Preparation method and application of self-repairing composite material surface film with automatic deicing function

Abstract

The application relates to a preparation method and application of a self-repairing composite material surface film with an automatic deicing function, and belongs to the field of automatic deicing self-repairing composite material surface films. The specific scheme is as follows: the self-repairing composite material surface film with the automatic deicing function comprises commercialized epoxy resin, a curing agent, insulating heat-conducting fillers, a toughening agent, a carrier and a metal resistance wire coated with a repairing agent, and the self-repairing composite material surface film with the automatic deicing function is prepared by a hot melting blending, grinding and dispersing, vacuum kneading and hot calendering composite film method. The application first designs and prepares an insulating heat-conducting repairing agent coated metal resistance wire, and a self-repairing composite material surface film with an automatic deicing function is prepared by controlling the structure and proportion of the epoxy resin, the structure and composition of the insulating heat-conducting fillers, the structure and composition of the insulating heat-conducting repairing agent layer, the structure of the repairing agent coated metal resistance wire and the structure and proportion of the toughening agent.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of automatic deicing self-repairing composite material surface film, and particularly relates to a preparation method and application of a self-repairing composite material surface film with automatic deicing function. BACKGROUND

[0002] Fiber reinforced resin-based composite materials have excellent mechanical properties, fatigue resistance, corrosion resistance, and light weight, and have been widely used in the field of aerospace. In addition, with the development of composite material technology, structural parts made of composite materials have been used as main load-bearing components. The extensive use of light composite materials greatly reduces the cost-effectiveness ratio of aircraft, saves a large amount of fuel, and makes a contribution to environmental protection. For example, the use of composite materials in foreign advanced civil aircraft is more than 50%, and China's independently developed civil aircraft also uses a large number of composite material manufactured parts. With the rapid development of unmanned aerial vehicles in recent years, in order to improve manufacturing efficiency and improve the performance of unmanned aerial vehicles, composite materials are used in a higher proportion in the field of unmanned aerial vehicles, and some models are entirely made of composite materials. The extensive use of composite materials is accompanied by the use of a large number of composite material surface films. When the aircraft is in the cold season or in a specific flight area, the wings or fuselage of the aircraft and other positions are prone to icing, and the presence of ice layers seriously affects the aerodynamic performance of the aircraft and increases the flight weight. The icing of the rotor of a helicopter can cause a decrease in lift and damage to the balance of the rotor. If icing is not removed in time, the aircraft may not be able to perform flight tasks, or even cause a major flight accident, which can cause great harm to the safety of the aircraft and passengers. Therefore, active icing identification and automatic deicing of aircraft in the composite material era are very important to the safety of the aircraft and passengers. At present, the design and use of the aircraft deicing system are independent of the composite material surface film, which has the following problems: first, it increases the manufacturing time and economic cost, second, it generally cannot start the automatic deicing function according to the icing condition, and third, the structure and function cannot be self-repaired after being damaged, and the deicing function is lost. SUMMARY

[0003] The application aims to solve the problems of the prior art that the surface film for composite materials does not have automatic deicing function, cannot be self-repaired after being damaged, has a complex repair process, and has high repair cost, and further provides a preparation method and application of a self-repairing composite material surface film with automatic deicing function.

[0004] In order to achieve the above-mentioned purpose, the application adopts the following technical solutions:

[0005] The application discloses a preparation method of a self-repairing composite material surface film with an automatic deicing function, and the self-repairing composite material surface film with the automatic deicing function comprises commercialized epoxy resin, a curing agent, insulating and heat-conducting filler I, a toughening agent, a carrier and a repair agent coated metal resistance wire, and is prepared by a hot melt blending, grinding dispersion, vacuum kneading and hot calendering composite film forming method.

