1, the electrical conductivity of the material is high, the corresponding temperature rise rate is good, the temperature difference is small, and the heating uniformity is good. At the same time, by comparing the data of comparative application example 4 and application example 1, it can be seen that the comprehensive performance of the carbon fiber cloth with oxidized carbon nanomaterials deposited by using a reducing agent is stronger.

[0142] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or make equivalent substitutions for part or all of the technical features; and these modifications or substitutions do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for preparing a high electrical contact matching electrothermal material for a load-bearing deicing integrated composite wing, characterized in that: include: Applying nano-carbon material to a fiber cloth formed of conductive fibers, then sandwiching the fiber cloth in a water-soluble resin, attaching electrodes and then pressing to obtain the electrothermal material; Wherein, the nanocarbon material includes carbon nanotubes, graphene oxide and carbon powder; After applying the nano-carbon material to the fiber cloth, the fiber cloth is sequentially subjected to a reducing agent and a drying treatment before being sandwiched between the fiber cloth and the water-soluble resin; The carbon nanotubes include oxidized carbon nanotubes and carbon nanotube powder; The preparation method comprises the following steps: Step 1: Desizing the fiber cloth formed of the conductive fibers using a Soxhlet extraction method, and then washing and drying the desizing fiber cloth in sequence; Step 2: Dispersing oxidized carbon nanotubes, graphene oxide, carbon nanotube powder, and carbon powder in water respectively to obtain an oxidized carbon nanotube suspension, a graphene oxide suspension, a carbon nanotube powder suspension, and a carbon powder suspension; Step 3: Use an electric spray gun to spray a mixture of carbon nanotube oxide suspension, carbon nanotube powder suspension, and carbon powder suspension onto the surface of the fiber cloth, then spray the graphene oxide suspension, and repeat the spraying operation after drying; Step 4: Apply the reducing agent to the fiber cloth by spraying, followed by washing and drying; Step 5: The material obtained in step 4 is sandwiched between two pieces of coated paper containing alkyd resin, copper electrodes are attached, and then placed in a double-roll mill. After the rolling is completed, the electric heating material is obtained.

2. The method for preparing a high electrical contact matching electrothermal material for a load-bearing and deicing integrated composite wing according to claim 1, characterized in that: The mass ratio of the oxidized carbon nanotubes, the graphene oxide, the carbon nanotube powder and the carbon powder is 2:2:1:1-3:3:1:

1.

3. The method for preparing a high electrical contact matching electrothermal material for a load-bearing and deicing integrated composite wing according to claim 1, characterized in that: The diameter of the oxidized carbon nanotube is 10-20 nm, the diameter of the graphene oxide is 1-3 μm, the diameter of the carbon nanotube powder is 10-20 nm, and the diameter of the carbon powder is 20-30 nm.

4. The method for preparing a high electrical contact matching electrothermal material for a load-bearing and deicing integrated composite wing according to claim 1, characterized in that: The concentrations of the oxidized carbon nanotube suspension, the oxidized graphene suspension, the carbon nanotube powder suspension and the carbon powder suspension are all 0.5-0.7 mg / mL.

5. The method for preparing a high electrical contact matching electrothermal material for a load-bearing and deicing integrated composite wing according to claim 1, characterized in that: Each suspension was sprayed evenly 5-10 times.

6. The method for preparing a high electrical contact matching electrothermal material for a load-bearing and deicing integrated composite wing according to claim 1, characterized in that: The conductive fibers include carbon fibers.

7. The method for preparing a high electrical contact matching electrothermal material for a load-bearing and deicing integrated composite wing according to claim 6, characterized in that: Carbon fiber cloth is obtained by weaving carbon fiber.

8. The method for preparing a high electrical contact matching electrothermal material for a load-bearing and deicing integrated composite wing according to claim 1, characterized in that: The electrode spacing is 70-75 mm.

9. The method for preparing a high electrical contact matching electrothermal material for a load-bearing and deicing integrated composite wing according to claim 1, characterized in that: The rolling temperature is 70-130°C and the roll gap is 0.4-0.5mm.

10. The method for preparing a high electrical contact matching electrothermal material for a load-bearing and deicing integrated composite wing according to claim 1, characterized in that: The reducing agent includes an ascorbic acid solution.

11. The method for preparing a high electrical contact matching electrothermal material for a load-bearing and deicing integrated composite wing according to claim 1, characterized in that: The mass ratio of the solute in the reducing agent to the nano-carbon material is 0.1:1-5:

1.

12. The method for preparing a high electrical contact matching electrothermal material for a load-bearing and deicing integrated composite wing according to claim 1, characterized in that: The concentration of the reducing agent is 50-3500 mg / L.

13. The method for preparing a high electrical contact matching electrothermal material for a load-bearing and deicing integrated composite wing according to claim 1, characterized in that: After applying the reducing agent, the drying temperature is 40-60°C and the drying time is 20-24 hours.

14. The electrothermal material prepared by the method for preparing an electrothermal material with high electrical contact matching for a load-bearing and deicing integrated composite wing according to any one of claims 1 to 13.

15. Use of the electric heating material according to claim 14 in preparing electric heating elements.

16. The use according to claim 15, characterized in that The electric heating element is a lamellar structure.

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