CN110885257A - Carbon/carbon composite material surface functional coating and preparation method thereof - Google Patents
Carbon/carbon composite material surface functional coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carbon/carbon composite material surface functional coating, which comprises a transition bonding layer arranged on the surface of a carbon/carbon composite material, an antioxidant structural layer arranged on the surface of the transition bonding layer, and an electromagnetic functional layer arranged on the surface of the antioxidant structural layer; the electromagnetic function layer is formed by a plurality of first electromagnetic function block groups and second electromagnetic function block groups which are arranged periodically to form a chessboard pattern. When the electromagnetic waves irradiate the surface of the material, the amplitudes of the reflected waves of the electromagnetic waves at the two chessboard units are close, the phases are completely opposite, the amplitudes and the phases are just offset in the normal direction, the energy directly reflected back by the electromagnetic waves is greatly reduced, the low detectability of the C/C composite material is endowed, and the electromagnetic function improvement of the thinning and high efficiency of the surface of the carbon/carbon composite material can be realized.
Description
Technical Field
The invention belongs to the technical field of inorganic materials, and particularly relates to a carbon/carbon composite material surface functional coating and a preparation method thereof.
Background
The carbon/carbon composite material (C/C) is a carbon-based composite material taking carbon fibers as reinforcements, and the theoretical density is only 2.2g/cm3Compared with high-temperature ceramics and high-temperature alloys, the high-temperature ceramic material has the advantage of light specific gravity, can keep high strength, high modulus, good fracture toughness, wear resistance and the like in a high-temperature inert environment, and is one of the most ideal high-temperature structural materials. Because the carbon-based composite material is completely composed of a single carbon element, high-temperature easy oxidation is the bottleneck of the application of the C/C composite material as a thermal structural member. Most of the current research focuses on the technology of the oxidation resistant coating on the surface of the C/C composite material. The functional requirements of low scattering property of electromagnetic wave are provided for high-temperature structural materials by parts such as a tail nozzle, an inner cone, turbine engine blades, a regulating sheet and the like of the aircraft engine. The realization of the low scattering function of the electromagnetic wave must depend on the absorption or deflection of the electromagnetic wave, and the C/C composite material is a good electric conductor, can generate direct reflection under the irradiation of the electromagnetic wave and is easy to be identified by radar. So far, few reports are made on the technical research of electromagnetic functional coatings of C/C composite materials at home and abroad. The Wells international corporation in America reports that the C/C composite material can be applied to high-temperature parts of a wing leading edge, a nose and a tail, can inhibit infrared radiation and has low detectability of radar target characteristics, but related technical details are difficult to inquire due to related technical secrets.
Patent document No. 201710051339.8 discloses MoSi2，Al2O3Al powder and SiO2MoSi fired as raw material2/Al2O3The high-temperature resistant electromagnetic functional layer can realize the electromagnetic function that the reflection loss value is lower than-5 dB within 9-11 GHz under the thickness of 2 mm. Patent document No. 201610398367.2 discloses Ti3AlC2And Al2O3The high-temperature resistant electromagnetic functional layer as the raw material can realize the reflection loss value lower than-6dB electromagnetic functionality. The patent document with the application number of 201410753360.9 discloses that a high-temperature-resistant electromagnetic functional layer containing nano tin dioxide is prepared by taking tin tetrachloride, deionized water, ethanol and acetylacetone as raw materials, and the electromagnetic function with the reflection loss value lower than-1 dB within 8-18 GHz can be realized under the thickness of 1 mm. The efficiency of the electromagnetic functional layer is closely related to the thickness of the coating.
If a high-temperature electromagnetic function layer is directly transplanted to a C/C composite material, the coating needs to have a thickness of more than 2mm to realize an efficient electromagnetic function, the problem of thermal stress and thermal mismatch of the coating and a base material at high temperature under the thickness is very serious, and even the coating and the base material directly fall off, so that the high efficiency and the thin layer facing the electromagnetic function coating are difficult to be compatible, and based on the problems, a composite coating based on a new mechanism needs to be developed to meet the multifunctional requirements of high temperature resistance, oxidation resistance and low scattering resistance of the C/C composite material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a multifunctional coating with high temperature resistance, oxidation resistance and low scattering on the surface of a carbon/carbon composite material, and a preparation method of the functional coating.