[0006] Specifically, the method comprises the following steps:

[0007] Step one, preparation of a hot melt blend

[0008] The bisphenol A type epoxy resin is heated and stirred in a hot melt dispersing machine, and after being heated to 160 DEG C, methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer is added; the mixture is melt-stirred in the hot melt dispersing machine until the methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer is completely melted in the bisphenol A type epoxy resin to form a uniform and transparent hot melt blend B, wherein the temperature of the hot melt dispersing machine is kept at 160-190 DEG C;

[0009] Step two, preparation of a ground blend resin

[0010] The insulating and heat-conducting filler I, the curing agent, the core-shell rubber particles and the bisphenol F epoxy resin and the brominated bisphenol A epoxy resin are mixed by stirring to form a coarse mixture, and the coarse mixture is ground and dispersed on a ceramic three-roll grinding machine for 3-5 times to obtain a ground blend resin C;

[0011] Step three, the hot melt blend B is preheated to 80-90 DEG C in a blast drying oven, the heating temperature of a vacuum kneader is set to 60-70 DEG C, and the preheating is performed for 4-6 h; the preheated hot melt blend B, the ground blend resin C, the phenolic type epoxy resin, the tetrafunctional epoxy AG-80 and EPOLEAD GT401, the epoxidized liquid rubber and the aminated liquid rubber are added into the preheated vacuum kneader, and are kneaded for 15-30 min; in the process, vacuum is drawn to exhaust to obtain a surface film size, wherein the temperature of the size is controlled to be 60-80 DEG C, and the vacuum degree is controlled to be-0.095 MPa to-0.090 MPa;

[0012] Step four, the surface film size is subjected to calendering film forming on a double roll calendering device and is compounded with the carrier and the repair agent coated metal resistance wire to obtain a self-repairing composite material surface film with the automatic deicing function which is not cured.

[0013] Further, the preparation method of the repair agent coated metal resistance wire is: vacuum drying ethylene-methacrylic acid copolymer and ethylene-acrylic acid copolymer particles at 70-80°C for 24-48h, vacuum drying polysulfoctanic acid at 40-60°C for 24-48h; uniformly mixing the dried ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer and polysulfoctanic acid, and then extruding and granulating by a double screw extruder to obtain granules A; vacuum drying the granules A at 40-60°C for 24-48h, uniformly mixing with the insulating and heat-conducting filler II, and then stretching and extruding by a double screw extruder to obtain a repair agent wire, and the repair agent coated metal resistance wire is printed by a coaxial 3D printer, taking the metal resistance wire as the center material and the repair agent wire as the outer coating material.

[0014] Further, the bisphenol A type epoxy resin, bisphenol F epoxy resin, brominated bisphenol A epoxy resin, phenolic type epoxy resin, tetrafunctional epoxy AG-80 and EPOLEAD GT401 are all commercialized epoxy resins, and the mass ratio is 100:10-30:5-10:3-5:5-10:5-10.

[0015] Further, the curing agent contains a mixture of one or more of dicyandiamide, m-xylylenediamine, diaminodiphenylmethane and diaminodiphenyl sulfone, and the molar ratio of -NH groups to epoxy groups in the curing agent is 1:1.

[0016] Further, the insulating and heat-conducting filler I includes alumina nanospheres, aluminum nitride nanosheets and boron nitride nanosheets, and the mass ratio is 100:50-70:20-50, and the insulating and heat-conducting filler I accounts for 10-20% of the total mass of the epoxy resin.

[0017] Further, the methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer, epoxidized liquid rubber, aminated liquid rubber and core-shell rubber particles are all toughening agents, and the mass ratio is 100:5-10:5-10:5-10, and the amount of the toughening agent accounts for 10-15% of the total mass of the epoxy resin.

[0018] Further, the mass ratio of the ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer and polysulfoctanic acid is: 100:50-70:10-20;

[0019] Further, the thickness of the repair agent layer in the repair agent coated metal resistance wire is 0.1-0.3mm, the metal resistance wire is a nickel-chromium alloy resistance wire, the diameter is 0.1-0.2mm, and the resistivity is 10-50Ω / m.

[0020] Further, the insulating and heat-conducting filler II includes aluminum nitride nanosheets and boron nitride nanosheets, and the mass ratio of the two is 100:30-50, and the amount of the insulating and heat-conducting filler II accounts for 10-20% of the mass of the repair agent.

