Magnetic heating deicing material, preparation method thereof and application of deicing coating

Abstract

The invention provides a magnetic heating deicing material as well as a preparation method and deicing coating application thereof. The magnetic heating deicing material comprises an inner core and a coating layer on the surface of the inner core, the inner core comprises an iron-manganese alloy doped with rare earth metal; the coating layer comprises reduced graphene oxide modified by an amino silane coupling agent. The magnetic heating deicing material has a low Curie point and can enable a magnetic heating deicing coating to rapidly increase the surface temperature in a low-temperature environment on one hand, and has excellent conductivity and can further increase the heating value of the coating on the other hand, so that the deicing effect is enhanced, the efficient deicing effect is achieved, and the service life of the coating is prolonged. And the magnetic heating deicing material can actively prevent the formation of an ice layer in a low-temperature environment, has dual functions of ice prevention and deicing, and can be prepared at low cost and in a large scale.

Description

Technical Field

[0001] The present invention belongs to the technical field of magnetic heating materials, and relates to a magnetic heating de-icing material, a preparation method thereof, and an application of a de-icing coating. Background Art

[0002] The problem of ice coating on transmission lines has always been a major challenge that needs to be solved urgently in the power industry. In recent years, with the frequent occurrence of extreme climate events, the current situation of ice coating on transmission lines has become increasingly severe. Ice coating can lead to accidents such as conductor galloping, insulator flashover, line overload, and even wire breakage and tower collapse of transmission lines, posing a huge threat to the safe and stable operation of the power system.

[0003] In order to address the problem of ice coating on transmission lines, a variety of de-icing technologies have been developed in the prior art. Traditional de-icing methods include mechanical de-icing, thermal de-icing, and coating de-icing, etc. The mechanical de-icing method removes ice coating through physical means, such as the vibration method and the pulley scraping method, but there are problems of low safety and efficiency. The thermal de-icing method melts the ice coating by heating the conductor, for example, using high-voltage direct current or alternating current to heat the conductor, but this method has high energy consumption and may cause damage to the conductor.

[0004] The de-icing coating can be directly sprayed or coated on the surface of the transmission line, which is convenient for construction and does not require complex equipment and operations. Among them, the magnetic heating coating utilizes the magnetic property of a low Curie point magnetic material when the temperature is lower than its Curie point. Under the action of the power frequency magnetic field generated by the transmission line, a strong magnetic induction intensity can be generated, resulting in hysteresis loss and eddy current loss, thereby generating heat and achieving the de-icing effect. This characteristic enables the magnetic heating coating to automatically respond in a low-temperature environment and will not cause additional energy consumption when de-icing is not required, having the advantage of energy conservation. Although the currently developed iron-nickel alloy low Curie material (20°C to 80°C) has potential, its Curie temperature is still much higher than the ideal value of 0°C, and there are bottlenecks in processing performance, and further optimization of material design and preparation process is required.

[0005] For example, CN101638549A discloses a heat-generating functional coating for preventing ice on transmission line conductors. A low Curie temperature ferromagnetic filler with heat-generating function under the action of the alternating magnetic field of high-voltage conductors is added to the coating and coated on the outer surface of the conductor or conductor single wire. According to the energy loss of the low Curie temperature ferromagnetic material under the action of the alternating magnetic field of high-voltage conductors, heat is released to prevent or delay the icing of freezing rain on the surface of the conductor.

[0006] For example, CN110699609A discloses a doped ferromagnetic alloy, ferromagnetic alloy wire anti-icing material with a Curie temperature near zero degrees (273 ± 10K), good processing performance, and high heat generation, and a preparation method thereof, but there are problems of high production cost and difficulty in large-scale production.

[0007] Although the low Curie point magnetic heating coating shows great potential in deicing transmission lines, this technology is still in the development stage with limited technological maturity. Existing magnetic heating coatings still have problems such as high Curie temperature, high production costs, difficulty in large-scale production and application, poor conductivity, limited deicing effect, and inability to prevent icing. Summary of the Invention

[0008] The purpose of the present invention is to provide a magnetic heating deicing material, its preparation method and the application of the deicing coating. On the one hand, the magnetic heating deicing material has a low Curie point, enabling the magnetic heating deicing coating to rapidly increase the surface temperature in a low-temperature environment. On the other hand, it has excellent conductivity, which can further increase the heat generation of the coating, thereby enhancing the deicing effect to achieve an efficient deicing effect. It is particularly suitable for large-scale production at a relatively low cost and can also actively prevent the formation of ice layers in a low-temperature environment, having the dual functions of anti-icing and deicing.

[0009] To achieve the purpose of this invention, the following technical solutions are adopted:

[0010] In the first aspect, the present invention provides a magnetic heating deicing material, which includes a core and a coating layer on the surface of the core;

[0011] The core includes an iron-manganese alloy doped with rare earth metals;

[0012] The coating layer includes reduced graphene oxide modified by an amino silane coupling agent.

[0013] On the one hand, the present invention uses an iron-manganese alloy doped with rare earth metals as the core. Among them, the doped rare earth metals can introduce additional magnetic moments into the iron-manganese alloy, interact with the magnetic moments of the iron-manganese alloy, thereby changing the overall magnetism of the magnetic heating deicing material, reducing the Curie point of the magnetic heating deicing material, enabling the coating to rapidly increase the surface temperature in a low-temperature environment, melting ice and snow, and achieving an efficient deicing effect. On the other hand, the present invention uses reduced graphene oxide modified by an amino silane coupling agent as the coating layer, which improves the conductivity and stability of the magnetic heating deicing material, further increases the heat generation of the material, thereby enhancing the deicing effect and stability. In addition, the magnetic heating deicing material of the present invention can not only be used for deicing, but also actively prevent the formation of ice layers in a low-temperature environment, delaying the occurrence of icing, and having the dual functions of anti-icing and deicing.

