Anti-atomic oxygen composite film and preparation method and application thereof

Abstract

The invention belongs to the technical field of aerospace materials, and particularly relates to an anti-atomic oxygen composite film and a preparation method and application thereof, and the anti-atomic oxygen composite film comprises an A / B / C structure, an A / C / B structure or an A / D structure. Wherein A is a polymer substrate, B is an organic silicon protective layer, C is a metal catalytic layer, and D is a composite functional layer formed by dispersing nano metal particles in an organic silicon matrix. The prepared atomic oxygen resistant composite film can timely reform and convert high-energy AO into O2 and release energy to reduce the strong oxidation effect of the high-energy AO on the coating, so that the chain degradation reaction of an organosilicon polymer is slowed down or even terminated, meanwhile, the diffusion rate of the AO is limited in cooperation with the flexible organosilicon coating, and oxidation denudation of the AO on a polymer substrate is expected to be inhibited. Through triple optimization of the structure, the material and the interface, the excellent and lasting atomic oxygen resistance is obtained, and the coating is suitable for spacecraft surface protection.

Description

Technical Field

[0001] This invention belongs to the field of aerospace materials technology, and specifically relates to an antigen-oxygen composite thin film, its preparation method, and its application. Background Technology

[0002] Polymer materials, represented by polyimide (PI), have been widely used in various spacecraft due to their excellent flexibility, optical properties, mechanical strength, thermal stability, and lightweight characteristics. Spacecraft must withstand harsh space environments during their service life, such as radiation from various charged particles, ultraviolet radiation, alternating high and low temperatures, high vacuum venting, space debris impacts, and high-energy atomic oxygen (AO) corrosion. Therefore, the tolerance of various structural and functional materials in spacecraft is subject to extremely high requirements. AO is mainly distributed in the low Earth Orbit (LEO, 200-700 km) environment where spacecraft such as space stations operate, and these particles have a significant corrosive and destructive effect on spacecraft. AO is caused by the dissociation of O2 molecules at the top of the atmosphere by ultraviolet light. Due to the relatively high vacuum conditions in this environment, the mean free path of AO is very large (~10⁸ m), making it difficult for AO to recombine into O2 or O3 molecules. This allows AO densities to reach up to 10⁻⁶. 9 atoms / cm 2 When a low-Earth orbit spacecraft (such as a space station) travels at a speed of approximately 8 km / s, the AO beam density impacting the spacecraft increases to 2.0 × 10⁻⁶. 15 atoms / cm 2 Unlike other X-ray particles, alpha (AO) is a highly reactive high-energy (4.2–5.1 eV) atom. When AO impacts polymer materials at high speed, it rapidly breaks the covalent bonds in the polymer molecular chains, causing chain breakage and fragment decomposition. This manifests as changes in the polymer material's mass, surface morphology, strength, and photoelectric properties—the AO effect. When spacecraft are exposed to such a high-energy, highly oxidizing AO atmosphere for extended periods, it directly impacts the performance and on-orbit lifespan of the spacecraft's major technical subsystems. NASA ground-based simulations and spaceflight tests show that at an altitude of 300–400 km in space station orbit, the erosion rate of AO on polyimide (PI) reaches as high as 3.0 × 10⁻⁶. -24 cm 3 The 25μm thick PI material will be eroded away by AO within six months, leading to the failure of the underlying load and making it unable to withstand 7.83×10⁻⁶ loads. 22 atom / cm 2Design requirements for irradiation flux (equivalent to 15 years). The significant impact of the AO effect has attracted great attention from the aerospace research and industry, especially for the development and research of long-life low-Earth orbit spacecraft and manned space stations. The AO effect is an important scientific and engineering problem that must be fully understood, studied, and solved. Specifically, how to further improve the AO resistance of PI-based protective layers on low-Earth orbit spacecraft is a major challenge facing the development of aerospace technology.

[0003] Highly flexible silicone / PI composite films are among the most efficient anti-aerosol (AO) protective coatings reported both domestically and internationally. These coatings not only possess strong interfacial adhesion, high transparency, and high flexibility, but also exhibit strong AO protection performance and self-healing properties. More importantly, certain coating models have met the design requirements for protection of low-Earth orbit (LEO) vehicles and have been successfully applied to multiple vehicle missions and commercialized. However, these protective films have a relatively long failure induction period; when the AO flux exceeds 2.5 × 10⁻⁶, the failure rate increases. 22 atom / cm 2 When the irradiation dose increases further (i.e., after an equivalent of 5 years) or continues to increase, the flexible organosilicon components on the surface further transform, or even completely transform, into high-modulus silica. This leads to interfacial separation and surface cracking under interfacial stress, ultimately resulting in the loss of effective protection for the underlying substrate. This poses a hidden danger to the safe operation of long-life aircraft. Therefore, developing new protection strategies to further improve the AO resistance of flexible organosilicon protective coatings has significant practical value. Summary of the Invention

[0004] To address the shortcomings of the existing technologies, the present invention aims to provide an antigen-oxygen composite thin film, its preparation method, and its applications. This approach departs from the traditional single-protection strategy, adopting a synergistic strategy of protection coupled with catalytic reforming. The prepared antigen-oxygen composite thin film is expected to fundamentally inhibit the oxidative ablation of polymer substrates by oxidative oxygen (AO). Through triple optimization of structure, materials, and interfaces, superior and durable antigen-oxygen capability is achieved, making it suitable for spacecraft surface protection.

[0005] To solve the above-mentioned technical problems, the present invention provides an antigen-oxygen composite film, wherein the antigen-oxygen composite film is one of the following: A / B / C structure, A / C / B structure or A / D structure; The A / B / C structure is formed by stacking a polyimide membrane substrate A, a polysiloxane protective layer B, and a metal catalytic layer C from bottom to top. The A / C / B structure is formed by stacking polyimide membrane substrate A, metal catalyst layer C and polysiloxane protective layer B from bottom to top. The A / D structure is formed by stacking a polyimide film substrate A and a nano-metal-polysiloxane composite functional layer D from bottom to top. In the A / B / C structure, the polyimide membrane substrate A and the polysiloxane protective layer B are modified at the interface by a silane coupling agent; in the A / C / B structure, the metal catalyst layer C is modified at the interface by a silane coupling agent; and in the A / D structure, the nano-metal-polysiloxane composite functional layer D is modified at the interface by a silane coupling agent.