[0021] Further, the carrier is a polyester fabric or a non-woven fabric, and the mass per unit area is 15-20 g / m2.

[0022] The application of the self-repairing composite material surface film with automatic deicing function prepared by the preparation method comprises the following steps: co-curing the uncured self-repairing composite material surface film with automatic deicing function with a prepreg, then connecting an internal metal wire with an icing automatic identification sensor, a signal converter, an intelligent switch device and a power supply in sequence to form an electric circuit, in addition, the two ends of the internal metal wire are connected with the positive and negative poles of the power supply, so that an automatic identification-automatic deicing self-repairing system is formed, the system can control the input power of the power supply by the intelligent switch according to the automatic identification of the icing thickness, and automatic electric heating deicing of the metal wire is realized.

[0023] Compared with the prior art, the self-repairing composite material surface film with automatic deicing function has the following beneficial effects:

[0024] The self-repairing composite material surface film with automatic deicing function is prepared by controlling the structure and proportion of the epoxy resin, the structure and composition of the insulating and heat-conducting filler I, the structure and composition of the insulating and heat-conducting repair agent layer, the structure of the repair agent coated metal resistance wire, and the structure and proportion of the toughening agent. In the resin system of the surface film, the insulating and heat-conducting filler I is introduced to improve the thermal conductivity of the matrix resin and the strength and hardness of the surface film. The insulating and heat-conducting repair agent coated metal resistance wire is used as a heating device, which can protect the metal resistance wire and improve its fatigue resistance, and the insulating and heat-conducting repair agent layer can quickly conduct Joule heat and isolate the metal resistance wire from the composite material to avoid potential corrosion caused by the potential difference between the metal wire and the composite material. The repair agent layer endows the surface film with excellent interlayer self-repairing performance, improves the interfacial bonding performance and durability between the surface film and the composite material. After co-curing the surface film with the prepreg, the internal metal wire is connected with the icing automatic identification sensor, the signal converter, the intelligent switch device and the power supply in sequence to form an electric circuit, in addition, the two ends of the internal metal wire are connected with the positive and negative poles of the power supply, so that an automatic identification-automatic deicing self-repairing system is formed. The input power of the power supply is controlled by the intelligent switch according to the automatic identification of the icing thickness, and deicing is realized. The combination of the above design ideas endows the composite material surface film of the application with self-repairing performance and excellent deicing function. In addition, based on the above synergistic effect, the prepared deicing self-repairing composite material surface film has excellent adhesion and surface hardness, the interfacial repair efficiency of the surface film is greater than or equal to 90%, and the interfacial repair frequency is greater than or equal to 10 times. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 is a structure diagram of the repair agent coated metal resistance wire.

[0026] Figure 2 is the automatic identification-automatic deicing self-repair system structure schematic diagram; DETAILED DESCRIPTION

[0027] The technical solutions in the present application will be described clearly and completely in combination with the drawings and embodiments. Obviously, the described embodiments are only a part of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work are within the protection scope of the present application.

[0028] Embodiment 1:

[0029] A preparation method of a self-repairing composite material surface film with automatic deicing function, the self-repairing composite material surface film with automatic deicing function comprises commercial epoxy resin, curing agent, insulating and heat-conducting filler I, toughening agent, carrier and metal resistance wire coated with repair agent, and the self-repairing composite material surface film with automatic deicing function is prepared by hot melt blending, grinding dispersion, vacuum kneading and hot calendering composite film forming method.

[0030] The specific preparation method is as follows:

[0031] Step one, preparation of hot melt blend

[0032] The bisphenol A type epoxy resin is heated and stirred in a hot melt dispersing machine, and after being heated to 160 DEG C, methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer is added. The mixture is melt-stirred in the hot melt dispersing machine until the methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer is completely melted in the bisphenol A type epoxy resin to form a uniform transparent hot melt blend B, wherein the temperature of the hot melt dispersing machine is kept at 160 DEG C.