In order to solve the technical problems, the invention adopts the following technical scheme:
a functional coating on the surface of a carbon/carbon composite material comprises a transition bonding layer arranged on the surface of the carbon/carbon composite material and an antioxidant structure layer arranged on the surface of the transition bonding layer;
the surface of the anti-oxidation structure layer is divided into a plurality of square grid units, a first electromagnetic function block group or a second electromagnetic function block group is arranged on each square grid unit, the square grid units and the first electromagnetic function block groups on the square grid units form 0 cell patterns, the square grid units and the second electromagnetic function block groups on the square grid units form 1 cell patterns, the 0 cell patterns are arranged to form a first n x n matrix pattern, the 1 cell patterns are arranged to form a second n x n matrix pattern, and the first n x n matrix patterns and the second n x n matrix patterns are alternately arranged to form an m x m matrix pattern;
the first electromagnetic function block group comprises two first 0 basic block and two second 0 basic block, and the first 0 basic block and the second 0 basic block are alternately arranged to form a 2 x 2 matrix structure; the second electromagnetic function block group comprises two first 1 basic element blocks and two second 1 basic element blocks, and the first 1 basic element blocks and the second 1 basic element blocks are alternately arranged to form a 2 x 2 matrix structure; the first 0 base element block, the second 0 base element block, the first 1 base element block and the second 1 base element block are all electromagnetic function blocks with a cube structure, the thickness of the cube block is 0.01-0.1 mm, the side length of the first 0 base element block is larger than that of the second 0 base element block, and the side length of the first 1 base element block is larger than that of the second 1 base element block.
Preferably, the side length of the square grid unit is 3-6 mm, the side lengths of the first 0-element block and the second 0-element block are 0.8-3 mm, and the side lengths of the first 1-element block and the second 1-element block are 1-4 mm.
The carbon/carbon composite surface functional coating is preferably n = 6.
Preferably, the electromagnetic functional block is made of a high-temperature conductor material, and the high-temperature conductor material comprises a conductive phase and a binder phase.
Preferably, the material of the conductive phase is one or more of Ag-Pd alloy, Mo-Si alloy, Zr-Si alloy, Ta-Si alloy and Ta-Hf alloy.
Preferably, the material of the binder phase is Bi2O3-B2O3-a ZnO mixture.
Preferably, the thickness of the transition bonding layer is 0.05-0.2 mm; the transition bonding layer is made of a bonding material, and the bonding material comprises C and SiC; the binding material is preferably C-SiC mixture or C-SiC-MoC-MoSi2Mixture, C-SiC-ZrC-ZrSi2Mixture, C-SiC-TaC-TaSi2One of the mixtures.
Preferably, the thickness of the oxidation resistant structure layer is 0.5-2 mm; the material of the oxidation-resistant coating is oxide or complex phase oxide, and the material of the oxidation-resistant coating is preferably Al2O3、SiO2-Al2O3Mixture, MAS (MgO-Al)2O3-SiO2）、LAS（Li2O-Al2O3-SiO2）、SiO2-ZrO2Mixture, SiO2-HfO2One of the mixtures.
As a general inventive concept, the present invention also provides a method for preparing the carbon/carbon composite surface functional coating, comprising the steps of:
(1) preparing a transition bonding layer on the surface of the carbon/carbon composite material;
(2) preparing an anti-oxidation structure layer on the surface of the transition bonding layer;
(3) and (3) screen-printing the high-temperature conductor slurry on the surface of the anti-oxidation structure layer through screen printing with a periodic structure to obtain the electromagnetic function layer.
In the above preparation method, preferably, in the step (3), the mesh number of the silk screen is 180 to 300 meshes, and the printing pass number is 1 to 3 times; the drying temperature is 120-300 ℃, and the drying time is 0.5-2 h; the sintering temperature in the sintering process is 500-1200 ℃, the temperature rising speed is 10-30 ℃/min, the sintering time is 30-60 min, and the sintering atmosphere is air.
In the above preparation method, preferably, in the step (3), the preparation process of the high-temperature conductor paste is as follows: 77-87 wt.% of conductive phase and 10-20 wt.% of Bi2O3-B2O3And ball-milling and mixing the ZnO mixture for 1-3 h, adding 3 wt.% of polyvinyl alcohol solution, and uniformly mixing to obtain the high-temperature conductor slurry.