[0014] The coating layer of the present invention includes reduced graphene oxide modified by an amino silane coupling agent. Among them, the modification by the amino silane coupling agent can improve the hydrophobicity of the magnetic heating deicing material, thereby providing the dispersibility of the material, avoiding material agglomeration, enabling the magnetic heating deicing material to be evenly distributed in the deicing coating, and ensuring the performance of the magnetic heating deicing material in the deicing coating.

[0015] Preferably, the content of the coating layer in the magnetic heat - generating de - icing material is 0.5 wt% to 10 wt%. For example, it can be 0.5 wt%, 1.5 wt%, 2.5 wt%, 3.5 wt%, 4.5 wt%, 5.5 wt%, 6.5 wt%, 7.5 wt%, 8.5 wt%, 9.5 wt% or 10 wt%, but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0016] The content of the coating layer in the magnetic heat - generating de - icing material of the present invention affects the conductivity, de - icing effect, stability and dispersibility of the material. Preferably, within a specific content range, it can ensure that the material has properties such as a low Curie temperature and high calorific value.

[0017] Preferably, in the rare - earth - metal - doped iron - manganese alloy, the content of the rare - earth metal is 3 wt% to 8 wt%. For example, it can be 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt% or 8 wt%, but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0018] The content of the rare - earth metal introduced into the iron - manganese alloy in the present invention affects the magnetic moment of the magnetic heat - generating de - icing material. If too little rare - earth metal is introduced, the effect of reducing the Curie point of the material will decline. However, if too much rare - earth metal is introduced, the magnetic domain structure of the iron - manganese matrix will be damaged.

[0019] Preferably, the Curie temperature of the rare - earth - metal - doped iron - manganese alloy is - 15°C to 10°C. For example, it can be - 15°C, - 13°C, - 11°C, - 9°C, - 7°C, - 5°C, - 3°C, - 1°C, 1°C, 3°C, 5°C, 7°C, 9°C or 10°C, but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0020] The rare - earth - metal - doped iron - manganese alloy of the present invention has a relatively low Curie point, enabling the magnetic heat - generating de - icing material to respond in a low - temperature environment, so that the magnetic heat - generating de - icing material can not only de - ice but also prevent icing.

[0021] Preferably, the rare - earth - metal - doped iron - manganese alloy includes iron, manganese, nickel and rare - earth metal.

[0022] The iron - manganese alloy of the present invention also includes a small amount of nickel. Exemplarily, in the iron - manganese alloy, the mass ratio of iron, manganese and nickel is 1:(0.2 - 0.5):(0.01 - 0.2). For example, it can be 1:0.2:0.01, 1:0.3:0.05, 1:0.4:0.1, 1:0.5:0.15 or 1:0.5:0.2, but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0023] Preferably, the rare earth metal includes any one or a combination of at least two of Nd, Ce, Gd, Dy, or La.

[0024] In a second aspect, the present invention provides a method for preparing the magnetic heat-generating deicing material as described in the first aspect. The preparation method includes the following steps:

[0025] (1) Using electrochemical deposition to coat graphene oxide on the surface of the inner core to obtain an inner core coated with graphene oxide;

[0026] (2) Reducing the inner core coated with graphene oxide in step (1) to obtain an inner core coated with reduced graphene oxide;

[0027] (3) Modifying the inner core coated with reduced graphene oxide in step (2) with an amino silane coupling agent to obtain the magnetic heat-generating deicing material.

[0028] The present invention uses electrochemical deposition to coat graphene oxide, which can tightly coat graphene oxide on the surface of the inner core. Then, the graphene oxide is reduced and modified. The amino group in the amino silane coupling agent used for modification can bond with the functional groups on the surface of the reduced graphene oxide, enabling the reduced graphene oxide to graft the silane coupling agent, thereby obtaining the magnetic heat-generating deicing material with a specific structure and composition of the present invention.

[0029] Preferably, the method for preparing the inner core in step (1) includes the following steps:

[0030] (i) Mixing, compacting, sintering, and tempering a matrix material and a rare earth metal in sequence to obtain an alloy, wherein the matrix material includes iron powder, manganese powder, and nickel powder;

[0031] (ii) Atomizing and granulating the alloy obtained in step (i) to obtain the inner core in step (1).

[0032] Preferably, the rare earth metal in step (i) is 0.5 wt% - 5 wt% of the mass of the matrix material. For example, it can be 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%, but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0033] Preferably, the mass ratio of the iron powder, manganese powder, and nickel powder in step (i) is 1:(0.2 - 0.5):(0.01 - 0.2). For example, it can be 1:0.2:0.01, 1:0.3:0.05, 1:0.4:0.1, 1:0.5:0.15, or 1:0.5:0.2, but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0034] Preferably, the method of sequentially mixing the matrix material and the rare earth metal in step (i) includes mechanical mixing, specifically using a ball mill for mechanical alloying, and the grinding time is 4 - 8 h, for example, it can be 4 h, 5 h, 6 h, 7 h or 8 h, but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0035] Preferably, the particle size of the mixed powder obtained by sequentially mixing the matrix material and the rare earth metal in step (i) is 250 mesh - 350 mesh, for example, it can be 250 mesh, 270 mesh, 290 mesh, 310 mesh, 330 mesh or 350 mesh, but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0036] Preferably, the cold isostatic pressing forming method is used for the pressing and forming in step (i), and the pressure for the pressing and forming is 500 MPa - 700 MPa, for example, it can be 500 MPa, 550 MPa, 600 MPa, 650 MPa or 700 MPa, but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0037] Preferably, the temperature for the sintering treatment in step (i) is 1100 °C - 1500 °C, for example, it can be 1100 °C, 1200 °C, 1300 °C, 1400 °C or 1500 °C, and the time is 2 h - 4 h, for example, it can be 2 h, 2.5 h, 3 h, 3.5 h or 4 h, but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0038] Preferably, the temperature for the tempering treatment in step (i) is 400 °C - 500 °C, for example, it can be 400 °C, 420 °C, 440 °C, 460 °C, 480 °C or 500 °C, and the time is 1 h - 2 h, for example, it can be 1 h, 1.25 h, 1.5 h, 1.75 h or 2 h, but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0039] The sintering treatment and the tempering treatment in the present invention are carried out in a vacuum, or are respectively and independently carried out in a mixed gas of any one or at least two of argon, nitrogen, hydrogen or carbon monoxide.