[0033] Step two, preparation of ground blend resin

[0034] The insulating and heat-conducting filler I, the curing agent, the core-shell rubber particles and the bisphenol F epoxy resin, and the brominated bisphenol A epoxy resin are mixed by stirring to form a coarse mixture, and the coarse mixture is ground and dispersed on a ceramic three-roll grinder for 3 times to obtain a ground blend resin C.

[0035] Step three,

[0036] The hot melt blend B is preheated to 80℃ in a blast drying oven, the vacuum kneader heating temperature is set to 60℃, and preheated for 4h. The preheated hot melt blend B, ground blend resin C, phenolic epoxy resin, tetra-functional epoxy AG-80 and EPOLEAD GT401, epoxidized liquid rubber, and aminated liquid rubber are added to the preheated vacuum kneader, kneaded for 15min, and vacuum exhaust during the kneading process to obtain a surface film adhesive, wherein the adhesive temperature is controlled at 60℃, and the vacuum degree is controlled at-0.095MPa.

[0037] Step four,

[0038] The surface film adhesive is rolled into a film on a double roller rolling equipment and is compounded with the carrier and the repair agent coated metal resistance wire to obtain an uncured self-repairing composite surface film with automatic deicing function.

[0039] Further, the preparation method of the repair agent coated metal resistance wire is as follows: ethylene-methacrylic acid copolymer and ethylene-acrylic acid copolymer particles are vacuum dried at 70℃ for 24h, and polythioctic acid is vacuum dried at 40℃ for 24h. The dried ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer and polythioctic acid are uniformly mixed and then extruded by a double screw extruder to obtain granules A. The granules A are vacuum dried at 40℃ for 24h, then uniformly mixed with the insulating and heat conducting filler II, and then stretched and extruded by a double screw extruder to obtain a repair agent wire. The repair agent coated metal resistance wire is printed by a coaxial 3D printer, with the metal resistance wire as the center material and the repair agent wire as the outer coating material.

[0040] Further, the bisphenol A type epoxy resin, bisphenol F epoxy resin, brominated bisphenol A epoxy resin, phenolic epoxy resin, tetra-functional epoxy AG-80 and EPOLEAD GT401 are all commercial epoxy resins, and the mass ratio is 100:10:5:3:5:5.

[0041] Further, the curing agent comprises dicyandiamide and m-xylylenediamine, and the mass ratio of dicyandiamide to m-xylylenediamine is 100:15, and the molar ratio of -NH groups to epoxy groups in the curing agent is 1:1.

[0042] Further, the insulating and heat conducting filler I comprises alumina nanospheres, aluminum nitride nanosheets and boron nitride nanosheets, and the mass ratio is 100:50:20, and the insulating and heat conducting filler I accounts for 10% of the total mass of the epoxy resin.

[0043] Further, the methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer, epoxidized liquid rubber, aminated liquid rubber and core-shell rubber particles are all toughening agents, and the mass ratio is 100:5:5:5, and the amount of the toughening agent accounts for 10% of the total mass of the epoxy resin.

[0044] Further, the carrier is polyester fabric or non-woven fabric, and the mass per unit area is 15 g / m2.

[0045] Further, the mass ratio of the ethylene-methacrylic acid copolymer, the ethylene-acrylic acid copolymer and the lipoic acid is 100:50:10.

[0046] Further, the insulating and heat-conducting filler II includes aluminum nitride nanosheets and boron nitride nanosheets, and the mass ratio of the two is 100:30, and the amount of the insulating and heat-conducting filler II accounts for 10% of the mass of the repairing agent.

[0047] Further, the thickness of the repairing agent layer in the metal resistance wire is 0.1 mm, the metal resistance wire is a nickel-chromium alloy resistance wire, the diameter is 0.1 mm, and the resistivity is 10 Ω / m.

[0048] The application of the self-repairing composite material surface film with automatic deicing function prepared by the preparation method, specifically, after the uncured self-repairing composite material surface film with automatic deicing function is co-cured with a prepreg, the internal metal wire is connected with an icing automatic identification sensor, a signal converter, an intelligent switch device and a power supply in sequence to form an electric circuit, in addition, the two ends of the internal metal wire are connected with the positive and negative poles of the power supply, so that an automatic identification-automatic deicing self-repairing system is formed. The intelligent switch is controlled according to the automatic identification of the icing thickness to control the power input of the power supply, so that the metal wire is automatically electrically heated to remove ice.