Preferably, in the step (1), the C/C composite material is ultrasonically cleaned and dried, then the composite material is embedded into the bonding powder in the graphite crucible, then the graphite crucible is placed in a high-temperature graphitization heat treatment furnace, argon is used as protective gas, the temperature is raised to 1900-2100 ℃, the temperature is kept for 1-2 hours, and the transition bonding layer is obtained after cooling.
In the preparation method, preferably, in the step (1), the bonding powder comprises the following components in parts by mass: 70-85% of Si powder or Si-containing alloy powder and 15-30% of C powder.
The Si-containing alloy powder is preferably one or more of Mo-Si alloy, Zr-Si alloy and Ta-Si alloy powder.
The bonding powder is mixed in a ball milling mode, and the ball milling time is 3-5 hours.
In the preparation method, preferably, in the step (2), the oxidation-resistant structure layer is prepared by a plasma spraying process. The plasma spraying process parameters are as follows: the ventilation flow of Ar is 20-50L/min, H2The ventilation flow rate is 7.5-12L/min; the powder feeding air flow Ar is 1.8-4.0L/min, and the powder feeding amount is 8% -30%; the current is 500-600A, and the power is 30-50 kW; the spraying distance is 80-150 mm.
In the above preparation method, preferably, in the step (2), the material of the oxidation-resistant structural layer is Al2O3、SiO2-Al2O3Mixture, MAS, LAS, SiO2-ZrO2Mixture, SiO2-HfO2One of the mixtures; the material mixing mode adopts ball milling mixing, and the ball milling time is 3-5 h.
Tests show that when electromagnetic waves irradiate the surface of the material, the amplitudes of reflected waves of the electromagnetic waves at two chessboard units (a first n multiplied by n matrix pattern and a second n multiplied by n matrix pattern) are similar, but the phases are completely opposite, the two reflected waves are just offset in the normal direction, the energy directly reflected back by the electromagnetic waves is greatly reduced, the low detectability of the C/C composite material can be endowed, and the electromagnetic function improvement of thinning and high efficiency of the surface of the C/C composite material is realized.
Compared with the prior art, the invention has the advantages that:
1. the multifunctional coating has the advantages of strong design, high temperature resistance, oxidation resistance, low scattering and the like. The multifunctional coating adopts a multilayer structure, and comprises a transition bonding layer, an antioxidant structure layer and an electromagnetic function layer from inside to outside in sequence from the surface of a C/C substrate. The transition bonding layer is used for solving the weak bonding problem between the C/C composite material and the coating, the high-temperature oxidation resistance characteristic of the C/C composite material is improved by the oxidation resistance structure layer, the electromagnetic wave interference cancellation principle among modules in the electromagnetic function layer is utilized, the reflection energy of electromagnetic waves in the vertical normal direction of the C/C composite material is reduced, the functional characteristic of reducing RCS (radar cross section) of the broadband of the C/C composite material is given, and the low scattering characteristic of the C/C composite material is realized.
2. The multifunctional coating disclosed by the invention is good in cooperativity, can improve the service performance of the C/C composite material in a high-temperature oxidation environment, also improves the electromagnetic function characteristic of the C/C composite material, meets the application requirements in a high-temperature oxidation and electromagnetic environment of 1000 ℃ below zero, can be used for resin matrix composite materials, metals and ceramic matrix composite materials, develops a new structural-function integrated material, and promotes the application of the new material in aviation high-temperature parts.
3. The preparation method has the advantages of good controllability of process parameters, easy realization and engineering advantages.
Drawings
Fig. 1 is a schematic structural diagram of the high temperature resistant, oxidation resistant and low scattering multifunctional coating of the present invention.
Fig. 2 is a schematic structural design diagram of an electromagnetic functional layer in the present invention.
Fig. 3 is a design diagram of a 0 cell pattern in embodiment 1.
Fig. 4 is a design diagram of a 1-cell pattern in embodiment 1.
Fig. 5 is a graph comparing the scattering effect of the multifunctional coating prepared in example 1 of the present invention and a carbon/carbon composite.