[0040] Preferably, the alloy in step (i) is atomized and granulated by vacuum plasma.

[0041] Preferably, the atomizing and granulating by vacuum plasma includes the following steps:

[0042] Preheat the alloy in step (i), then melt the alloy by plasma, and then atomize the melted alloy to obtain the core.

[0043] Specifically, in the present invention, vacuum plasma is used for atomization granulation. The alloy is preheated, and the preheated and melted alloy is put into a plasma generator. The plasma jet is used to further heat and melt the alloy to form fine metal droplets. In the molten state, the molten metal is atomized by a high-speed gas flow passing through a nozzle. The metal droplets are rapidly condensed in the atomization chamber to form spherical alloy powder. Then, a cyclone separator is used to collect the atomized alloy powder, and screening is carried out to obtain spherical powder that meets the particle size requirements.

[0044] Preferably, the temperature of the preheating is 400°C to 500°C. For example, it can be 400°C, 420°C, 440°C, 460°C, 480°C or 500°C, but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0045] Preferably, the temperature of the melting is 1500°C to 2000°C. For example, it can be 1500°C, 1600°C, 1700°C, 1800°C, 1900°C or 2000°C, but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0046] Preferably, the flow rate of the carrier gas during atomization is 2 L / min to 6 L / min. For example, it can be 2 L / min, 3 L / min, 4 L / min, 5 L / min or 6 L / min. The pressure of the atomization is 0.3 Mpa to 0.6 MPa. For example, it can be 0.3 MPa, 0.4 MPa, 0.5 MPa or 0.6 MPa, but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0047] Preferably, the core is spherical and / or quasi-spherical, and the particle size is 0.5 μm to 5 μm. For example, it can be 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm or 5 μm, but is not limited to the listed values. Other unlisted values within the numerical range are equally applicable.

[0048] Preferably, the step of coating graphene oxide on the surface of the core by the electrochemical deposition method in step (1) includes the following steps:

[0049] Prepare an electroplating solution by mixing deionized water, metal salt, graphene oxide and the core;

[0050] Place the electroplating solution in an electroplating bath. After connecting the electroplating electrode to a DC power supply and turning on the power, electroplating is carried out. After the electroplating is completed, filtration, washing and drying are carried out to obtain the core coated with graphene oxide.

[0051] Preferably, in the electroplating solution, the mass fraction of the metal salt is 15wt% - 25wt%, for example, it can be 15wt%, 17.5wt%, 20wt%, 22.5wt% or 25wt%, the mass fraction of graphene oxide is 2wt% - 6wt%, for example, it can be 2wt%, 3wt%, 4wt%, 5wt% or 6wt%, and the mass fraction of the core is 5wt% - 10wt%, for example, it can be 5wt%, 6.25wt%, 7.5wt%, 8.75wt% or 10wt%, but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0052] Preferably, the metal salt includes sodium sulfate.

[0053] Preferably, the DC voltage for power-on is 2V - 4V, for example, it can be 2V, 2.5V, 3V, 3.5V or 4V, and the DC current is 5A - 15A, for example, it can be 5A, 7.5A, 10A, 12.5A or 15A, but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0054] Preferably, the electroplating time is 3min - 60min, for example, it can be 3min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0055] Preferably, in the core coated with graphene oxide, the thickness of the graphene oxide coating layer is 0.3345nm - 10nm, for example, it can be 0.3345nm, 0.5nm, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm or 10nm, but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0056] Preferably, the reduction temperature in step (2) is 600°C - 1000°C, for example, it can be 600°C, 700°C, 800°C, 900°C or 1000°C, and the time is 1h - 4h, for example, it can be 1h, 1.5h, 2h, 2.5h, 3h, 3.5h or 4h, but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0057] Preferably, the reduction in step (2) is carried out in a hydrogen and nitrogen atmosphere.

[0058] Preferably, the modification in step (3) includes the following steps:

[0059] The hydrolysis solution of the aminosilane coupling agent is mixed with the dispersion liquid containing the core coated with reduced graphene oxide, followed by solid-liquid separation, washing, and drying to obtain the magnetic heat-generating deicing material.

[0060] Preferably, the core coated with reduced graphene oxide is added to absolute ethanol and ultrasonically dispersed for 10 - 20 min, such as 10 min, 12 min, 14 min, 16 min, 18 min, or 20 min, to obtain the dispersion liquid containing the core coated with reduced graphene oxide.

[0061] Preferably, the aminosilane coupling agent is added to deionized water and absolute ethanol to obtain the hydrolysis solution of the aminosilane coupling agent.

[0062] Preferably, the mass of the aminosilane coupling agent is 1 wt% - 5 wt% of the mass of the core coated with reduced graphene oxide, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt%, but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0063] Preferably, the temperature for mixing the hydrolysis solution of the aminosilane coupling agent with the dispersion liquid containing the core coated with reduced graphene oxide is 60°C - 80°C, such as 60°C, 65°C, 70°C, 75°C, or 80°C, and the time is 4 h - 8 h, such as 4 h, 5 h, 6 h, 7 h, or 8 h, but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0064] Preferably, the aminosilane coupling agent includes 3-aminopropyltriethoxysilane and / or 3-aminopropyltrimethoxysilane.

[0065] In a third aspect, the present invention provides an anti-icing coating, and the magnetic heat-generating anti-icing coating includes the magnetic heat-generating anti-icing material as described in the first aspect, or includes the magnetic heat-generating anti-icing material prepared by the preparation method as described in the second aspect.