[0049] Embodiment 2:

[0050] A preparation method of a self-repairing composite material surface film with automatic deicing function, the self-repairing composite material surface film with automatic deicing function includes commercial epoxy resin, curing agent, insulating and heat-conducting filler I, toughening agent, carrier and metal resistance wire coated with repairing agent, and the self-repairing composite material surface film with automatic deicing function is prepared by a hot melt blending, grinding and dispersing, vacuum kneading and hot calendering composite film method.

[0051] The specific preparation method is as follows:

[0052] Step one, preparation of hot melt blend

[0053] The bisphenol A type epoxy resin is heated and stirred in a hot melt dispersing machine, methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer is added after heating to 160℃, and the mixture is melt-stirred in the hot melt dispersing machine until the methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer is completely melted in the bisphenol A type epoxy resin to form a uniform transparent hot melt blend B, wherein the temperature of the hot melt dispersing machine is kept at 190℃;

[0054] Step two, preparation of the ground blend resin

[0055] The insulating and heat-conducting filler I, the curing agent, the core-shell rubber particles, and the bisphenol F epoxy resin, the brominated bisphenol A epoxy resin were mixed by stirring to form a coarse mixture, and the coarse mixture was ground and dispersed on a ceramic three-roll grinder for 5 times to obtain the ground blend resin C;

[0056] Step three,

[0057] The hot melt blend B was preheated to 90℃ in a forced air drying oven, and the temperature of the vacuum kneader was set to 70℃ and preheated for 6h. The preheated hot melt blend B, the ground blend resin C, the phenolic epoxy resin, the tetrafunctional epoxy AG-80 and EPOLEAD GT401, the epoxidized liquid rubber, and the aminated liquid rubber were added to the preheated vacuum kneader, and kneaded for 30min. The temperature of the glue was controlled at 80℃, and the vacuum degree was controlled at-0.090MPa during the kneading process to obtain the surface film glue.

[0058] Step four,

[0059] The surface film glue was rolled into a film on a double roller rolling equipment and was compounded with the carrier and the repair agent coated metal resistance wire to obtain the uncured self-repairing composite surface film with automatic deicing function.

[0060] Further, the preparation method of the repair agent coated metal resistance wire is as follows: the ethylene-methacrylic acid copolymer and ethylene-acrylic acid copolymer particles were vacuum dried at 80℃ for 48h, and the polysulphoxides were vacuum dried at 60℃ for 48h. The dried ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer and polysulphoxides were mixed uniformly and then were extruded and granulated by a double screw extruder to obtain the granules A. The granules A were vacuum dried at 60℃ for 48h, and then were mixed uniformly with the insulating and heat-conducting filler II and were stretched and extruded by a double screw extruder to obtain the repair agent wire. The repair agent coated metal resistance wire was printed by a coaxial 3D printer, and the metal resistance wire was used as the center material, and the repair agent wire was used as the outer coating material.

[0061] Further, the bisphenol A type epoxy resin, the bisphenol F epoxy resin, the brominated bisphenol A epoxy resin, the phenolic epoxy resin, the tetrafunctional epoxy AG-80 and EPOLEAD GT401 are all commercial epoxy resins, and the mass ratio is 100:30:10:5:10:10.

[0062] Further, the curing agent is dicyandiamide, and the molar ratio of -NH group to epoxy group in the curing agent is 1:1.

[0063] Further, the insulating and heat-conducting filler I includes aluminum oxide nanospheres, aluminum nitride nanosheets, and boron nitride nanosheets, with a mass ratio of 100:70:50, and the insulating and heat-conducting filler I accounts for 20% of the total mass of the epoxy resin.

[0064] Further, the methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer, the epoxidized liquid rubber, the aminated liquid rubber, and the core-shell rubber particle are all toughening agents, with a mass ratio of 100:10:10:10, and the toughening agent accounts for 15% of the total mass of the epoxy resin.