[0006] Preferably, the silane coupling agent used for interface modification of the polyimide film substrate A is an aminosilane coupling agent, the silane coupling agent used for interface modification of the polysiloxane protective layer B is bis-[3-(triethoxysilane)propyl] disulfide, and the silane coupling agent used for interface modification of the metal catalyst layer C or the nano-metal-polysiloxane composite functional layer D is a mercaptosilane coupling agent. The reason why mercaptosilane coupling agent is used for interface modification of metal catalyst layer C is that mercapto can form the strongest covalent bond (Au-S bond) with gold surface, while siloxane end can form Si-O-Si bond with polydimethylsiloxane through hydrolysis, thus building the strongest "molecular bridge" between the two. The reason why mercaptosilane coupling agent is used for interface modification of nano metal-polysiloxane composite functional layer D is that mercaptosilane coupling agent anchors metal particles through strong covalent bond formation with metal particles through its mercapto group, while silane end covalently crosslinks with polydimethylsiloxane, thus constructing a strong organic-inorganic hybrid interface at the nanoscale, fundamentally solving the problems of particle agglomeration and interface debonding.

[0007] Aminosilane coupling agents are used because the amino groups in the aminosilane coupling agent can catalyze the curing of polysiloxane protective layer B to form chemical bonds; one end of the bis-[3-(triethoxysilane)propyl] disulfide can chemically bond with polysiloxane protective layer B, and the other end of the bis-[3-(triethoxysilane)propyl] disulfide (through disulfide bonds) can form extremely strong covalent bonds with the gold surface, similar to "gold-sulfur" self-assembled monolayers (SAMs).

[0008] Preferably, the silane coupling agent for interface modification of the polyimide membrane substrate A is 3-aminopropyltriethoxysilane. This is because the ethoxy group in 3-aminopropyltriethoxysilane hydrolyzes slowly, making it easier to form a uniform and dense monomolecular film on the polyimide membrane substrate A, with stable and controllable results.

[0009] Preferably, the silane coupling agent used for interface modification of the metal catalyst layer C or the nano-metal-polysiloxane composite functional layer D is 3-mercaptopropyltrimethoxysilane.

[0010] The reason for using 3-mercaptopropyltrimethoxysilane for interface modification of metal catalyst layer C is that 3-mercaptopropyltrimethoxysilane has a moderate molecular length and balanced reactivity, and can form an ideal interface layer that is both strong and tough between gold and polydimethylsiloxane.

[0011] The reason for using 3-mercaptopropyltrimethoxysilane for interface modification in the nano-metal-polysiloxane composite functional layer D is that the propyl chain length of 3-mercaptopropyltrimethoxysilane provides sufficient flexibility to buffer stress while ensuring the compactness of the interface layer; the methoxy hydrolysis rate is moderate, which is conducive to forming a uniform and stable monomolecular modification layer on the particle surface; and as a monofunctional thiol reagent, it can avoid agglomeration caused by multiple bonds, thereby achieving efficient, stable and strong interfacial dispersion of nano-metal particles in polydimethylsiloxane.

[0012] Preferably, the metal catalyst layer C is made of one of gold, zinc, cobalt, manganese, copper, nickel, or silver. Preferably, the polysiloxane protective layer B is made of one of polydimethylsiloxane, comb-like alkyl polysiloxane, or plasma-polymerized hexamethyldisiloxane; The comb-shaped alkyl polysiloxane is obtained by crosslinking polymethylhydrosiloxane with terminal olefins via hydrosilylation reaction. The side chain of the comb-shaped alkyl polysiloxane is C6-C. 14 The straight-chain alkyl group; and the straight-chain alkyl group is one of hexyl, heptyl, octyl, decyl, dodecyl or tetradecyl.

[0013] This invention provides a method for preparing an antigen-oxygen composite film. When the antigen-oxygen composite film has an A / B / C structure, the preparation method includes the following steps: After plasma activation, polyimide film layer A is immersed in a 1%~8% silane coupling agent hydrolysate for 5 min~10 min, then removed, rinsed and cured at 50℃~100℃ for 10 min~60 min to obtain silane coupling agent modified polyimide film layer A. The preparation steps for forming a polysiloxane protective layer B on a silane coupling agent modified polyimide film layer A to obtain product 1 are as follows: The main agent of polydimethylsiloxane and the curing agent are mixed at a mass ratio of 5~50:1, and after stirring, heating, and vacuum degassing, the mixture is coated onto the silane coupling agent modified polyimide film layer A, and cured at 60℃~80℃ for 10min~60min; or polymethylhydrosiloxane is mixed with C6~C 14 Terminal olefins undergo hydrosilylation reactions at 50°C–80°C in the presence of a platinum catalyst to obtain grafted polymers. Subsequently, a crosslinking agent is added to the reaction system to induce a crosslinking reaction, yielding a casting solution. This casting solution is then coated onto a silane coupling agent-modified polyimide film layer A and cured at 50°C–80°C to form the final film. Alternatively, hexamethyldisiloxane can be deposited onto the silane coupling agent-modified polyimide film layer A using plasma-enhanced chemical vapor deposition (PECVD), with the vacuum level of the vacuum chamber set to 4 × 10⁻⁶. −3Pa, the hexamethyldisiloxane monomer is heated to 20℃~50℃ in a water bath and turned into steam. The monomer flow rate is set to 25sccm~60sccm. It is mixed with oxygen at a flow rate of 40sccm~70sccm and added to the vacuum chamber. The working pressure of the vacuum chamber is 5Pa. After plasma activation of product 1, a 1% to 8% silane coupling agent hydrolysate was sprayed onto the activated product 1 2 to 3 times. After natural drying at room temperature for 20 to 60 minutes, the product 2 was obtained by heating and curing at 50 to 100°C for 10 to 60 minutes. Product 2 was subjected to vacuum magnetron sputtering of metallic gold for 10s to 150s to obtain an A / B / C structure.

[0014] Preferably, when the antigen-oxygen composite film has an A / C / B structure, the preparation method includes the following steps: The polyimide thin film layer A was subjected to ultra-vacuum magnetron sputtering of metallic gold for 10s to 150s to form a metal catalyst layer C on the polyimide thin film layer A, resulting in product 3. After activating product 3 with plasma, it is immersed in a 1% to 8% silane coupling agent hydrolysate for 5 to 10 minutes. After being removed, it is rinsed and cured at 50°C to 100°C for 10 to 60 minutes to obtain product 4. The steps for forming a polysiloxane protective layer B on product 4 are as follows: The main agent of polydimethylsiloxane and the curing agent are mixed at a mass ratio of 5~50:1. After stirring, heating, and vacuum degassing, the mixture is applied to product 4 and cured at 60℃~80℃ for 10min~60min to obtain an A / C / B structure; or polymethylhydrosiloxane is combined with C6~C 14 The terminal olefins underwent a hydrosilylation reaction at 50℃~80℃ in the presence of a platinum catalyst to obtain a grafted polymer; subsequently, a crosslinking agent was added to the reaction system to carry out a crosslinking reaction, yielding a casting solution; the casting solution was then coated onto product 4 and cured at 50℃~80℃ to obtain an A / C / B structure; or hexamethyldisiloxane was deposited onto product 4 using plasma-enhanced chemical vapor deposition equipment, with the vacuum degree of the equipment vacuum chamber being 4×10⁻⁶. −3 Pa, hexamethyldisiloxane monomer is heated to 20℃~50℃ in a water bath to become steam, the monomer flow rate is set to 25~60 sccm, mixed with oxygen at a flow rate of 40~70 sccm, and added to a vacuum chamber with a working pressure of 5 Pa, to form a polysiloxane protective layer B on the metal catalyst layer C, thus obtaining the A / C / B structure.