[0066] Preferably, the anti-icing coating further includes a resin material.

[0067] Preferably, by weight, the coating for preparing the anti-icing coating includes 20 - 40 parts of resin material, such as 20 parts, 25 parts, 30 parts, 35 parts, or 40 parts, 20 - 50 parts of magnetic heat-generating anti-icing material, such as 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, or 50 parts, 10 - 20 parts of solvent, such as 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, or 20 parts, and 3 - 5 parts of additives, such as 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts, but not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0068] Preferably, the solvent includes any one or a combination of at least two of ethyl acetate, butyl acetate, acetone, toluene, or xylene.

[0069] Preferably, the resin material includes fluorocarbon resin, such as polyvinylidene fluoride and / or polytetrafluoroethylene.

[0070] Preferably, the additives include a leveling agent and an antifoaming agent.

[0071] Preferably, the leveling agent is a silicone leveling agent, which has excellent surface activity and smoothness, can significantly reduce the surface tension of the coating, and thus improve the fluidity and leveling property of the coating.

[0072] Preferably, the silicone leveling agent includes polydimethylsiloxane, polymethylalkylsiloxane, organically modified polysiloxane, etc., and the addition amount is 0.5% - 1.5% (calculated based on the total mass of the coating). For example, it can be 0.5%, 1.0%, or 1.5%, but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0073] Preferably, the antifoaming agent is a silicone antifoaming agent, which has little influence on the stability of the coating system and can maintain the defoaming effect within a wide temperature and pH value range; the antifoaming agent can be, for example, BYK - 024.

[0074] Preferably, the mass ratio of the antifoaming agent to the leveling agent is 1:(1 - 2). For example, it can be 1:1, 1:1.5, or 1:2, but is not limited to the listed values, and other unlisted values within the numerical range are equally applicable.

[0075] Compared with the prior art, the present invention has the following beneficial effects:

[0076] The magnetic heating de - icing material of the present invention has a low Curie point, can rapidly increase the surface temperature of the transmission line in a low - temperature environment, melt ice and snow, and achieve an efficient de - icing effect; the coating layer in the magnetic heating de - icing material can also improve the conductivity of the coating, further increase the calorific value of the coating, thereby enhancing the de - icing effect. Moreover, the magnetic heating de - icing material of the present invention can not only be used for de - icing, but also actively prevent the formation of ice layers in a low - temperature environment, delay the occurrence of icing, and has the dual functions of anti - icing and de - icing. Therefore, the magnetic heating de - icing material of the present invention has the advantages of environmental friendliness, low energy consumption, and long - term reliable performance, and the magnetic heating de - icing material can be produced at low cost and on a large scale. Detailed Embodiments

[0077] The technical solution of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0078] The information of some raw materials used in the following examples and comparative examples is as follows:

[0079] Iron powder, purity 99.9%, Hunan Fujia Technology Co., Ltd.;

[0080] Manganese powder, purity 99.99%, Hunan Fujia Technology Co., Ltd.;

[0081] Nickel powder, purity 99.9%, Hunan Fujia Technology Co., Ltd.;

[0082] Neodymium powder, purity 99.9%, Zhuozhou Yourong New Materials Technology Co., Ltd.;

[0083] 3-Aminopropyltriethoxysilane, Guangzhou Yuanda New Materials Co., Ltd.

[0084] Example 1

[0085] This example provides a magnetic heating deicing material, which includes a core and a coating on the surface of the core. The core includes a neodymium-doped iron-manganese alloy, and the coating includes reduced graphene oxide modified by an amino silane coupling agent;

[0086] In the magnetic heating deicing material, the content of the coating is 3 wt%, and in the neodymium-doped iron-manganese alloy, the content of neodymium is 4 wt%;

[0087] The preparation method of the magnetic heating deicing material includes the following steps:

[0088] (1) Neodymium-doped iron-manganese alloy:

[0089] Mix 2 kg of iron powder, 0.6 kg of manganese powder, 0.2 kg of nickel powder, and 0.1 kg of neodymium powder. Among them, the neodymium powder is 3.6 wt% of the total mass of the iron powder, manganese powder, and nickel powder, and the mass ratio of the iron powder, manganese powder, and nickel powder is 1:0.3:0.1. Use a ball mill for mechanical alloying and grind for 5 hours; then, adopt a cold isostatic pressing method to press the mixed powder into a shape at a pressure of 550 MPa; finally, sinter in an argon atmosphere, the sintering temperature is 1300 °C, and sinter for 3 hours; after sintering, perform a tempering treatment at 400 °C in an argon atmosphere for 2 hours, and naturally cool to room temperature to obtain a neodymium-doped iron-manganese alloy;

[0090] (2) Plasma atomization granulation:

[0091] Preheat the neodymium-doped iron-manganese alloy at 500 °C, put the preheated alloy into a plasma generator, and use a plasma jet to further heat it to 1500 °C to melt the alloy; in the molten state, atomize the molten metal through a nozzle with a carrier gas flow rate of 4 L / min; the metal droplets rapidly condense in the atomization chamber to form spherical neodymium-doped iron-manganese alloy powder; use a cyclone separator to collect the atomized neodymium-doped iron-manganese alloy powder, screen the generated powder, and obtain spherical powder with a particle size of 3 μm;

[0092] (3) Primary modification (coating magnetic powder with graphene oxide):

[0093] Prepare an electroplating solution using 16.75 kg of deionized water, 4.5 kg of sodium sulfate, 1.25 kg of graphene oxide, and 2.5 kg of neodymium-doped iron-manganese alloy powder. Among them, the mass fraction of sodium sulfate in the electroplating solution is 18 wt%, the mass fraction of graphene oxide is 5 wt%, and the mass fraction of neodymium-doped iron-manganese alloy powder is 10 wt%; place the electroplating solution in an electroplating tank, connect the electroplating electrode to a DC power supply, and perform electroplating at a voltage of 5 V and a current of 10.5 A for 30 min; after electroplating, filter, wash, and dry to obtain graphene oxide-neodymium-doped iron-manganese alloy powder with a coating thickness of 3 nm.