[0065] Further, the carrier is a polyester fabric or a non-woven fabric, with a unit area mass of 20 g / m2.

[0066] Further, the ethylene-methacrylic acid copolymer, the ethylene-acrylic acid copolymer, and the polysulfoctanic acid have a mass ratio of 100:70:20.

[0067] Further, the insulating and heat-conducting filler II includes aluminum nitride nanosheets and boron nitride nanosheets, with a mass ratio of 100:50, and the insulating and heat-conducting filler II accounts for 20% of the mass of the repair agent.

[0068] Further, the thickness of the repair agent layer in the repair agent-coated metal resistance wire is 0.3 mm, the metal resistance wire is a nickel-chromium alloy resistance wire, with a diameter of 0.2 mm and a resistivity of 50 Ω / m.

[0069] The application of the self-repairing composite material surface film with automatic deicing function prepared by the preparation method, specifically, after the uncured self-repairing composite material surface film with automatic deicing function is co-cured with a prepreg, the internal metal wire is connected with an icing automatic identification sensor, a signal converter, an intelligent switch device, and a power supply in sequence to form an electric circuit, in addition, the two ends of the internal metal wire are connected with the positive and negative electrodes of the power supply, thereby forming an automatic identification-automatic deicing self-repairing system. The intelligent switch is controlled according to the automatic identification of the icing thickness to control the power input of the power supply, thereby realizing automatic electric heating deicing of the metal wire.

[0070] Embodiment 3:

[0071] A preparation method of a self-repairing composite material surface film with automatic deicing function, the self-repairing composite material surface film with automatic deicing function including commercialized epoxy resin, a curing agent, an insulating and heat-conducting filler I, a toughening agent, a carrier, and a metal resistance wire coated with a repair agent, the self-repairing composite material surface film with automatic deicing function being prepared by a hot melt blending, grinding and dispersing, vacuum kneading, and hot calendering composite film forming method.

[0072] The specific preparation method is as follows:

[0073] Step one, preparation of hot melt blend

[0074] The bisphenol A type epoxy resin is heated and stirred in a hot melt disperser. After heating to 160℃, methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer is added. The mixture is melt-stirred in the hot melt disperser until the methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer is completely melted in the bisphenol A type epoxy resin to form a uniform transparent hot melt blend B, wherein the temperature of the hot melt disperser is maintained at 175℃.

[0075] Step two, preparation of ground blend resin

[0076] The insulating and heat-conducting filler I, curing agent, core-shell rubber particles, and bisphenol F epoxy resin, brominated bisphenol A epoxy resin are mixed by stirring to form a coarse mixture. The coarse mixture is ground and dispersed on a ceramic three-roll grinding machine for 4 times to obtain a ground blend resin C.

[0077] Step three,

[0078] The hot melt blend B is preheated to 85℃ in a forced air drying oven. The heating temperature of the vacuum kneader is set to 65℃ and preheated for 5h. The preheated hot melt blend B, ground blend resin C, phenolic epoxy resin, tetrafunctional epoxy AG-80 and EPOLEAD GT401, epoxidized liquid rubber, and aminated liquid rubber are added to the preheated vacuum kneader, and kneaded for 23min. During the kneading process, vacuum is applied to exhaust the air to obtain a surface film adhesive, wherein the adhesive temperature is controlled at 70℃ and the vacuum degree is controlled at -0.093MPa.

[0079] Step four,

[0080] The surface film adhesive is rolled into a film on a double roll rolling equipment and is compounded with a carrier and a repair agent coated metal resistance wire to obtain an uncured self-repairing composite surface film with automatic deicing function.

[0081] Further, the preparation method of the repair agent coated metal resistance wire is as follows: ethylene-methacrylic acid copolymer and ethylene-acrylic acid copolymer particles are vacuum dried at 75℃ for 36h, and polythioctic acid is vacuum dried at 50℃ for 36h. The dried ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer and polythioctic acid are mixed uniformly and then extruded by a twin-screw extruder to obtain granules A. The granules A are vacuum dried at 50℃ for 36h, then mixed uniformly with the insulating and heat-conducting filler II, and then stretched and extruded by a twin-screw extruder to obtain a repair agent wire. The repair agent coated metal resistance wire is printed by a coaxial 3D printer, taking the metal resistance wire as the center material and the repair agent wire as the outer coating material.