[0015] Preferably, when the antigen-oxygen composite film has an A / D structure, the preparation method includes the following steps: After plasma activation, polyimide film layer A is immersed in a 1% to 8% silane coupling agent hydrolysate for 5 to 10 minutes. After rinsing and curing at 50°C to 100°C for 10 to 60 minutes, silane coupling agent modified polyimide film layer A is obtained. The nano-gold triangle sheet was surface modified with a 2%–8% silane coupling agent / ethanol solution. After stirring overnight, it was mixed with the polydimethylsiloxane main agent and a curing agent was added. After being mixed evenly and degassed, it was coated onto a silane coupling agent modified polyimide film layer A after being activated by plasma. After being heated and cured at 60℃–80℃ for 10 min–60 min, a nano-metal-polysiloxane composite functional layer D was formed on the polyimide film layer A, resulting in an A / D structure. The mass ratio of polydimethylsiloxane main agent to curing agent was 5–50:1. Or combine polymethylhydrosiloxane with C6-C 14 Terminal olefins undergo hydrosilylation in the presence of a platinum catalyst at 50°C–80°C to obtain a grafted polymer. Subsequently, nano-gold triangular sheets modified with a 2%–8% silane coupling agent / ethanol solution and stirred overnight are added to the reaction system and stirred until homogeneous. Then, a crosslinking agent is added to carry out a crosslinking reaction to obtain a casting solution. The casting solution is coated onto a silane coupling agent modified polyimide film layer A after plasma activation. After curing at 50°C–80°C, a nano-metal-polysiloxane composite functional layer D is formed on the polyimide film layer A, resulting in an A / D structure.

[0016] This invention provides the application of antigen-oxygen composite films in spacecraft surface protection.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: The A / B / C structured antigenic oxygen composite films, A / C / B structured antigenic oxygen composite films, or A / D structured antigenic oxygen composite films prepared by this invention combine the diffusion-restricted strategy of the polysiloxane protective layer and the catalytic reforming strategy of the metal catalytic layer. Specifically, the organic layer restricts the diffusion of AO in the composite film, and after being oxidized by AO, it forms a dense, rigid structure similar to SiO2 and acts as a flexible stress buffer layer, effectively absorbing and redistributing the interfacial stress caused by irradiation and oxidation. Simultaneously, the metal catalytic layer catalytically reforms the highly oxidizing AO into O2, significantly reducing its oxidizing power on the material. These two mechanisms are closely coupled spatially and functionally: the metal catalytic layer provides a mild service environment for the organic protective layer, extending its durability; the organic protective layer, in turn, ensures the structural integrity of the metal catalytic layer by inhibiting stress concentration and crack initiation. It is this synergistic effect that allows the film to enter a stable protective state from the initial stage of irradiation, without a significant failure-inducing period, and to maintain the integrity of interfacial bonding and surface morphology even under ultra-high cumulative flux, thereby significantly improving the overall reliability and lifespan of the protective system.

[0018] The A / B / C structure antigenic oxygen composite film, A / C / B structure antigenic oxygen composite film, or A / D structure antigenic oxygen composite film prepared by the present invention, by composite catalytic active layer on flexible organosilicon structural coating, timely reforms high-energy AO into O2 and releases energy to reduce the strong oxidizing effect of high-energy AO on the coating, thereby slowing down or even terminating the chain degradation reaction of organosilicon polymer. At the same time, the flexible organosilicon coating restricts the diffusion rate of AO, which is expected to fundamentally inhibit the oxidative erosion of polymer substrate by AO, and is suitable for spacecraft surface protection. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the structure of the A / B / C type composite film prepared in Examples 1 to 3 of the present invention; Figure 2 This is a schematic diagram of the structure of the A / C / B type composite film prepared in Examples 4 to 6 of the present invention.

[0020] Figure 3 This is a schematic diagram of the structure of the A / D type composite film prepared in Examples 7 to 9 of the present invention.

[0021] Figure 4 This is a scanning electron microscope image of gold nanotriangular pieces.

[0022] Figure 5 These are atomic force microscopy images of the A / B / C type composite thin film prepared in Example 1 before and after AO irradiation, wherein... Figure 5 The left image in the image is an atomic force microscopy photograph of the A / B / C type composite thin film before AO irradiation. Figure 5 The right image in the image is an atomic force microscope photograph of the A / B / C type composite film after AO irradiation.

[0023] Figure 6 The infrared spectra of the A / B / C type composite film prepared in Example 1 before and after AO irradiation are shown.

[0024] Figure 7 The graphs show the cross-cut adhesion test results for six composite films: Example 1, Example 4, Comparative Examples 2-4, and Comparative Example 12. Figure 7 The top left image in the diagram is a cross-cut adhesion test result from Comparative Example 2. Figure 7 The lower left image in the figure shows the adhesion test results of the cross-cut adhesion test in Comparative Example 3. Figure 7 The upper middle image shows the adhesion test results of the cross-cut adhesion test in Comparative Example 4. Figure 7 The lower middle figure is a cross-cut adhesion test diagram of Example 1. Figure 7 The upper right image in the figure shows the adhesion test results of the cross-cut adhesion test in Comparative Example 12. Figure 7The lower right figure in the image is a cross-cut adhesion test diagram of Example 4.

[0025] Figure 8 The image shows the cross-cut adhesion test results of the composite film with the A / D type composite structure prepared in Example 7. Detailed Implementation

[0026] The specific embodiments of the present invention are described in detail below, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention. Unless otherwise specified, the experimental methods described in the embodiments of the present invention are conventional methods.

[0027] It should be noted that when numerical ranges are involved in this invention, it should be understood that both endpoints of each numerical range and any value between the two endpoints can be selected. Since the steps and methods used are the same as in Examples 1 to 9, preferred embodiments are described in this invention to avoid redundancy. However, this invention is not limited to these, but can be implemented in other ways within the scope of the technical solutions defined in the appended claims. All raw materials, reagents, instruments, and equipment used in the following embodiments of this invention can be purchased from the market or prepared by existing methods.

[0028] The following detailed description, in conjunction with embodiments of the present invention and accompanying drawings, provides a clear and complete illustration of the technical solutions in these embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0029] Example 1 A method for preparing an antigen-oxygen composite thin film, employing a dry-wet composite process, with a composite structure of type A / B / C, specifically includes the following steps: Step 1: Prepare a 2% KH550 hydrolysate. After activating the polyimide film layer A using a plasma generator, immerse it in the 2% KH550 hydrolysate for 8 minutes. After removal, rinse with ethanol and place in a forced-air oven at 80°C for 30 minutes to cure, obtaining the KH550 modified polyimide film layer A.