FIG. 6 is a normalized single station RCS curve for a multifunctional coating prepared in accordance with example 2 of the present invention.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
A carbon/carbon composite material surface functional coating is shown in figure 1 and comprises a transition bonding layer 2 arranged on the surface of a carbon/carbon composite substrate 1, an anti-oxidation structural layer 3 arranged on the surface of the transition bonding layer 2, and an electromagnetic functional layer 4 arranged on the surface of the anti-oxidation structural layer 3. The electromagnetic function layer 4 is formed by a plurality of first electromagnetic function block groups and second electromagnetic function block groups which are arranged periodically. Specifically, the method comprises the following steps:
as shown in fig. 2, the surface of the anti-oxidation structure layer is divided into a plurality of square grid units, the side length of each square grid unit is 3-6 mm, each square grid unit is provided with a first electromagnetic function block group (identified by "0" in fig. 2) or a second electromagnetic function block group (identified by "1" in fig. 2), each square grid unit and the first electromagnetic function block group on the square grid unit form a 0-cell pattern, each square grid unit and the second electromagnetic function block group on the square grid unit form a 1-cell pattern, a plurality of 0-cell patterns are arranged to form a first 6 × 6 matrix pattern, a plurality of 1-cell patterns are arranged to form a second 6 × 6 matrix pattern, and a plurality of first 6 × 6 matrix patterns and a plurality of second 6 × 6 matrix patterns are alternately arranged to form an m × m matrix pattern.
As shown in fig. 3, the first electromagnetic function block group includes two first 0 cell blocks 41 and two second 0 cell blocks 42, and the first 0 cell blocks 41 and the second 0 cell blocks 42 are alternately arranged to form a 2 × 2 matrix structure. As shown in fig. 4, the second electromagnetic function block group includes two first 1-element blocks 43 and two second 1-element blocks 44, and the first 1-element blocks 43 and the second 1-element blocks 44 are alternately arranged to form a 2 × 2 matrix structure; the first 0-element block 41, the second 0-element block 42, the first 1-element block 43 and the second 1-element block 44 are all electromagnetic function blocks with a cube structure, the thickness of the cube block is 0.01-0.1 mm, the side lengths of the first 0-element block 41 and the second 0-element block 42 are 0.8-3 mm, the side length of the first 0-element block 41 is larger than that of the second 0-element block 42, the side lengths of the first 1-element block 43 and the second 1-element block 44 are 1-4 mm, and the side length 43 of the first 1-element block is larger than that of the second 1-element block 44.
Tests show that when electromagnetic waves irradiate the surface of the material, the amplitudes of reflected waves of the electromagnetic waves at two chessboard units (a first n multiplied by n matrix pattern and a second n multiplied by n matrix pattern) are similar, but the phases are completely opposite, the two reflected waves are just offset in the normal direction, the energy directly reflected back by the electromagnetic waves is greatly reduced, the low detectability of the C/C composite material can be endowed, and the electromagnetic function improvement of thinning and high efficiency is realized.
Example 1:
in the embodiment, the transition bonding layer 1 is a C-SiC transition bonding layer, and the thickness of the transition bonding layer is 0.1 mm; the oxidation resistant structure layer 3 is Al2O3The thickness of the anti-oxidation structure layer is 0.8 mm; the electromagnetic function block is mainly made of Ag-Pd alloy, and the thickness of the electromagnetic function block is 0.08 mm. The electromagnetic function blocks are arranged periodically to form a pattern with two checkerboard units distributed in a staggered manner, as shown in fig. 2, the checkerboard unit space occupation ratio is 1, each checkerboard unit comprises 6 × 6 primitive sequences (the primitive sequences refer to 0 primitive pattern or 1 primitive pattern), the side lengths of square grid units are both 4mm, in the 0 primitive pattern, the side lengths of a first 0 primitive block 41 and a second 0 primitive block 42 are respectively 1.8mm and 1.6mm, and in the 1 primitive pattern, the side lengths of a first 1 primitive block 43 and a second 1 primitive block 44 are respectively 1.2mm and 1 mm.