[0082] Further, the bisphenol A type epoxy resin, bisphenol F epoxy resin, brominated bisphenol A epoxy resin, phenolic type epoxy resin, tetrafunctional epoxy AG-80 and EPOLEAD GT401 are all commercial epoxy resins, and the mass ratio is 100:20:7.5:4:7.5:7.5.

[0083] Further, the curing agent comprises dicyandiamide and diaminodiphenyl sulfone, and the mass ratio of dicyandiamide and diaminodiphenyl sulfone is 100:10, and the molar ratio of -NH groups to epoxy groups in the curing agent is 1:1.

[0084] Further, the insulating and heat-conducting filler I comprises alumina nanospheres, aluminum nitride nanosheets and boron nitride nanosheets, and the mass ratio is 100:60:35, and the insulating and heat-conducting filler I accounts for 15% of the total mass of the epoxy resin.

[0085] Further, the methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer, epoxidized liquid rubber, aminated liquid rubber and core-shell rubber particles are all toughening agents, and the mass ratio is 100:7.5:7.5:7.5, and the amount of the toughening agent accounts for 12.5% of the total mass of the epoxy resin.

[0086] Further, the carrier is a polyester fabric or a non-woven fabric, and the unit area mass is 17.5g / m2.

[0087] Further, the ethylene methacrylate copolymer, ethylene acrylic acid copolymer and polysulfoctanic acid have a mass ratio of 100:60:15.

[0088] Further, the insulating and heat-conducting filler II comprises aluminum nitride nanosheets and boron nitride nanosheets, and the mass ratio of the two is 100:40, and the amount of the insulating and heat-conducting filler II accounts for 15% of the mass of the repair agent.

[0089] Further, the thickness of the repair agent layer in the metal resistance wire coated with the repair agent is 0.2mm, the metal resistance wire is a nickel-chromium alloy resistance wire, the diameter is 0.15mm, and the resistivity is 50Ω / m.

[0090] The application of the self-repairing composite material surface film with automatic deicing function prepared by the preparation method, specifically: after the uncured self-repairing composite material surface film with automatic deicing function is co-cured with a prepreg, the internal metal wire is connected with an icing automatic identification sensor, a signal converter, an intelligent switch device and a power supply in sequence to form an electric circuit, in addition, the two ends of the internal metal wire are connected with the positive and negative electrodes of the power supply, respectively, so as to form an automatic identification-automatic deicing self-repairing system. The intelligent switch is controlled according to the automatic identification of the icing thickness to control the input power of the power supply, so as to realize automatic electric heating deicing of the metal wire.

[0091] Furthermore, it should be understood that although the specification is described in terms of embodiments, not every embodiment includes every feature or implementation described herein. The specification can include implicit combinations of explicitly mentioned features and / or implicit combinations of implicitly mentioned features. Such combinations are also expressly included within the scope of the specification and an embodiment.