[0030] Step 2: Mix the main agent and curing agent of polydimethylsiloxane at a mass ratio of 10:1, stir evenly, and place in a 30℃ vacuum oven for 20 minutes for vacuum degassing. Take an appropriate amount of the degassed polydimethylsiloxane and use a 5μm doctor blade to evenly coat it onto the KH550 modified polyimide film layer A. Place it in a forced-air oven at 70℃ for curing for 20 minutes to form a polydimethylsiloxane layer B on the polyimide film layer A, thus obtaining product 1.

[0031] Step 3: Activate product 1 using plasma, prepare a 3% BTESPD hydrolysate, spray the 3% BTESPD hydrolysate three times onto the activated product 1 using a spray bottle, allow it to air dry at room temperature for 30 minutes, and then place it in a forced-air oven at 80℃ for 50 minutes to cure, thus obtaining product 2.

[0032] Step 4: Place product 2 obtained in Step 3 into an ultra-vacuum magnetron sputtering instrument and sputter gold for 100 seconds to form a metallic gold catalyst layer C on the polydimethylsiloxane layer B, resulting in the product shown below. Figure 1 The A / B / C structure is shown.

[0033] Example 2 A method for preparing an antigen-oxygen composite thin film, employing a dry-wet composite process, with a composite structure of type A / B / C, specifically includes the following steps: A 1% KH550 hydrolysate was prepared. The polyimide film was activated using a plasma generator and then immersed in the 1% KH550 hydrolysate for 5 minutes. After removal, it was rinsed with ethanol and placed in a forced-air oven at 50°C for 10-60 minutes to obtain KH550 modified polyimide film layer A.

[0034] Step 2: Mix the main agent and curing agent of polydimethylsiloxane at a mass ratio of 5:1, stir evenly, and place in a 25℃ vacuum oven for 10 minutes for vacuum degassing. Take an appropriate amount of the degassed polydimethylsiloxane and use a 5μm doctor blade to evenly coat it onto the KH550 modified polyimide film layer A. Place it in a forced-air oven at 60℃ for curing for 10 minutes to form a polydimethylsiloxane layer B on the polyimide film layer A, thus obtaining product 1.

[0035] Step 3: Activate product 1 using plasma, prepare a 1% BTESPD hydrolysate, spray the 1% BTESPD hydrolysate twice onto the activated product 1 using a spray bottle, allow it to air dry at room temperature for 20 minutes, and then place it in a forced-air oven at 50°C for 10 minutes to cure, thus obtaining product 2.

[0036] Step 4: Place product 2 obtained in Step 3 into an ultra-vacuum magnetron sputtering instrument and sputter gold for 10 seconds to form a metallic gold catalyst layer C on the polydimethylsiloxane layer B, resulting in the product shown below. Figure 1 The A / B / C structure is shown.

[0037] Example 3 A method for preparing an antigen-oxygen composite thin film, employing a dry-wet composite process, with a composite structure of type A / B / C, specifically includes the following steps: Prepare an 8% KH550 hydrolysate, activate the polyimide film using a plasma generator, and then immerse it in the 8% KH550 hydrolysate for 10 minutes. After removal, rinse with ethanol and place in a forced-air oven at 100°C for 60 minutes to cure, obtaining KH550 modified polyimide film layer A.

[0038] Step 2: Mix the main agent and curing agent of polydimethylsiloxane at a mass ratio of 50:1, stir evenly, and place in a 40℃ vacuum oven for 30 minutes for vacuum degassing. Take an appropriate amount of the degassed polydimethylsiloxane and use a 5μm doctor blade to evenly coat it onto the KH550 modified polyimide film layer A. Place it in a forced-air oven at 80℃ for 60 minutes to cure, forming a polydimethylsiloxane layer B on the polyimide film layer A, thus obtaining product 1.

[0039] Step 3: Activate product 1 using plasma, prepare an 8% BTESPD hydrolysate, spray the 8% BTESPD hydrolysate three times onto the activated product 1 using a spray bottle, allow it to air dry at room temperature for 60 minutes, and then place it in a forced-air oven at 100℃ for 60 minutes to cure, thus obtaining product 2.

[0040] Step 4: Place product 2 obtained in Step 3 into an ultra-vacuum magnetron sputtering instrument and sputter gold for 150 seconds to form a metallic gold catalyst layer C on the polydimethylsiloxane layer B, resulting in the product shown below. Figure 1 The A / B / C structure is shown.

[0041] Example 4 The only difference between Example 4 and Example 1 is that the gold metal catalyst layer is replaced with zinc.

[0042] Example 5 The only difference between Example 5 and Example 1 is that the gold metal catalyst layer is replaced with cobalt.

[0043] Example 6 The only difference between Example 6 and Example 1 is that the gold metal catalyst layer is replaced with manganese.

[0044] Example 7 The only difference between Example 7 and Example 1 is that the gold metal catalyst layer is replaced with copper.

[0045] Example 8 The only difference between Example 8 and Example 1 is that the gold metal catalyst layer is replaced with nickel.

[0046] Example 9 The only difference between Example 9 and Example 1 is that the gold metal catalyst layer is replaced with silver.

[0047] Example 10 The difference between Example 10 and Example 1 is only that in step two, polydimethylsiloxane is replaced with polyhexylmethylsiloxane in the polysiloxane protective layer B. A 3% hexane solution of polymethylhydrosiloxane and a 15% hexane solution of 1-hexene are subjected to a hydrosilylation reaction at 60°C for 2 hours in the presence of a platinum catalyst to obtain a grafted polymer. Subsequently, a 10% hexane solution of 1,7-octadiene is added to the reaction system and a crosslinking reaction is carried out for 1 hour to obtain a casting solution, wherein the molar ratio of olefin to crosslinking agent is 95:5. The casting solution is coated onto a silane coupling agent modified polyimide film layer A and cured at 60°C to form polysiloxane protective layer B, resulting in product 1.

[0048] Example 11 The difference between Example 11 and Example 1 is only that in step two, polydimethylsiloxane is replaced with polyheptylmethylsiloxane in the polysiloxane protective layer B. A 3% hexane solution of polymethylhydrosiloxane and a 15% hexane solution of 1-heptene are subjected to a hydrosilylation reaction at 50°C for 2 hours in the presence of a platinum catalyst to obtain a grafted polymer. Subsequently, a 10% hexane solution of 1,7-octadiene is added to the reaction system and a crosslinking reaction is carried out for 1 hour to obtain a casting solution, wherein the molar ratio of olefin to crosslinking agent is 95:5. The casting solution is coated onto a silane coupling agent modified polyimide film layer A and cured at 50°C to form polysiloxane protective layer B, resulting in product 1.