[0094] Reduce the graphene oxide-neodymium-doped iron-manganese alloy powder at a temperature of 800 °C for 3 h in an atmosphere of hydrogen and nitrogen with a volume ratio of 6:4 to obtain reduced graphene oxide-neodymium-doped iron-manganese alloy powder.

[0095] (4) Secondary modification (graft modification of rGO-magnetic powder):

[0096] Add 100 g of reduced graphene oxide-neodymium-doped iron-manganese alloy powder to 1000 g of absolute ethanol and perform ultrasonic dispersion for 15 min to obtain a dispersion of reduced graphene oxide-neodymium-doped iron-manganese alloy powder; add 3 g of 3-aminopropyltriethoxysilane to deionized water and absolute ethanol to obtain a silane coupling agent hydrolysis solution, where the mass of 3-aminopropyltriethoxysilane is 3 wt% of the mass of the reduced graphene oxide-neodymium-doped iron-manganese alloy powder; slowly drip the hydrolysis solution into the dispersion, heat to 65 °C, stir and react for 6 hours, filter, wash, and vacuum dry to obtain the magnetic heat-generating deicing material.

[0097] This embodiment also provides a magnetic heat-generating deicing coating, and the preparation method of the magnetic heat-generating deicing coating includes the following steps:

[0098] Mix 25 g of fluorocarbon resin (specifically polyvinylidene fluoride), 40 g of the magnetic heat - generating de - icing material described in this example, 10 g of acetone, and 3 g of additives (specifically 2 g of polymethylalkylsiloxane and 1 g of BYK - 024), stir - mix them, spray - coat the surface of the wire insulation layer to form a de - icing coating, and then spray - coat the insulation layer.

[0099] Example 2

[0100] This example provides a magnetic heat - generating de - icing material. The magnetic heat - generating de - icing material includes a core and a coating layer on the surface of the core. The core includes a neodymium - doped iron - manganese alloy, and the coating layer includes reduced graphene oxide modified by an amino - silane coupling agent;

[0101] In the magnetic heat - generating de - icing material, the content of the coating layer is 2 wt%, and in the neodymium - doped iron - manganese alloy, the content of neodymium is 6 wt%;

[0102] The preparation method of the magnetic heat - generating de - icing material includes the following steps:

[0103] (1) Neodymium - doped iron - manganese alloy:

[0104] Mix 2 kg of iron powder, 0.4 kg of manganese powder, 0.1 kg of nickel powder, and 0.125 kg of neodymium powder. Among them, the neodymium powder is 5 wt% of the total mass of the iron powder, manganese powder, and nickel powder, and the mass ratio of the iron powder, manganese powder, and nickel powder is 1:0.2:0.05. Use a ball mill for mechanical alloying and grind for 6 hours; then, adopt a cold isostatic pressing method to press the mixed powder into a shape at a pressure of 700 MPa; finally, sinter in an argon atmosphere, the sintering temperature is 1500 °C, and sinter for 3 hours; after sintering, conduct a tempering treatment at 450 °C in an argon atmosphere for 2 hours, and naturally cool to room temperature to obtain a neodymium - doped iron - manganese alloy;

[0105] (2) Plasma atomization granulation:

[0106] Preheat the neodymium - doped iron - manganese alloy at 450 °C, put the pre - heated alloy into a plasma generator, and use a plasma jet to further heat it to 1800 °C to melt the alloy; in the molten state, use a carrier gas flow rate of 6 L / min to atomize the molten metal through a nozzle; the metal droplets quickly condense in the atomization chamber to form spherical neodymium - doped iron - manganese alloy powder; use a cyclone separator to collect the atomized neodymium - doped iron - manganese alloy powder, and screen the generated powder to obtain spherical powder with a particle size of 1 μm;

[0107] (3) Primary modification (coating magnetic powder with graphene oxide):

[0108] 16.75 kg of deionized water, 5.5 kg of sodium sulfate, 1.5 kg of graphene oxide and 1.25 kg of neodymium-doped iron-manganese alloy powder are used to prepare an electroplating solution. Among them, the mass fraction of sodium sulfate in the electroplating solution is 22 wt%, the mass fraction of graphene oxide is 6 wt%, and the mass fraction of neodymium-doped iron-manganese alloy powder is 5 wt%. The electroplating solution is placed in an electroplating tank, and the electroplating electrode is connected to a DC power supply. Electroplating is carried out at a voltage of 4 V and a current of 5 A for 60 min. After electroplating, filtration, washing and drying are carried out to obtain neodymium-doped iron-manganese alloy powder coated with graphene oxide with a thickness of 6 nm.

[0109] The neodymium-doped iron-manganese alloy powder coated with graphene oxide is reduced at a temperature of 600 °C for 4 h in an atmosphere of hydrogen and nitrogen with a volume ratio of 6:4 to obtain reduced graphene oxide-neodymium-doped iron-manganese alloy powder.

[0110] (4) Secondary modification (graft modification of rGO-magnetic powder):

[0111] 100 g of the reduced graphene oxide-neodymium-doped iron-manganese alloy powder is added to 1000 g of absolute ethanol and ultrasonically dispersed for 20 min to obtain a dispersion of the reduced graphene oxide-neodymium-doped iron-manganese alloy powder. 1 g of 3-aminopropyltriethoxysilane is added to deionized water and absolute ethanol to obtain a hydrolyzed solution of the silane coupling agent. Among them, the mass of 3-aminopropyltriethoxysilane is 1 wt% of the mass of the reduced graphene oxide-neodymium-doped iron-manganese alloy powder. The hydrolyzed solution is slowly added dropwise to the dispersion, heated to 80 °C, and stirred and reacted for 4 hours. After filtration, washing and vacuum drying, the magnetic heat-generating deicing material is obtained.