Claims

1. A method for preparing a self-healing composite material surface film having an automatic de-icing function, characterized by, The method comprises the following steps: Step one, preparation of hot melt blend The bisphenol A type epoxy resin is heated and stirred in a hot melt disperser. After heating to 160℃, methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer is added. The mixture is melt-stirred in the hot melt disperser until the methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer is completely melted in the bisphenol A type epoxy resin to form a uniform transparent hot melt blend B, wherein the temperature of the hot melt disperser is maintained at 160-190℃. Step two, preparation of ground blend resin The insulating and heat-conducting filler I, curing agent, core-shell rubber particles, bisphenol F epoxy resin, and brominated bisphenol A epoxy resin are mixed by stirring to form a coarse mixture, and the coarse mixture is ground uniformly to obtain a ground blend resin C. Step three, the hot melt blend B is preheated to 80-90℃ in a forced air drying oven. The heating temperature of the vacuum kneader is set to 60-70℃, and preheated for 4-6h. The preheated hot melt blend B, ground blend resin C, phenolic epoxy resin, tetrafunctional epoxy AG-80, EPOLEAD GT401, epoxidized liquid rubber, and aminated liquid rubber are added to the preheated vacuum kneader, and kneaded for 15-30 min. During the kneading process, vacuum is applied to exhaust to obtain a surface film adhesive, wherein the adhesive temperature is controlled at 60-80℃, and the vacuum degree is controlled at -0.095MPa to -0.090MPa. Step four, the surface film adhesive is film-pressed on a double-roller calendering equipment to form a film and is compounded with a carrier and a repair agent coated metal resistance wire to obtain an uncured self-repairing composite surface film with automatic deicing function. The preparation method of the repair agent coated metal resistance wire is as follows: ethylene-methacrylic acid copolymer and ethylene-acrylic acid copolymer particles are vacuum dried at 70-80℃ for 24-48h, and polythioctic acid is vacuum dried at 40-60℃ for 24-48h. The dried ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer, and polythioctic acid are mixed uniformly and then extruded by a twin-screw extruder to obtain granules A. The granules A are vacuum dried at 40-60℃ for 24-48h, then mixed uniformly with an insulating and heat-conducting filler II, and then stretched and extruded by a twin-screw extruder to obtain a repair agent wire. The repair agent coated metal resistance wire is printed by a coaxial 3D printer, taking the metal resistance wire as the center material and the repair agent wire as the outer coating material.

2. The method of claim 1, wherein: The bisphenol A type epoxy resin, bisphenol F epoxy resin, brominated bisphenol A epoxy resin, phenolic epoxy resin, tetrafunctional epoxy AG-80, and EPOLEAD GT401 are all commercial epoxy resins, and the mass ratio is 100:10-30:5-10:3-5:5-10:5-10.

3. The method of claim 1, wherein: The curing agent comprises a mixture of one or more of dicyandiamide, m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenyl sulfone, and the molar ratio of -NH groups to epoxy groups in the curing agent is 1:

1.

4. The method of claim 1, wherein: The insulating and heat-conducting filler I comprises alumina nanospheres, aluminum nitride nanosheets and boron nitride nanosheets, and the mass ratio is 100:50-70:20-50, and the insulating and heat-conducting filler I accounts for 10-20% of the total mass of the epoxy resin.

5. The method of claim 1, wherein: The methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer, epoxidized liquid rubber, aminated liquid rubber and core-shell rubber particles are all toughening agents, and the mass ratio is 100:5-10:5-10:5-10, and the amount of the toughening agent accounts for 10-15% of the total mass of the epoxy resin.

6. The method of claim 1, wherein: The mass ratio of the ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer and polysulfoctanic acid is 100:50-70:10-20.

7. The method of claim 1, wherein: The thickness of the repair agent layer in the repair agent coated metal resistance wire is 0.1-0.3mm, the metal resistance wire is a nickel-chromium alloy resistance wire, the diameter is 0.1-0.2mm, and the resistivity is 10-50Ω / m.

8. The method of claim 1, wherein: The insulating and heat-conducting filler II comprises aluminum nitride nanosheets and boron nitride nanosheets, and the mass ratio is 100:30-50, and the amount of the insulating and heat-conducting filler II accounts for 10-20% of the mass of the repair agent.

9. Use of a self-healing composite surface film having a self- deicing function produced by the production method according to any one of claims 1 to 8, characterized in that: After the uncured surface film of the self-repairing composite material with the automatic deicing function is co-cured with the prepreg, the internal metal wire is connected with the ice automatic identification sensor, the signal converter, the intelligent switch device and the power supply in sequence to form an electric circuit, in addition, the two ends of the internal metal wire are connected with the positive and negative poles of the power supply, respectively, so that the automatic identification-automatic deicing self-repairing system is formed, the system can control the intelligent switch to regulate the power input according to the automatic identification of the ice thickness, and the automatic electric heating deicing of the metal wire is realized.

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