Preparation method of anti-laser ablation coating based on C / C-SiC paper

Abstract

The invention belongs to the technical field of environmental barrier coatings, and particularly relates to a preparation method of an anti-laser ablation coating based on C / C-SiC paper, the coating is prepared through single-layer or laminated pasting of prefabricated C / C-SiC paper, the C / C-SiC paper is composed of carbon fibers, a carbon matrix, SiC, a modifier and a binder, and the fibers in the paper are lapped and entangled to form two-dimensional net paper. The preparation method of the coating comprises the following steps: S1, manufacturing C / C-SiC paper; and S2, attaching the C / C-SiC paper to the surface of the base material, and performing hot-pressing curing to prepare the coating which is mechanically interlocked and combined with the surface of the base material. According to the method, the C / C-SiC paper is prefabricated, the anti-laser ablation coating is prepared through a paper pasting method, the anti-scouring capacity of the coating is effectively improved through lap joint and entanglement of fibers in the paper, the coating is prepared through the paster conveniently and rapidly, the paster can adapt to any shape through cutting, the preparation efficiency is high, the equipment requirement is low, and the paster can also be used for rapidly repairing the damaged coating; and the anti-laser real-time protection requirement can be met.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of anti-laser ablation, and relates to an environmental barrier coating, in particular to a preparation method of an anti-laser ablation coating based on C / C-SiC paper. BACKGROUND

[0002] The laser weapon has the advantages of energy concentration, long transmission distance, high striking precision, fast response speed, strong anti-interference ability and high efficiency and cost ratio. With the rapid development and popularization of the equipment, the traditional confrontation of the spear and the shield presents a new form, and the anti-laser damage has become an urgent problem of many types of equipment including unmanned aerial vehicles. Laser can make the material of the target heat up through strong irradiation, and then directly melt and even gasify to cause damage, or cause the strength and modulus of the material to decrease, so that the material is broken and fails under the action of its own working load stress. At present, the anti-laser ablation damage capacity of the material is mainly improved in the ways of hindering energy input, dredging and consuming heat, resisting high energy with a high melting point and the like.

[0003] Coating is a convenient and effective way to improve the laser ablation damage resistance of existing materials. Currently, coating (CN202110535567.9, CN202210578973.8), thermal spraying (CN202310365999.9, CN202310419151.X, CN202311079749.5, CN202411086773.6), vapor deposition (CN01133732.X), electrodeposition and conversion (CN202111287189.3) and other methods can be used to prepare the coating. Among them, coating method is simple to operate and can use various techniques such as spraying (Optics and Laser Technology 2025, 181: 112069; CN201510547116.1), dipping (CN202411473979.4), brushing (Polycarbosilane composite coating against laser ablation, Space Materials and Technology 2008, (2): 39-42; CN202410499229.8, CN200810244070.6), spin coating (CN202411272741.5) and blade coating (Ceramics International 2020, 46: 23457-23462), and has developed rapidly. However, the coating prepared by the above methods has the following problems: 1. The functional filler particles or fibers, whiskers and nanowires of carbon, ceramic and metal are adhered to the surface of the substrate by high molecular materials, and the components of the coating are dispersed except the high molecular materials, which has poor resistance to high temperature airflow erosion and is quickly scattered under the condition of laser coupling airflow erosion, losing the protection effect. 2. The coating prepared by the above coating method needs to be dried and cured for several hours, especially in the case of thick coating, the next layer of construction can only be carried out after the previous layer of coating is dry and even cured, and during this period, it cannot be subjected to any slight external force to prevent problems such as uneven thickness and local damage, and the preparation process is troublesome, and it is also troublesome to repair. In addition, long-time drying and curing treatment at high temperature (80-260℃) can easily cause overaging of part of the substrate and thus reduce the mechanical properties, so it is difficult to treat the substrate in real time.

[0004] Therefore, improving the erosion resistance of the coating prepared by the coating method and providing immediate protection is the core problem to be solved by the present application. SUMMARY

[0005] In order to solve the technical problems of the existing anti-laser coating with poor performance in the coupling airflow erosion environment and insufficient real-time protection, the present application provides a preparation method of an anti-laser ablation coating based on C / C-SiC paper.