[0049] Example 12 The difference between Example 12 and Example 1 is that in step two, polydimethylsiloxane is replaced with polyoctylmethylsiloxane in the polysiloxane protective layer B. A 3% hexane solution of polymethylhydrosiloxane and a 15% hexane solution of 1-octene are subjected to a hydrosilylation reaction at 80°C for 2 hours in the presence of a platinum catalyst to obtain a grafted polymer. Subsequently, a 10% hexane solution of 1,7-octadiene is added to the reaction system and a crosslinking reaction is carried out for 1 hour to obtain a casting solution, wherein the molar ratio of olefin to crosslinking agent is 95:5. The casting solution is coated onto a silane coupling agent modified polyimide film layer A and cured at 80°C to form polysiloxane protective layer B, resulting in product 1.

[0050] Example 13 The only difference between Example 13 and Example 10 is that in step two, the polysiloxane protective layer B is replaced with polydecylmethylsiloxane instead of polyhexylmethylsiloxane.

[0051] Example 14 The only difference between Example 14 and Example 10 is that in step two, the polysiloxane protective layer B is replaced with polyhexylmethylsiloxane instead of polydodecylmethylsiloxane.

[0052] Example 15 The only difference between Example 15 and Example 10 is that in step two, the polysiloxane protective layer B is replaced with polyhexylmethylsiloxane instead of polytetradecylmethylsiloxane.

[0053] Example 16 The only difference between Example 16 and Example 1 is that in step two, the polysiloxane protective layer B is replaced with plasma-polymerized hexamethyldisiloxane instead of polydimethylsiloxane. Hexamethyldisiloxane is deposited on the silane coupling agent modified polyimide film layer A using plasma-enhanced chemical vapor deposition equipment, and the vacuum degree of the equipment vacuum chamber is 4 × 10⁻⁶. −3 Pa, the hexamethyldisiloxane monomer is heated to 35°C in a water bath and turned into steam. The monomer flow rate is set to 30 sccm. It is mixed with oxygen at a flow rate of 50 sccm and added to a vacuum chamber. The working pressure of the vacuum chamber is 5 Pa. A polysiloxane protective layer B is formed on the polyimide film layer A to obtain product 1.

[0054] Example 17 The only difference between Example 17 and Example 1 is that in step two, the polysiloxane protective layer B is replaced with plasma-polymerized hexamethyldisiloxane instead of polydimethylsiloxane. Hexamethyldisiloxane is deposited onto the silane coupling agent modified polyimide film layer A using plasma-enhanced chemical vapor deposition equipment, and the vacuum level of the equipment vacuum chamber is 4 × 10⁻⁶. −3 Pa, the hexamethyldisiloxane monomer is heated to 20°C in a water bath and turned into steam. The monomer flow rate is set to 25 sccm. It is mixed with oxygen at a flow rate of 40 sccm and added to a vacuum chamber. The working pressure of the vacuum chamber is 5 Pa. A polysiloxane protective layer B is formed on the polyimide film layer A to obtain product 1.

[0055] Example 18 The only difference between Example 18 and Example 1 is that in step two, the polysiloxane protective layer B is replaced with plasma-polymerized hexamethyldisiloxane instead of polydimethylsiloxane. Hexamethyldisiloxane is deposited onto the silane coupling agent modified polyimide film layer A using plasma-enhanced chemical vapor deposition equipment, and the vacuum level of the equipment vacuum chamber is 4 × 10⁻⁶. −3Pa, the hexamethyldisiloxane monomer is heated to 50°C in a water bath and turned into steam. The monomer flow rate is set to 60 sccm. It is mixed with oxygen at a flow rate of 70 sccm and added to a vacuum chamber. The working pressure of the vacuum chamber is 5 Pa. A polysiloxane protective layer B is formed on the polyimide film layer A to obtain product 1.

[0056] Comparative Example 1 The only difference between Comparative Example 1 and Example 1 is that no silicone protective layer was established between the polyimide film and the metal catalyst layer.

[0057] A method for preparing an antigen-oxygen composite thin film with a metal catalyst layer combined with a polymer substrate, employing a dry process, specifically includes the following steps: The polyimide thin film layer A was placed in an ultra-vacuum magnetron sputtering instrument and sputtered gold for 100 seconds.

[0058] Comparative Example 2 The only difference between Comparative Example 2 and Example 1 is that KH550 was not used to modify the interface of the polyimide.

[0059] A method for preparing an antigen-oxygen composite film with an organic layer bonded to a polymer substrate, employing a wet process, specifically includes the following steps: Mix the polydimethylsiloxane main agent and curing agent at a mass ratio of 10:1, stir evenly, and place in a 30℃ vacuum oven for 20 minutes for vacuum degassing. Take an appropriate amount of the degassed polydimethylsiloxane and use a 5μm doctor blade to evenly coat it onto a polyimide film. Place in a forced-air oven at 70℃ for curing for 20 minutes.

[0060] Comparative Example 3 The only difference between Comparative Example 3 and Example 1 is that no metal catalyst layer was formed on top of the organosilicon protective layer.

[0061] A method for preparing an antigen-oxygen composite film with an organic layer bonded to a polymer substrate, employing a wet process, specifically includes the following steps: Step 1: Prepare a 2% KH550 hydrolysate. After activating the polyimide film layer A using a plasma generator, immerse it in the 2% KH550 hydrolysate for 8 minutes. After removing it, rinse it with ethanol and place it in a forced-air oven at 80°C for 30 minutes to cure it, thus obtaining the KH550 modified polyimide film layer A.

[0062] Step 2: Mix the main agent and curing agent of polydimethylsiloxane at a mass ratio of 10:1, stir evenly, and place in a 30℃ vacuum oven for 20 minutes for vacuum degassing. Take an appropriate amount of the degassed polydimethylsiloxane and use a 5μm scraper to evenly coat it onto the KH550 modified polyimide film layer A, and place it in a forced-air oven at 70℃ for curing for 20 minutes.

[0063] Comparative Example 4 The only difference between Comparative Example 4 and Example 1 is that the silicone protective layer was not modified with BTESPD.

[0064] A method for preparing an antigen-oxygen composite film with a polymer substrate modified by combining a metal catalytic layer and an organic layer, employing a dry-wet composite method, with a composite structure of type A / B / C, specifically including the following steps: Step 1: Prepare a 2% KH550 hydrolysate. After activating the polyimide film layer A using a plasma generator, immerse it in the 2% KH550 hydrolysate for 8 minutes. After removal, rinse with ethanol and place in a forced-air oven at 80°C for 30 minutes to cure, obtaining the KH550 modified polyimide film layer A.

[0065] Step 2: Mix the main agent and curing agent of polydimethylsiloxane at a mass ratio of 10:1, stir evenly, and place in a 30℃ vacuum oven for 20 minutes for vacuum degassing. Take an appropriate amount of the degassed polydimethylsiloxane and use a 5μm doctor blade to evenly coat it onto the KH550 modified polyimide film layer A. Place it in a forced-air oven at 70℃ for curing for 20 minutes to form a polydimethylsiloxane layer B on the polyimide film layer A, thus obtaining product 1.