The preparation method of the high-temperature-resistant, oxidation-resistant and low-scattering multifunctional coating comprises the following steps:
(1) preparing a transition bonding layer containing C-SiC: sequentially grinding and polishing the C/C composite material with the size of 144mm multiplied by 5mm by using No. 200, No. 500 and No. 1000 abrasive paper, ultrasonically cleaning the composite material for 20 minutes by using absolute ethyl alcohol, and drying the composite material in an oven for later use; putting 70% of Si powder and 30% of C powder in mass percent into a ball mill, ball-milling and mixing for 2 hours, and uniformly stirring for later use; and then embedding the C/C composite material into the mixed powder in a graphite crucible, placing the graphite crucible in a high-temperature graphitization heat treatment furnace, taking argon as protective gas, raising the temperature to 1900 ℃ at the heating rate of 30 ℃/min, preserving the heat for 1h, turning off a power supply, and naturally cooling to the normal temperature to obtain the transition bonding layer containing C-SiC.
(2) Preparing an oxidation resistant structure layer: spraying and preparing Al on the surface of the C-SiC bonding layer obtained in the step (1) by adopting a plasma spraying process2O3An anti-oxidation structure layer, wherein the plasma spraying process parameters are as follows: the aeration flow of Ar is 30L/min, H2The aeration flow of (2) is 8L/min; the powder feeding air flow Ar is 2L/min, and the powder feeding amount is 16 percent; electric currentThe size is 550A, and the power is 38 kW; the spraying distance was 100 mm.
(3) Preparing an electromagnetic functional layer: 80 wt.% Ag-Pd alloy and 17 wt.% Bi2O3-B2O3Ball-milling and mixing ZnO for 2h, and then adding 3 wt.% of polyvinyl alcohol solution to uniformly mix to obtain high-temperature conductor slurry; and (3) printing the high-temperature conductor paste on the surface of the anti-oxidation structure layer in the step (2) according to a pattern designed by a periodic patch structure, as shown in fig. 2, printing for 2 times by using a screen with 200 meshes, drying for 2 hours at 120 ℃, heating to 820 ℃ at a heating rate of 10 ℃/min in air, and sintering for 30min to complete the preparation of the multifunctional coating.
The scattering property of the high-temperature-resistant oxidation-resistant low-scattering multifunctional coating obtained in the embodiment is shown in fig. 5, it can be seen from the left figure of the figure that when electromagnetic waves irradiate the surface of the C/C composite material, concentrated vertical reflection occurs, and from the right figure of the figure, when the electromagnetic waves irradiate the surface of the C/C composite material loaded with the multifunctional coating, most of the electromagnetic waves are diffusely reflected to the periphery under the adjustment effect of the electromagnetic function layer, compared with the C/C composite material, the broadband RCS reduction performance is achieved, the-10 dB single-station RCS reduction frequency band is 13-20GHz, and in the broadband range of 13-20GHz, the radar echo energy is only 10% and the excellent low-scattering property is shown; meanwhile, the coating is subjected to a high-temperature oxidation experiment at 800 ℃, the weight loss is only 1.86 percent after 10 hours of air oxidation, the coating is complete, the electromagnetic performance is basically maintained unchanged, and the coating has good comprehensive performance and good application prospect.
Example 2:
in this embodiment, the transition bonding layer 1 is C-SiC-ZrC-ZrSi2The thickness of the transition bonding layer is 0.1 mm; the anti-oxidation structure layer 3 is an MAS anti-oxidation structure layer, and the thickness of the MAS anti-oxidation structure layer is 1 mm; the electromagnetic functional block is mainly made of Mo-Si alloy, and the thickness of the electromagnetic functional block is 0.02 mm. The electromagnetic function blocks are arranged periodically to form two checkerboard unit staggered patterns, the space occupation ratio of the checkerboard units is 1, each checkerboard unit comprises 6 multiplied by 6 primitive sequences (the primitive sequence refers to 0 primitive pattern or 1 primitive pattern), the side length of each square grid unit is 5mm, in the 0 primitive pattern, a first 0 primitive block 41 and a second 0 primitive block 41 are arrangedThe side lengths of the 0-element block 42 are 2.2mm and 2mm, respectively, and the side lengths of the first 1-element block 43 and the second 1-element block 44 are 1.5mm and 1.2mm, respectively, in the 1-element pattern.