[0006] To achieve the above object, the technical scheme provided by the present application is: a preparation method of a laser ablation resistant coating based on C / C-SiC paper, comprising the following steps: Step one, C / C-SiC paper manufacturing: First, carbon fibers are made into two-dimensional net paper; then carbon matrix, SiC and binder are added into a solvent and stirred uniformly, and then introduced into the two-dimensional net paper and dried; and then the two-dimensional net paper is short-time hot-pressed to form C / C-SiC paper; In the raw materials, the carbon fibers are 10-50 parts by mass; the carbon matrix is 1-50 parts; the SiC is 1-50 parts with a particle size less than 50 microns; the modifier is 1-50 parts; and the binder is 10-50 parts; Step two, coating preparation: The C / C-SiC paper of the 1-N layer obtained in step one is attached to the surface of the pretreated substrate, and after the paper and the substrate and the air bubbles between the papers are scraped off using a scraper, the coating is formed by hot-pressing and curing, which forms a mechanical interlocking combination with the surface of the substrate.

[0007] Further, the short-time hot-pressing in step one is 0.1-1h, the pressure is 0.5-50MPa, and the temperature is 80-200℃.

[0008] Further, the hot-pressing and curing in step two is 0.1-1h, the pressure is 0.5-50MPa, and the temperature is 80-200℃. Further, the length of the carbon fibers in step one is 1-30mm.

[0009] Further, the two-dimensional net paper in step one is made by wet papermaking or dry forming, and the thickness is 0.05-2mm.

[0010] Further, the method of uniformly introducing the carbon matrix, SiC and binder into the two-dimensional net paper is by using the impregnation method or the brushing method.

[0011] Further, the carbon matrix in step one is graphite or diamond with a particle size less than 50 microns, or one or any combination of carbon nanotubes, carbon nanowires and graphene.

[0012] Further, the binder in step one is one or any combination of thermosetting resins such as epoxy resin, phenolic resin, urea-formaldehyde resin, furan resin, silicone resin and bismaleimide resin.

[0013] Further, in the step one, the modifier is Ti, Ni, Cu, Al, Ba2SmTaO6, etc. reflective component, or ZrC, HfC, TaC, ZrB2, HfB2, MoSi2, etc. heat-resistant and oxidation-resistant component, or ZrO2, HfO2, Al2O3, etc. low-thermal-conductivity component, one or any combination thereof is selected, and the form is one or any combination of fiber, whisker, nanowire, and particle with a particle size less than 50 microns.

[0014] Further, the pretreatment in the step two is polishing, cleaning or sand blasting, and the roughness Ra of the substrate after the treatment is 0.3-20.

[0015] Compared with the prior art, the present application has the following beneficial effects: (1) The present application creatively proposes that the coating is prepared into a planar structure C / C-SiC paper in advance, which is convenient to carry and is completely different from the existing on-site full-process coating preparation idea. A new method is provided for real-time protection and maintenance in special occasions.

[0016] (2) The coating is composed of the C / C-SiC paper, the one-dimensional toughening components such as fibers in the prepared C / C-SiC paper are directly connected and intertwined to form a two-dimensional network, which has a certain strength, so that the coating still has good tear resistance when the binder is carbonized in a high-temperature environment, thereby effectively improving the airflow scouring resistance of the coating.

[0017] (3) The real-time protection capability is strong: the C / C-SiC paper for the coating is prepared in advance and the binder therein is solidified to a certain extent, the coating is quickly prepared by the paper pasting method on the substrate, without the need for long-time drying and solidification under protection conditions, the preparation can be completed immediately in the field and the like, the pasting is convenient and fast, easy to construct and has low requirements on equipment, that is, by preparing the coating into a paper, the real-time preparation time of the coating is shortened, the real-time preparation requirements are reduced, in addition, the C / C-SiC paper can be cut to adapt to the shape of any structure, and any thickness can be achieved by stacking. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 is a structural schematic diagram (a) and a macroscopic photograph (b) of the carbon fiber two-dimensional net paper prepared by the embodiment 1 of the present application; Figure 2 is a structural schematic diagram of the C / C-SiC paper prepared by the embodiment 1 of the present application; Figure 3 is a photograph of the C / C-SiC paper prepared by the embodiment 1 of the present application, wherein Figure 3 (a) is a photograph of the planar C / C-SiC paper; Figure 3 (b) is a photograph of the curved C / C-SiC paper; Figure 4These are comparative photographs of the laser ablation morphology of a C / C-SiC sticker coating on an aluminum substrate obtained through Example 1 of this invention and a brush-coated coating of the same composition; wherein... Figure 4 (a) is a macroscopic photograph of the C / C-SiC sticker coating after ablation. Figure 4 (b) is a scanning electron microscope image of the ablation center after the C / C-SiC sticker coating was ablated. Figure 4 (c) is a macroscopic photograph of a coating with the same composition as the C / C-SiC sticker after ablation. Figure 4 (d) is a scanning electron microscope image of the ablation center of a coating with the same composition as the C / C-SiC sticker after ablation. Detailed Implementation