[0112] This embodiment also provides a magnetic heat-generating deicing coating. The preparation method of the magnetic heat-generating deicing coating includes the following steps:

[0113] 40 g of fluorocarbon resin (specifically polyvinylidene fluoride), 20 g of the magnetic heat-generating deicing material of this embodiment, 15 g of acetone, and 4 g of additives (specifically 2 g of polydimethylsiloxane and 2 g of BYK-024) are stirred and mixed, sprayed on the surface of the wire insulation layer to form a deicing coating, and then the insulation layer is sprayed.

[0114] Example 3

[0115] This embodiment provides a magnetic heat-generating deicing material. The magnetic heat-generating deicing material includes a core and a coating layer on the surface of the core. The core includes neodymium-doped iron-manganese alloy, and the coating layer includes reduced graphene oxide modified with an amino silane coupling agent;

[0116] The content of the coating layer in the magnetic heat-generating deicing material is 5 wt%, and in the neodymium-doped iron-manganese alloy, the content of neodymium is 0.5 wt%;

[0117] The preparation method of the magnetic heat - generating de - icing material comprises the following steps:

[0118] (1) Neodymium - doped iron - manganese alloy:

[0119] Mix 2 kg of iron powder, 1 kg of manganese powder, 0.4 kg of nickel powder, and 0.017 kg of neodymium powder. Among them, the neodymium powder is 0.5 wt% of the total mass of the iron powder, manganese powder, and nickel powder, and the mass ratio of the iron powder, manganese powder, and nickel powder is 1:0.5:0.2. Use a ball mill for mechanical alloying and grind for 8 hours. Then, adopt the cold isostatic pressing method to press the mixed powder into a shape at a pressure of 500 MPa. Finally, sinter in an argon atmosphere at a sintering temperature of 1100 °C for 3 hours. After sintering, conduct a tempering treatment at 500 °C in an argon atmosphere for 1 hour and cool naturally to room temperature to obtain the neodymium - doped iron - manganese alloy;

[0120] (2) Plasma atomization granulation:

[0121] Preheat the neodymium - doped iron - manganese alloy at 400 °C, put the pre - heated alloy into a plasma generator, and use a plasma jet to further heat it to 2000 °C to melt the alloy. In the molten state, use a carrier gas flow rate of 2 L / min to atomize the molten metal through a nozzle. The metal droplets are quickly condensed in the atomization chamber to form spherical neodymium - doped iron - manganese alloy powder. Use a cyclone separator to collect the atomized neodymium - doped iron - manganese alloy powder, and screen the generated powder to obtain spherical powder with a particle size of 5 μm;

[0122] (3) Primary modification (coating magnetic powder with graphene oxide):

[0123] Prepare an electroplating solution using 16.75 kg of deionized water, 5.25 kg of sodium sulfate, 0.5 kg of graphene oxide, and 2.5 kg of neodymium - doped iron - manganese alloy powder. Among them, the mass fraction of sodium sulfate in the electroplating solution is 21 wt%, the mass fraction of graphene oxide is 2 wt%, and the mass fraction of neodymium - doped iron - manganese alloy powder is 10 wt%. Place the electroplating solution in an electroplating bath, connect the electroplating electrode to a DC power supply, and conduct electroplating at a voltage of 2 V and a current of 15 A for 10 min. After electroplating, filter, wash, and dry to obtain graphene oxide - neodymium - doped iron - manganese alloy powder with a coating thickness of 1 nm.

[0124] Reduce the graphene oxide - neodymium - doped iron - manganese alloy powder in an atmosphere of hydrogen and nitrogen with a volume ratio of 6:4 at a temperature of 1000 °C for 1 h to obtain reduced graphene oxide - neodymium - doped iron - manganese alloy powder.

[0125] (4) Secondary modification (graft - modification of rGO - magnetic powder):

[0126] 100 g of reduced graphene oxide-doped neodymium iron manganese alloy powder was added to 1000 g of absolute ethanol and ultrasonically dispersed for 10 min to obtain a dispersion of reduced graphene oxide-doped neodymium iron manganese alloy powder; 5 g of 3-aminopropyltriethoxysilane was added to deionized water and absolute ethanol to obtain a hydrolysis solution of the silane coupling agent, where the mass of 3-aminopropyltriethoxysilane was 5 wt% of the mass of the reduced graphene oxide-doped neodymium iron manganese alloy powder; the hydrolysis solution was slowly added dropwise to the dispersion, heated to 60 °C, and stirred and reacted for 8 h. After filtration, washing, and vacuum drying, the magnetic heating de-icing material was obtained.

[0127] This example also provides a magnetic heating de-icing coating, and the preparation method of the magnetic heating de-icing coating includes the following steps:

[0128] 20 g of fluorocarbon resin (specifically polyvinylidene fluoride), 50 g of the magnetic heating de-icing material of this example, 20 g of acetone, and 5 g of additives (specifically 3 g of polydimethylsiloxane and 2 g of BYK-024) were stirred and mixed, sprayed on the surface of the wire insulation layer to form a de-icing coating, and then an insulating layer was sprayed.

[0129] Example 4

[0130] This example provides a magnetic heating de-icing material. Except that in step (1) of its preparation method, 2 kg of iron powder, 0.8 kg of manganese powder, 0.4 kg of nickel powder, and 0.1 kg of neodymium powder were mixed to make the obtained magnetic heating de-icing material adaptively change, the rest were the same as in Example 1.

[0131] This example also provides a magnetic heating de-icing coating. Except that the magnetic heating de-icing material of this example was used in its preparation method, the rest were the same as in Example 1.

[0132] Example 5

[0133] This example provides a magnetic heating de-icing material. Except that in step (3) of its preparation method, 16 kg of deionized water, 5.0 kg of sodium sulfate, 1.5 kg of graphene oxide, and 2.5 kg of doped neodymium iron manganese alloy powder were used to prepare an electroplating solution to make the obtained magnetic heating de-icing material adaptively change, the rest were the same as in Example 1.