The preparation method of the high-temperature-resistant, oxidation-resistant and low-scattering multifunctional coating comprises the following steps:
(1) preparation of C-SiC-ZrC-ZrSi-containing2Transition bonding layer of (a): sequentially grinding and polishing the C/C composite material with the size of 180mm multiplied by 5mm by using No. 200 abrasive paper, No. 500 abrasive paper and No. 1000 abrasive paper, ultrasonically cleaning the composite material for 30 minutes by using absolute ethyl alcohol, and drying the composite material in an oven for later use; ZrSi with the mass fraction of 80 percent2Putting 20% of powder C in a ball mill, ball-milling and mixing for 2 hours, and uniformly stirring for later use; then embedding the C/C composite material into the mixed powder in a graphite crucible, placing the graphite crucible in a high-temperature graphitization heat treatment furnace, taking argon as protective gas, raising the temperature to 2100 ℃ at the heating rate of 30 ℃/min, preserving the heat for 2 hours, turning off a power supply, and naturally cooling to the normal temperature to obtain the material containing C-SiC-ZrC-ZrSi2The transition bonding layer of (1).
(2) Preparing an oxidation resistant structure layer: adopting a plasma spraying process to obtain C-SiC-ZrC-ZrSi in the step (1)2Spraying the surface of the bonding layer to prepare an MAS (Multi-agent Multi-site) antioxidant structure layer, wherein the plasma spraying process parameters are as follows: the aeration flow of Ar is 40L/min, H2The aeration flow of (2) is 10L/min; the powder feeding air flow Ar is 3L/min, and the powder feeding amount is 25 percent; the current is 560A, and the power is 40 kW; the spraying distance was 120 mm.
(3) Preparing an electromagnetic functional layer: mixing 80 wt.% Mo-Si alloy with 17 wt.% Bi2O3-B2O3Ball-milling and mixing ZnO for 2h, and then adding 3 wt.% of polyvinyl alcohol solution to uniformly mix to obtain high-temperature conductor slurry; and (3) printing the high-temperature conductor slurry on the surface of the anti-oxidation structure layer in the step (2) according to a pattern designed by a periodic patch structure, printing for 2 times with the mesh number of a silk screen being 300 meshes, drying for 1h at 150 ℃, heating to 980 ℃ at the heating rate of 10 ℃/min in the air, and sintering for 30min to complete the preparation of the multifunctional coating.
The high-temperature-resistant oxidation-resistant low-scattering multifunctional coating obtained by the embodiment can realize that the-10 dB single-station RCS reduced frequency band is 14-22GHz, which means that only 10% of the forward radar echo energy is left in a 14-24GHz broadband range, and the excellent low-scattering characteristic is shown; meanwhile, the coating is subjected to a high-temperature oxidation experiment at 1000 ℃, the weight loss is only 1.48 percent after 5 hours of air oxidation, the coating is complete, the electromagnetic performance is basically maintained unchanged, and the coating has good comprehensive performance and good application prospect.
The single-station RCS curve of the multifunctional coating obtained in the embodiment is shown in FIG. 4, and it can be seen from the graph that compared with a C/C composite material, the multifunctional coating has broadband RCS reduction performance, the C/C composite material loaded with the multifunctional coating for protection can realize-10 dB reduction in a 13-20GHz broadband range, the maximum reduction amplitude reaches-29 dB, and the multifunctional coating shows excellent low scattering property; meanwhile, the coating is subjected to a high-temperature oxidation experiment at 800 ℃, the weight loss is only 0.86 percent after 10 hours of air oxidation, the coating is complete, the electromagnetic performance is basically maintained unchanged, and the coating has good comprehensive performance and good application prospect.
The above description is only for the preferred embodiment of the present application and should not be taken as limiting the present application in any way, and although the present application has been disclosed in the preferred embodiment, it is not intended to limit the present application, and those skilled in the art should understand that they can make various changes and modifications within the technical scope of the present application without departing from the scope of the present application, and therefore all the changes and modifications can be made within the technical scope of the present application.