[0019] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below in conjunction with specific embodiments and accompanying drawings. However, the embodiments described are not intended to limit the present invention.

[0020] Unless otherwise specified, the experimental and detection methods described in the following embodiments are conventional methods; unless otherwise specified, the reagents and materials are commercially available.

[0021] The above-mentioned content of the present invention will be specifically described below through the following embodiments.

[0022] Example 1: A method for preparing a laser ablation resistant coating on an aluminum alloy surface based on C / C-SiC paper, comprising the following steps: Step 1: C / C-SiC paper manufacturing: First, 10 grams of 10mm long carbon fibers were evenly dispersed in 500 grams of water. A 1mm thick carbon fiber two-dimensional mesh was then produced by wet papermaking and dried in a 100℃ oven for 2 hours. A schematic diagram of the resulting carbon fiber two-dimensional mesh structure is shown below. Figure 1 As shown in (a), it can be seen that before the matrix is ​​added, the fibers have already formed a network through overlapping and entanglement, such as Figure 1 (b) shows a macroscopic photograph of the actual object. The two-dimensional mesh paper can be placed independently in the hand, and it is flat without bending or wrinkles, indicating that the carbon fiber forms a two-dimensional mesh paper with a certain strength through overlapping and entanglement. Next, a total of 90 grams of powder, including 1 gram of graphite particles (1-5 micrometers), 1 gram of SiC particles (1-5 micrometers), 50 grams of ZrO2 particles (1-5 micrometers), and 38 grams of boron-modified phenolic resin (10-150 micrometers), was mixed with 90 grams of anhydrous ethanol (solvent) to prepare a slurry. The slurry was then evenly coated onto carbon fiber two-dimensional mesh paper using a brush and dried in an oven at 80°C for 5 hours before use. Then, the two-dimensional net paper is hot-pressed at 120℃, 5MPa for 0.5h to form a C / C-SiC paper with a thickness of 1mm and a multi-functional property of high thermal conductivity, heat resistance, high reflectivity and low thermal conductivity.

[0023] Referring to Figure 2 , the C / C-SiC paper is composed of a two-dimensional net paper formed by carbon fiber lapping and entangling, and a graphite-SiC-ZrO2-phenolic resin hybrid matrix. Figure 3 (a) and Figure 3 (b) can be seen that the C / C-SiC paper is dense and can be flat or curved as needed.

[0024] Step two, C / C-SiC paper pasting: First, the surface of the substrate is pretreated: the surface of the aluminum alloy piece is polished with sandpaper to a roughness of Ra=0.5, then washed with anhydrous ethanol and blown dry, and then used; Then, 1 layer of C / C-SiC paper is spread out and attached to the surface of the aluminum alloy piece under the action of electrostatic attraction and surface tension. After removing the bubbles between the paper and the aluminum substrate using a plastic scraper, the coating is cured at a temperature of 150℃, a pressure of 5MPa, and a duration of 2h to form a 1mm thick coating.