[0066] Step 3: Place the product 1 obtained in Step 2 into an ultra-vacuum magnetron sputtering instrument and sputter gold for 100 seconds.

[0067] Comparative Example 5 Commercially available pure PI film.

[0068] Examples 1 to 18 all successfully prepared antigen-oxygen composite films with an A / B / C structure. The antigen-oxygen composite films prepared in Examples 1 and 4 to 9 are preferred, and their composite films prepared in Comparative Examples 1 to 5 are subjected to antigen-oxygen performance testing and ISO shedding level testing. The test structures are detailed in Table 1.

[0069] Atomic oxygen performance testing: The atomic oxygen ablation performance test was conducted in a space environment simulator built on the ground. The atomic oxygen flux was 1.23E21 atoms / cm². 2 The erosion rate is calculated by dividing the mass loss during atomic irradiation by the irradiated area, then by the atomic oxygen flux, and finally by the film density.

[0070] ISO Peel-off Grade Test: The ISO grade test is conducted according to the cross-cut test - ISO 2409. Eleven parallel lines are cut into the coating surface using a cross-cutting tool, then the sample is rotated 90° and cut again to form a grid pattern. 3M tape is applied to the grid area, and then the tape is quickly peeled off at a specified angle and speed. The degree of coating peeling in the grid area is observed and compared with the pictures and descriptions in the standard to determine the grade.

[0071] Table 1 shows the performance comparison results of the composite films of Example 1 and Comparative Examples 1 to 5. As shown in Table 1, after modifying the polyimide substrate with a combination of a metal catalyst layer and an organosilicon protective layer, the atomic oxygen ablation rate of the composite film prepared in Example 1 was only 1-2E-26 (cm). 3 After KH550 modification of the polyimide substrate, the ISO peeling level of the silicone protective layer was 0, indicating no peeling occurred. After BTESPD modification of the silicone protective layer, the ISO peeling level of the metal catalyst layer was also 0, indicating no peeling occurred. The atomic oxygen performance of the composite film with the A / B / C type composite structure was far superior to that of the composite film obtained in Comparative Example 1 without a silicone protective layer and Comparative Example 3 without a metal catalyst layer. When gold was used as the metal catalyst layer, the atomic oxygen performance was superior to that of the other six metals, such as the atomic oxygen ablation rate of Examples 1 and 4-9. This shows that after interface modification with silane coupling agent, the interlayer interface problem was perfectly solved, and no peeling occurred.

[0072] Example 19 A method for preparing an antigen-oxygen composite thin film, employing a dry-wet composite process, with a composite structure of type A / C / B, specifically includes the following steps: Step 1: Place the polyimide thin film layer A into an ultra-vacuum magnetron sputtering instrument and sputter gold for 100 seconds to form a metallic gold layer C on the polyimide thin film layer A, thus obtaining product 3.

[0073] Step 2: Prepare a 2% MPTMS hydrolysate. After activating the polyimide film layer A (product 3) with a metal gold layer C on its surface using plasma, immerse it in the 2% MPTMS hydrolysate for 8 minutes. After removing it, rinse it with ethanol and place it in a forced-air oven at 70°C for 30 minutes to cure it and obtain product 4.

[0074] Step 3: Mix the main agent and curing agent of polydimethylsiloxane at a mass ratio of 10:1, stir evenly, and place in a 30℃ vacuum oven for 20 minutes for vacuum degassing. Take an appropriate amount of the degassed polydimethylsiloxane and use a 5μm scraper to evenly coat it onto product 4. Place in a forced-air oven at 70℃ for curing for 40 minutes to obtain the desired product. Figure 2 The A / C / B structure is shown.

[0075] Example 20 A method for preparing an antigen-oxygen composite thin film, employing a dry-wet composite process, with a composite structure of type A / C / B, specifically includes the following steps: Step 1: Place the polyimide thin film layer A into an ultra-vacuum magnetron sputtering instrument and sputter gold for 10 seconds to form a metallic gold layer C on the polyimide thin film layer A, thus obtaining product 3.

[0076] Step 2: Prepare a 1% MPTMS hydrolysate. After activating the polyimide film layer A (product 3) with a metal gold layer C on its surface using plasma, immerse it in the 1% MPTMS hydrolysate for 5 minutes. After removing it, rinse it with ethanol and place it in a forced-air oven at 50°C for 10 minutes to cure it, thus obtaining product 4.

[0077] Step 3: Mix the main agent and curing agent of polydimethylsiloxane at a mass ratio of 5:1, stir evenly, and place in a 25℃ vacuum oven for 10 minutes for vacuum degassing. Take an appropriate amount of the degassed polydimethylsiloxane and use a 5μm scraper to evenly coat it onto product 4. Place it in a forced-air oven at 60℃ for curing for 10 minutes to obtain the desired product. Figure 2 The A / C / B structure is shown.

[0078] Example 21 A method for preparing an antigen-oxygen composite thin film, employing a dry-wet composite process, with a composite structure of type A / C / B, specifically includes the following steps: Step 1: Place the polyimide thin film layer A into an ultra-vacuum magnetron sputtering instrument and sputter gold for 150 seconds to form a metallic gold layer C on the polyimide thin film layer A, thus obtaining product 3.

[0079] Step 2: Prepare an 8% MPTMS hydrolysate. After activating the polyimide film layer A (product 3) with a metal gold layer C on its surface using plasma, immerse it in the 8% MPTMS hydrolysate for 10 minutes. After removing it, rinse it with ethanol and place it in a forced-air oven at 100°C for 60 minutes to cure it, thus obtaining product 4.

[0080] Step 3: Mix the main agent and curing agent of polydimethylsiloxane at a mass ratio of 50:1, stir evenly, and place in a 40℃ vacuum oven for 30 minutes for vacuum degassing. Take an appropriate amount of the degassed polydimethylsiloxane and use a 5μm scraper to evenly coat it onto product 4. Place in a forced-air oven at 80℃ for curing for 60 minutes to obtain the desired product. Figure 2 The A / C / B structure is shown.

[0081] Example 22 The only difference between Example 22 and Example 19 is that in step three, the polysiloxane protective layer B is replaced with polyhexylmethylsiloxane instead of polydimethylsiloxane. A 3% hexane solution of polymethylhydrosiloxane and a 15% hexane solution of 1-hexene are subjected to a hydrosilylation reaction at 60°C for 2 hours in the presence of a platinum catalyst to obtain a grafted polymer. Subsequently, a 10% hexane solution of 1,7-octadiene, a crosslinking agent, is added to the reaction system for a crosslinking reaction for 1 hour to obtain a casting solution, wherein the molar ratio of olefin to crosslinking agent is 95:5. The casting solution is then coated onto product 4 and cured at 50°C to form a film as shown in the figure. Figure 2 The A / C / B structure is shown.