Claims (10)
1. A functional coating on the surface of a carbon/carbon composite material, which comprises a transition bonding layer arranged on the surface of the carbon/carbon composite material and an anti-oxidation structure layer arranged on the surface of the transition bonding layer, and is characterized in that,
the surface of the anti-oxidation structure layer is divided into a plurality of square grid units, a first electromagnetic function block group or a second electromagnetic function block group is arranged on each square grid unit, the square grid units and the first electromagnetic function block groups on the square grid units form 0 cell patterns, the square grid units and the second electromagnetic function block groups on the square grid units form 1 cell patterns, the 0 cell patterns are arranged to form a first n x n matrix pattern, the 1 cell patterns are arranged to form a second n x n matrix pattern, and the first n x n matrix patterns and the second n x n matrix patterns are alternately arranged to form an m x m matrix pattern;
the first electromagnetic function block group comprises two first 0 basic block and two second 0 basic block, and the first 0 basic block and the second 0 basic block are alternately arranged to form a 2 x 2 matrix structure; the second electromagnetic function block group comprises two first 1 basic element blocks and two second 1 basic element blocks, and the first 1 basic element blocks and the second 1 basic element blocks are alternately arranged to form a 2 x 2 matrix structure; the first 0 base element block, the second 0 base element block, the first 1 base element block and the second 1 base element block are all electromagnetic function blocks with a cube structure, the thickness of the cube block is 0.01-0.1 mm, the side length of the first 0 base element block is larger than that of the second 0 base element block, and the side length of the first 1 base element block is larger than that of the second 1 base element block.
2. The carbon/carbon composite material surface functional coating according to claim 1, wherein the square grid unit has a side length of 3 to 6mm, the first 0-element block and the second 0-element block have a side length of 0.8 to 3mm, and the first 1-element block and the second 1-element block have a side length of 1 to 4 mm.
3. The carbon/carbon composite surface functional coating of claim 2, wherein n = 6.
4. The carbon/carbon composite material surface functional coating according to any one of claims 1 to 3, wherein the material of the electromagnetic functional block is a high-temperature conductor material, and the components of the high-temperature conductor material comprise a conductive phase and a binding phase.
5. The carbon/carbon composite surface functional coating of claim 4, wherein the conductive phase is one or more of Ag-Pd alloy, Mo-Si alloy, Zr-Si alloy, Ta-Si alloy and Ta-Hf alloy, and the binder phase is Bi2O3-B2O3-a ZnO mixture.
6. The carbon/carbon composite surface functional coating according to any one of claims 1 to 4, wherein the thickness of the transition bonding layer is 0.05 to 0.2 mm; the transition bonding layer is made of a bonding material, and the bonding material comprises C and SiC; the binding material is preferably C-SiC mixture or C-SiC-MoC-MoSi2Mixture, C-SiC-ZrC-ZrSi2Mixture, C-SiC-TaC-TaSi2One of the mixtures.
7. The carbon/carbon composite material surface functional coating according to any one of claims 1 to 4, wherein the thickness of the oxidation resistant structural layer is 0.5 to 2 mm; the material of the oxidation-resistant coating is oxide or complex phase oxide, and the material of the oxidation-resistant coating is preferably Al2O3、SiO2-Al2O3Mixture, MAS, LAS, SiO2-ZrO2Mixture, SiO2-HfO2One of the mixtures.
8. A method for preparing the carbon/carbon composite surface functional coating according to any one of claims 1 to 7, comprising the steps of:
(1) preparing a transition bonding layer on the surface of the carbon/carbon composite material;
(2) preparing an anti-oxidation structure layer on the surface of the transition bonding layer;
(3) and (3) screen-printing the high-temperature conductor slurry on the surface of the anti-oxidation structure layer through screen printing with a periodic structure to obtain the electromagnetic function layer.
9. The manufacturing method according to claim 8, wherein in the step (3), the mesh number of the silk screen is 180-300 meshes, and the printing pass number is 1-3 times; the drying temperature is 120-300 ℃, and the drying time is 0.5-2 h; the sintering temperature in the sintering process is 500-1200 ℃, the temperature rising speed is 10-30 ℃/min, the sintering time is 30-60 min, and the sintering atmosphere is air.
10. The method according to claim 8, wherein in the step (3), the high-temperature conductive paste is prepared as follows: 77-87 wt.% of conductive phase and 10-20 wt.% of Bi2O3-B2O3And ball-milling and mixing the ZnO mixture for 1-3 h, adding 3 wt.% of polyvinyl alcohol solution, and uniformly mixing to obtain the high-temperature conductor slurry.
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