[0025] The laser ablation-resistant coating prepared in this example has a morphology as shown in Figure 4 (a) after ablation for 5s under the conditions of a laser power density of 1000W / cm 2 , a gas flow of 0.5m 3 / h. Compared with a conventional coating of the same composition and thickness prepared by direct brushing ( Figure 4 (c)), the macroscopic morphology shows that the ablation area of the coating with the two-dimensional net of carbon fibers introduced by the paper pasting method is a regular elliptical ring around the rectangle, and no obvious expansion occurs, while the ablation area of the direct brushing coating is no longer a regular shape corresponding to the light spot, and obvious expansion and peeling occur. The microscopic morphology shows that after ablation of the coating with C / C-SiC paper ( Figure 4 (b)), there is still a large amount of residue, and the paper-free coating ( Figure 4 (d)) exposes the aluminum alloy substrate, indicating that the paper pasting coating has better ablation resistance. Based on the above information, it can be seen that the two-dimensional network formed by the C / C-SiC paper effectively improves the erosion and peeling problem of the coating in the laser coupling gas flow environment.

[0026] Example 2, a method for preparing an aluminum alloy surface laser ablation-resistant coating based on C / C-SiC paper, comprising the following steps: Step one, C / C-SiC paper manufacturing: Firstly, 50 grams of 1mm long carbon fibers were evenly dispersed in 500 grams of water, and a carbon fiber two-dimensional net paper with a thickness of 2mm was prepared by dry papermaking, and then dried in an oven at 120°C for 2h; Next, 80 grams of powder, including 1 gram of carbon nanotubes, 10 grams of SiC whiskers, 9 grams of ZrC particles (1-5 microns), 10 grams of MoSi2 particles (1-5 microns), and 50 grams of silicone resin (100-200 microns), were mixed with 80 grams of anhydrous ethanol to prepare a slurry; the slurry was evenly impregnated into the carbon fiber two-dimensional net paper using the impregnation method, and then dried in an oven at 80°C for 10h; Then, the two-dimensional net paper was hot-pressed at 80°C, 5kPa pressure for 1h to prepare a C / C-SiC paper with a thickness of 0.05mm.

[0027] Step two, C / C-SiC paper pasting: First, the surface of the substrate was pretreated: the surface of the D406A steel plate was sandblasted to remove surface grease, rust and make the roughness Ra=2, ready for use; Then, 2 layers of C / C-SiC paper were spread and attached to the surface of the D406A steel plate, and after removing the bubbles between the paper and the steel plate substrate and the 2 layers of paper with a wooden scraper, the coating was cured at a temperature of 200°C, a pressure of 5kPa, and a duration of 0.1h.

[0028] The laser ablation-resistant coating prepared in this example has a thickness of about 0.1mm, and under the conditions of laser power density 1000W / cm 2 , 2m 3 / h airflow erosion, after ablation for 5s, compared with the conventional coating of the same composition and thickness prepared by direct brushing, the ablation area is reduced by 26% and the mass ablation rate is reduced by 30%.

[0029] Example 3, a method for preparing an aluminum alloy surface laser ablation-resistant coating based on C / C-SiC paper, comprising the following steps: Step one, C / C-SiC paper manufacturing: Firstly, 20 grams of 30mm long carbon fibers were evenly dispersed in 500 grams of water, and a carbon fiber two-dimensional net paper with a thickness of 2mm was prepared by dry papermaking, and then dried in an oven at 120°C for 2h; Next, 80 grams of powder, including 1 gram of carbon nanotubes, 10 grams of SiC whiskers, 9 grams of ZrC particles (1-5 microns), 10 grams of MoSi2 particles (1-5 microns), and 50 grams of silicone resin (100-200 microns), were mixed with 80 grams of anhydrous ethanol to prepare a slurry; the slurry was evenly impregnated into the carbon fiber two-dimensional net paper using the impregnation method, and then dried in an oven at 80°C for 10h; Then the two-dimensional net paper is hot-pressed at 200 DEG C, a pressure of 5 MPa and for 0.5 h to prepare a C / C-SiC paper with a thickness of 2 mm.

[0030] Step two, C / C-SiC paper pasting: First, the substrate surface is pretreated: the TC4 plate surface is subjected to laser cleaning treatment to remove surface grease and rust and to make the roughness reach Ra=3, and then the plate is ready for use; Then, one layer of C / C-SiC paper is spread and attached to the TC4 plate surface, the bubbles between the paper and the steel plate substrate are removed using a wooden spatula, and then the coating is cured at a temperature of 80 DEG C, a pressure of 10 MPa and for 1 h to prepare the coating.