[0134] This example also provides a magnetic heating de-icing coating. Except that the magnetic heating de-icing material of this example was used in its preparation method, the rest were the same as in Example 1.

[0135] Example 6

[0136] This embodiment provides a magnetic heat - generating de - icing material. Except that in step (4) of its preparation method, 4.5 g of 3 - aminopropyltriethoxysilane is added to deionized water and absolute ethanol, which makes the obtained magnetic heat - generating de - icing material have an adaptive change, the rest is the same as in Example 1.

[0137] This embodiment also provides a magnetic heat - generating de - icing coating. Except that the magnetic heat - generating de - icing material described in this embodiment is used in its preparation method, the rest is the same as in Example 1.

[0138] Example 7

[0139] This embodiment provides a magnetic heat - generating de - icing material, which is the same as that in Example 1.

[0140] This embodiment also provides a magnetic heat - generating de - icing coating. Except that 45 g of the magnetic heat - generating de - icing material described in this embodiment is used in its preparation method, the rest is the same as in Example 1.

[0141] Example 8

[0142] This embodiment provides a magnetic heat - generating de - icing material. Except that in step (1) of its preparation method, 2 kg of iron powder, 0.6 kg of manganese powder, 0.2 kg of nickel powder, and 0.0028 kg of neodymium powder are mixed, where the neodymium powder is 0.1 wt% of the total mass of the iron powder, manganese powder, and nickel powder, which makes the obtained magnetic heat - generating de - icing material have an adaptive change, the rest is the same as in Example 1.

[0143] This embodiment also provides a magnetic heat - generating de - icing coating. Except that the magnetic heat - generating de - icing material described in this embodiment is used in its preparation method, the rest is the same as in Example 1.

[0144] Example 9

[0145] This embodiment provides a magnetic heat - generating de - icing material. Except that in step (1) of its preparation method, 2 kg of iron powder, 0.6 kg of manganese powder, 0.2 kg of nickel powder, and 0.196 kg of neodymium powder are mixed, where the neodymium powder is 7 wt% of the total mass of the iron powder, manganese powder, and nickel powder, which makes the obtained magnetic heat - generating de - icing material have an adaptive change, the rest is the same as in Example 1.

[0146] This embodiment also provides a magnetic heat - generating de - icing coating. Except that the magnetic heat - generating de - icing material described in this embodiment is used in its preparation method, the rest is the same as in Example 1.

[0147] Example 10

[0148] This embodiment provides a magnetic heating de-icing material. Except that in step (3) of its preparation method, 16.75 kg of deionized water, 5.5 kg of sodium sulfate, 0.25 kg of graphene oxide and 2.5 kg of neodymium-doped iron-manganese alloy powder are used to prepare an electroplating solution, wherein the mass fraction of sodium sulfate in the electroplating solution is 22 wt%, the mass fraction of graphene oxide is 1 wt%, and the mass fraction of neodymium-doped iron-manganese alloy powder is 10 wt%, resulting in an adaptable change in the obtained magnetic heating de-icing material, the rest is the same as in Embodiment 1.

[0149] This embodiment also provides a magnetic heating de-icing coating. Except that the magnetic heating de-icing material described in this embodiment is used in its preparation method, the rest is the same as in Embodiment 1.

[0150] Embodiment 11

[0151] This embodiment provides a magnetic heating de-icing material. Except that in step (3) of its preparation method, 16.75 kg of deionized water, 4.25 kg of sodium sulfate, 2 kg of graphene oxide and 2 kg of neodymium-doped iron-manganese alloy powder are used to prepare an electroplating solution, wherein the mass fraction of sodium sulfate in the electroplating solution is 17 wt%, the mass fraction of graphene oxide is 8 wt%, and the mass fraction of neodymium-doped iron-manganese alloy powder is 8 wt%, resulting in an adaptable change in the obtained magnetic heating de-icing material, the rest is the same as in Embodiment 1.

[0152] This embodiment also provides a magnetic heating de-icing coating. Except that the magnetic heating de-icing material described in this embodiment is used in its preparation method, the rest is the same as in Embodiment 1.

[0153] Comparative Example 1

[0154] This comparative example provides a magnetic heating de-icing material. In the preparation method of the magnetic heating de-icing material, neodymium powder is not added in step (1), so that the magnetic heating de-icing material is not doped with rare earth metals, and the rest is the same as in Embodiment 1.

[0155] This comparative example also provides a magnetic heating de-icing coating. Except that the magnetic heating de-icing material described in this comparative example is used in its preparation method, the rest is the same as in Embodiment 1.

[0156] Comparative Example 2

[0157] This comparative example provides a magnetic heating de-icing material. In the preparation method of the magnetic heating de-icing material, step (4) is not carried out, so that the surface coating layer of the magnetic heating de-icing material is reduced graphene oxide, and the rest is the same as in Embodiment 1.

[0158] This comparative example also provides a magnetic exothermic deicing coating, which is the same as Example 1 except that the magnetic exothermic deicing material described in this comparative example is used in its preparation method.

[0159] Comparative Example 3

[0160] This comparative example provides a magnetic exothermic deicing material. In the preparation method of the magnetic exothermic deicing material, step (3) and step (4) are not performed, so that the magnetic exothermic deicing material does not contain a coating layer. The rest is the same as Example 1.

[0161] This comparative example also provides a magnetic exothermic deicing coating, which is the same as Example 1 except that the magnetic exothermic deicing material described in this comparative example is used in its preparation method.