[0082] Example 23 The only difference between Example 23 and Example 19 is that in step three, the polysiloxane protective layer B is replaced with polyheptanylmethylsiloxane instead of polydimethylsiloxane. A 3% hexane solution of polymethylhydrosiloxane and a 15% hexane solution of 1-heptene are subjected to a hydrosilylation reaction at 60°C for 2 hours in the presence of a platinum catalyst to obtain a grafted polymer. Subsequently, a 10% hexane solution of 1,7-octadiene, a crosslinking agent, is added to the reaction system for a crosslinking reaction for 1 hour to obtain a casting solution, wherein the molar ratio of olefin to crosslinking agent is 95:5. The casting solution is then coated onto product 4 and cured at 60°C to form a film as shown in the figure. Figure 2 The A / C / B structure is shown.

[0083] Example 24 The only difference between Example 24 and Example 19 is that in step three, the polysiloxane protective layer B is replaced with polyoctylmethylsiloxane instead of polydimethylsiloxane. A 3% hexane solution of polymethylhydrosiloxane and a 15% hexane solution of 1-octene are subjected to a hydrosilylation reaction at 60°C for 2 hours in the presence of a platinum catalyst to obtain a grafted polymer. Subsequently, a 10% hexane solution of 1,7-octadiene, a crosslinking agent, is added to the reaction system for a crosslinking reaction for 1 hour to obtain a casting solution, wherein the molar ratio of olefin to crosslinking agent is 95:5. The casting solution is then coated onto product 4 and cured at 80°C to form a film as shown in the figure. Figure 2 The A / C / B structure is shown.

[0084] Example 25 The only difference between Example 25 and Example 22 is that in step three, the polysiloxane protective layer B is replaced with polydecylmethylsiloxane instead of polyhexylmethylsiloxane.

[0085] Example 26 The only difference between Example 26 and Example 22 is that in step three, the polysiloxane protective layer B is replaced with polyhexylmethylsiloxane instead of polydodecylmethylsiloxane.

[0086] Example 27 The only difference between Example 27 and Example 22 is that in step three, the polysiloxane protective layer B is replaced with polyhexylmethylsiloxane instead of polytetradecylmethylsiloxane.

[0087] Example 28 The only difference between Example 28 and Example 19 is that in step three, the polysiloxane protective layer B is replaced with plasma-polymerized hexamethyldisiloxane instead of polydimethylsiloxane. Hexamethyldisiloxane is deposited onto product 4 using plasma-enhanced chemical vapor deposition equipment, with the vacuum level of the equipment's vacuum chamber being 4 × 10⁻⁶. −3 Pa, hexamethyldisiloxane monomer is heated to 20°C in a water bath to turn it into steam. The monomer flow rate is set to 30 sccm. It is mixed with oxygen at a flow rate of 50 sccm and added to a vacuum chamber. The working pressure of the vacuum chamber is 5 Pa. A polysiloxane protective layer B is formed on product 4 to obtain the following result: Figure 2 The A / C / B structure is shown.

[0088] Example 29 The only difference between Example 29 and Example 19 is that in step three, the polysiloxane protective layer B is replaced with plasma-polymerized hexamethyldisiloxane instead of polydimethylsiloxane. Hexamethyldisiloxane is deposited onto product 4 using plasma-enhanced chemical vapor deposition equipment, with a vacuum level of 4 × 10⁻⁶ in the equipment's vacuum chamber. −3 Pa, hexamethyldisiloxane monomer is heated to 50°C in a water bath to turn it into steam. The monomer flow rate is set to 25 sccm. It is mixed with oxygen at a flow rate of 40 sccm and added to a vacuum chamber. The working pressure of the vacuum chamber is 5 Pa. A polysiloxane protective layer B is formed on product 4 to obtain the desired result. Figure 2 The A / C / B structure is shown.

[0089] Example 30 The only difference between Example 30 and Example 19 is that in step three, the polysiloxane protective layer B is replaced with plasma-polymerized hexamethyldisiloxane instead of polydimethylsiloxane. Hexamethyldisiloxane is deposited onto product 4 using plasma-enhanced chemical vapor deposition equipment, with a vacuum level of 4 × 10⁻⁶ in the equipment's vacuum chamber. −3 Pa, hexamethyldisiloxane monomer is heated to 30°C in a water bath to turn it into steam. The monomer flow rate is set to 60 sccm. It is mixed with oxygen at a flow rate of 70 sccm and added to a vacuum chamber. The working pressure of the vacuum chamber is 5 Pa. A polysiloxane protective layer B is formed on product 4 to obtain the desired result. Figure 2 The A / C / B structure is shown.

[0090] Example 31 A method for preparing an antigen-oxygen composite thin film, using a wet process, wherein the composite structure is A / D type, specifically includes the following steps: Step 1: Prepare a 2% KH550 hydrolysate. After activating the polyimide film layer A using a plasma generator, immerse it in the 2% KH550 hydrolysate for 8 minutes. After removing it, rinse it with ethanol and place it in a forced-air oven at 80°C for 30 minutes to cure it, thus obtaining the silane coupling agent modified polyimide film layer A.

[0091] Step 2, Preparation as follows Figure 4 The gold nanoparticles shown were surface-modified using a 3% MPTMS / ethanol solution, stirred overnight, and then mixed with the main component of polydimethylsiloxane. A curing agent was added, and the mixture was stirred thoroughly. The mixture was then placed in a 30°C vacuum oven for 20 minutes for vacuum degassing. An appropriate amount of the degassed polydimethylsiloxane was then uniformly coated onto a silane coupling agent-modified polyimide film layer A, which had been activated by plasma. The film was then cured in a forced-air oven at 70°C for 50 minutes, forming a gold nanoparticle-polydimethylsiloxane composite layer D on polyimide film layer A, resulting in the desired product. Figure 3 The A / D structure shown indicates that the main agent and curing agent of the mixed polydimethylsiloxane are in a mass ratio of 10:1.

[0092] Example 32 A method for preparing an antigen-oxygen composite thin film, using a wet process, wherein the composite structure is A / D type, specifically includes the following steps: Step 1: Prepare a 1% KH550 hydrolysate. After activating the polyimide film layer A using a plasma generator, immerse it in a 2% KH550 hydrolysate for 5 minutes. After removing it, rinse it with ethanol and place it in a forced-air oven at 50°C for 10 minutes to cure it, thus obtaining the silane coupling agent modified polyimide film layer A.

[0093] Step 2, Preparation as follows Figure 4 The gold nanoparticles shown were surface-modified using a 4% MPTMS / ethanol solution, stirred overnight, and then mixed with the main component of polydimethylsiloxane. A curing agent was added, and the mixture was stirred thoroughly. The mixture was then placed in a 25°C vacuum oven for 10 minutes to remove air bubbles. An appropriate amount of the degassed polydimethylsiloxane was then evenly coated onto a silane coupling agent-modified polyimide film layer A, which had been activated by plasma. The film was then cured in a forced-air oven at 60°C for 10 minutes, resulting in a gold nanoparticle-polydimethylsiloxane composite layer D on polyimide film layer A. Figure 3 The A / D structure shown indicates that the main agent and curing agent of the mixed polydimethylsiloxane are in a mass ratio of 5:1.