[0031] The anti-laser ablation coating prepared in the embodiment has a thickness of about 2 mm, and under the condition of a laser power density of 1000 W / cm 2 , a 4 m 3 / h airflow scouring, the ablation area is 22% smaller and the mass ablation rate is reduced by 26% compared with a conventional coating prepared by direct brushing and having the same composition and thickness.

[0032] The above examples show that the coating prepared by pasting C / C-SiC paper on the substrate surface has excellent anti-ablation ability in the laser impact + airflow scouring environment.

[0033] Obviously, those skilled in the art can make various modifications and variations to the present application without departing from the spirit and scope of the present application. Thus, if these modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, these modifications and variations are also intended to be included in the present application.

Claims

1. A method for preparing a laser ablation resistant coating based on C / C-SiC paper, characterized in that: Includes the following steps: Step 1: C / C-SiC paper manufacturing: First, carbon fiber is made into a two-dimensional mesh paper; then, carbon matrix, SiC and binder are added to solvent and stirred evenly, uniformly introduced into the two-dimensional mesh paper and dried; then the two-dimensional mesh paper is subjected to short-time hot pressing to form C / C-SiC paper. In terms of parts by weight, the raw materials contain 10-50 parts of carbon fiber. The carbon matrix is ​​1-50 parts; the SiC is 1-50 parts with a particle size of less than 50 micrometers; the modifier is 1-50 parts; and the binder is 10-50 parts. Step 2: Coating preparation: The 1-N layers of C / C-SiC paper obtained in step one are attached to the surface of the pretreated substrate. After removing the air bubbles between the paper and the substrate and between the paper using a scraper, the paper is cured by hot pressing to form a coating that forms a mechanical interlocking bond with the surface of the substrate.

2. The method for preparing a laser ablation resistant coating based on C / C-SiC paper according to claim 1, characterized in that: The short-time hot pressing in step one lasts for 0.1-1 hours, with a pressure of 0.5-50 MPa and a temperature of 80-200℃.

3. The method for preparing a laser ablation resistant coating based on C / C-SiC paper according to claim 2, characterized in that: The hot-press curing time in step two is 0.1-1h, the pressure is 0.5-50MPa, and the temperature is 80-200℃.

4. The method for preparing a laser ablation resistant coating based on C / C-SiC paper according to claim 3, characterized in that: The length of the carbon fiber in step one is 1-30mm.

5. The method for preparing a laser ablation resistant coating based on C / C-SiC paper according to claim 4, characterized in that: The two-dimensional paper in step one is formed by wet papermaking or dry forming, and has a thickness of 0.05-2mm.

6. The method for preparing a laser ablation resistant coating based on C / C-SiC paper according to claim 5, characterized in that: The carbon matrix, SiC, and binder are uniformly introduced into the two-dimensional mesh paper using an impregnation or coating method.

7. The method for preparing a laser ablation resistant coating based on C / C-SiC paper according to claim 6, characterized in that: The carbon matrix in step one is graphite or diamond with a particle size of less than 50 micrometers, or one or any combination of carbon nanotubes, carbon nanowires, and graphene.

8. The method for preparing a laser ablation resistant coating based on C / C-SiC paper according to claim 7, characterized in that: The adhesive used in step one is one or any combination of thermosetting resins such as epoxy resin, phenolic resin, urea-formaldehyde resin, furan resin, silicone resin, and bismaleimide resin.

9. The method for preparing a laser ablation resistant coating based on C / C-SiC paper according to claim 8, characterized in that, In step one, the modifier includes Ti, Ni, Cu, Al, Ba2SmTaO6, ZrC, HfC, TaC, ZrB2, HfB2, MoSi2, ZrO2, HfO2, and Al2O3, and one of them or any combination thereof is selected, and its morphology is one of fibers, whiskers, nanowires, or particles with a particle size of less than 50 micrometers or any combination thereof.

10. The method for preparing a laser ablation resistant coating based on C / C-SiC paper according to claim 9, characterized in that: The pretreatment in step two is grinding, cleaning or sandblasting, and the roughness of the substrate after treatment is Ra=0.3-20.

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