[0162] The magnetic heating and deicing coatings obtained in the above embodiments and comparative examples were tested for their saturation magnetic induction intensity using the method of GB / T 13012 "Measurement Method for DC Magnetic Properties of Soft Magnetic Materials", and the Curie temperature was tested using GB / T 43870.2-2024 "Measurement Method for Curie Temperature of Magnetic Materials Part 2: Soft Magnetic Materials". The test results are shown in Table 1:

[0163] Table 1

[0164]

[0165]

[0166] From Table 1 we can see that:

[0167] It can be seen from Example 1 and Comparative Example 1 that the additional magnetic moment introduced by doping rare earth metals in the present invention can further improve the saturation magnetic induction intensity of the material and reduce the Curie temperature; it can be seen from Example 1 and Comparative Example 2 that the present invention uses aminosilane coupling agent to graft and modify the reduced graphene oxide in the coating layer, which can improve the dispersibility of the material in the magnetic heat-generating deicing coating, avoid particle agglomeration, and ensure the effect of the magnetic heat-generating deicing material; it can be seen from Example 1 and Comparative Example 3 that the provision of the coating layer in the material of the present invention can further improve the deicing effect; it can be seen from Example 1 and Examples 8-9 that the present invention preferably incorporates a specific content of rare earth metal to ensure the interaction between the rare earth metal and the iron-manganese alloy, improve the saturation magnetic induction intensity of the material, and reduce the Curie temperature; it can be seen from Example 1 and Examples 10-11 that the content of the coating layer in the magnetic heat-generating deicing material of the present invention will affect the performance of the magnetic heat-generating deicing coating.

[0168] The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A magnetic heat - generating de - icing material, characterized in that, The magnetic heat - generating de - icing material includes a core and a coating layer on the surface of the core; The core includes an iron - manganese alloy doped with rare - earth metals; The coating layer includes reduced graphene oxide modified by an amino - silane coupling agent.

2. The magnetic heat - generating de - icing material according to claim 1, characterized in that, In the magnetic heat - generating de - icing material, the content of the coating layer is 0.5wt% - 10wt%; Preferably, in the iron - manganese alloy doped with rare - earth metals, the content of the rare - earth metal is 3wt% - 8wt%; Preferably, the Curie temperature of the iron - manganese alloy doped with rare - earth metals is - 15°C - 10°C; Preferably, the iron - manganese alloy doped with rare - earth metals includes iron, manganese, nickel, and rare - earth metals; Preferably, the rare - earth metal includes any one or a combination of at least two of Nd, Ce, Gd, Dy, or La.

3. A preparation method of the magnetic heat - generating de - icing material as described in claim 1 or 2, characterized in that, The preparation method includes the following steps: (1) Using the electrochemical deposition method to coat graphene oxide on the surface of the core to obtain a core coated with graphene oxide; (2) Reducing the core coated with graphene oxide in step (1) to obtain a core coated with reduced graphene oxide; (3) Using an amino - silane coupling agent to modify the core coated with reduced graphene oxide in step (2) to obtain the magnetic heat - generating de - icing material.

4. The preparation method according to claim 3, wherein The method for preparing the core in step (1) includes the following steps: (i) Mixing, compacting, sintering, and tempering a matrix material and rare - earth metals in sequence to obtain an alloy, where the matrix material includes iron powder, manganese powder, and nickel powder; (ii) Atomizing and granulating the alloy obtained in step (i) to obtain the core in step (1).

5. The preparation method according to claim 4, wherein The rare - earth metal in step (i) is 0.5wt% - 5wt% of the mass of the matrix material; Preferably, the mass ratio of the iron powder, manganese powder, and nickel powder in step (i) is 1:(0.2 - 0.5):(0.01 - 0.2); Preferably, the temperature of the sintering treatment in step (i) is 1100°C - 1500°C, and the time is 2h - 4h; Preferably, the temperature of the tempering treatment in step (i) is 400°C - 500°C, and the time is 1h - 2h.

6. The preparation method according to claim 4 or 5, characterized in that, The alloy in step (i) is atomized and granulated using vacuum plasma; Preferably, the atomizing and granulating using vacuum plasma includes the following steps: Preheating the alloy in step (i), then melting the alloy using plasma, and then atomizing the melted alloy to obtain the core; Preferably, the core is spherical and / or quasi - spherical, and the particle size is 0.5μm - 5μm.

7. The preparation method according to claim 3 or 4, characterized in that, The step of coating graphene oxide on the surface of the core using the electrochemical deposition method in step (1) includes the following steps: Preparing an electroplating solution by mixing deionized water, metal salt, graphene oxide, and the core; Placing the electroplating solution in an electroplating bath, connecting the electroplating electrode to a DC power supply and energizing for electroplating; after electroplating, filtering, washing, and drying to obtain a core coated with graphene oxide; Preferably, in the electroplating solution, the mass fraction of the metal salt is 15wt% - 25wt%, the mass fraction of graphene oxide is 2wt% - 6wt%, and the mass fraction of the core is 5wt% - 10wt%; Preferably, in the graphene oxide-coated inner core, the thickness of the graphene oxide coating layer is 0.3345 nm to 10 nm.

8. The preparation method according to claim 3 or 4, characterized in that, The reduction temperature in step (2) is 600° C. to 1000° C. and the time is 1 h to 4 h; Preferably, the reduction in step (2) is carried out in a hydrogen and nitrogen atmosphere; Preferably, the modification in step (3) comprises the following steps: The hydrolyzate of the aminosilane coupling agent is mixed with the dispersion containing the core coated with reduced graphene oxide, and then solid-liquid separation, washing and drying are performed to obtain the magnetic exothermic deicing material; Preferably, the mass of the aminosilane coupling agent is 1wt%-5wt% of the mass of the core coated with reduced graphene oxide.

9. An anti-icing coating, characterized in that, The deicing coating comprises the magnetic exothermic deicing material as claimed in claim 1 or 2, or comprises the magnetic exothermic deicing material prepared by the preparation method according to any one of claims 3-8.

10. The de-icing coating according to claim 9, characterized in that, The deicing coating further comprises a resin material; Preferably, the coating for preparing the deicing coating comprises, by weight, 20 to 40 parts of resin material, 20 to 50 parts of magnetic exothermic deicing material, 10 to 20 parts of solvent and 3 to 5 parts of auxiliary agent.

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