[0094] Example 33 A method for preparing an antigen-oxygen composite thin film, using a wet process, wherein the composite structure is A / D type, specifically includes the following steps: Step 1: Prepare an 8% KH550 hydrolysate. After activating the polyimide film using a plasma generator, immerse it in a 4% KH550 hydrolysate for 10 minutes. After removing it, rinse it with ethanol and place it in a forced-air oven at 100°C for 60 minutes to cure.

[0095] Step 2, Preparation as follows Figure 4 The gold nanoparticles shown were surface-modified using an 8% MPTMS / ethanol solution, stirred overnight, and then mixed with the main component of polydimethylsiloxane. A curing agent was added, and the mixture was stirred thoroughly. The mixture was then placed in a 40°C vacuum oven for 30 minutes to remove air bubbles. An appropriate amount of the degassed polydimethylsiloxane was then evenly coated onto a silane coupling agent-modified polyimide film layer A, which had been activated by plasma. The film was then cured in a forced-air oven at 80°C for 60 minutes, resulting in a gold nanoparticle-polydimethylsiloxane composite layer D on polyimide film layer A. Figure 3 The A / D structure shown indicates that the main agent and curing agent of the mixed polydimethylsiloxane are in a mass ratio of 50:1.

[0096] Example 34 The difference between Example 34 and Example 31 is only that in step two, the polysiloxane protective layer B is replaced with polyhexylmethylsiloxane instead of polydimethylsiloxane. A 3% hexane solution of polymethylhydrosiloxane and a 15% hexane solution of 1-hexene are subjected to a hydrosilylation reaction at 60°C for 2 hours in the presence of a platinum catalyst to obtain a grafted polymer. Subsequently, nano-gold triangular sheets modified with a 2% silane coupling agent / ethanol solution after overnight stirring are added to the reaction system and stirred evenly. Then, a 10% hexane solution of 1,7-octadiene is added to the crosslinking agent and a crosslinking reaction is carried out for 1 hour to obtain a casting solution in which the molar ratio of olefin to crosslinking agent is 95:5. The casting solution is coated onto a silane coupling agent modified polyimide film layer A after plasma activation. After curing at 60°C, a nano-metal-polysiloxane composite functional layer D is formed on the polyimide film layer A, resulting in the desired product. Figure 3 The A / D structure is shown.

[0097] Example 35 The difference between Example 35 and Example 31 is only that in step two, the polysiloxane protective layer B is replaced with polyheptanylmethylsiloxane instead of polydimethylsiloxane. A 3% hexane solution of polymethylhydrosiloxane and a 15% hexane solution of 1-heptene are subjected to a hydrosilylation reaction at 60°C for 2 hours in the presence of a platinum catalyst to obtain a grafted polymer. Subsequently, nano-gold triangular sheets modified with a 6% silane coupling agent / ethanol solution after overnight stirring are added to the reaction system and stirred evenly. Then, a 10% hexane solution of 1,7-octadiene is added to the crosslinking agent and a crosslinking reaction is carried out for 1 hour to obtain a casting solution in which the molar ratio of olefin to crosslinking agent is 95:5. The casting solution is coated onto a silane coupling agent modified polyimide film layer A after plasma activation. After curing at 70°C, a nano-metal-polysiloxane composite functional layer D is formed on the polyimide film layer A, resulting in the desired product. Figure 3 The A / D structure is shown.

[0098] Example 36 The difference between Example 36 and Example 31 is only that in step two, the polysiloxane protective layer B is replaced with polyoctylmethylsiloxane instead of polydimethylsiloxane. A 3% hexane solution of polymethylhydrosiloxane and a 15% hexane solution of 1-octene are subjected to a hydrosilylation reaction at 60°C for 2 hours in the presence of a platinum catalyst to obtain a grafted polymer. Subsequently, nano-gold triangular sheets modified with an 8% silane coupling agent / ethanol solution after overnight stirring are added to the reaction system and stirred evenly. Then, a 10% hexane solution of 1,7-octadiene is added to perform a crosslinking reaction for 1 hour to obtain a casting solution in which the molar ratio of olefin to crosslinking agent is 95:5. The casting solution is coated onto a silane coupling agent modified polyimide film layer A after plasma activation. After curing at 80°C, a nano-metal-polysiloxane composite functional layer D is formed on the polyimide film layer A, resulting in the desired product. Figure 3 The A / D structure is shown.

[0099] Example 37 The only difference between Example 37 and Example 34 is that in step two, the polysiloxane protective layer B is replaced with polydecylmethylsiloxane instead of polyhexylmethylsiloxane.

[0100] Example 38 The only difference between Example 38 and Example 34 is that in step two, the polysiloxane protective layer B is replaced with polyhexylmethylsiloxane instead of polydodecylsiloxane.

[0101] Example 39 The only difference between Example 39 and Example 34 is that in step two, the polysiloxane protective layer B is replaced with polyhexylmethylsiloxane instead of polytetradecylmethylsiloxane.

[0102] Comparative Example 6 The only difference between Comparative Example 6 and Example 19 is that MPTMS was not used to modify the interface of the metal catalyst layer.

[0103] A method for preparing an antigen-oxygen composite film with a polymer substrate modified by combining a metal catalytic layer and an organic layer, employing a dry-wet composite method, with a composite structure of type A / C / B, specifically including the following steps: Step 1: Place the polyimide thin film layer A into an ultra-vacuum magnetron sputtering instrument and sputter gold for 100 seconds to form a metallic gold layer C on the polyimide thin film layer A, thus obtaining product 3.

[0104] Step 2: Mix the main agent and curing agent of polydimethylsiloxane at a mass ratio of 10:1, stir evenly, and place in a 30℃ vacuum oven for 20 minutes for vacuum degassing. Take an appropriate amount of the degassed polydimethylsiloxane and use a 5μm scraper to evenly coat it onto product 3, then place it in a forced-air oven at 70℃ for curing for 40 minutes.

[0105] Comparative Example 7 The only difference between Comparative Example 7 and Example 31 is that MPTMS was not used to modify the interface of the gold nanoparticles.

[0106] A method for preparing an antigen-oxygen composite thin film with a metal catalytic layer and an organic layer combined and modified on a polymer substrate, using a wet process, wherein the composite structure is of type A / D, specifically including the following steps: Step 1: Prepare a 2% KH550 hydrolysate. After activating the polyimide film layer A using a plasma generator, immerse it in the 2% KH550 hydrolysate for 8 minutes. After removing it, rinse it with ethanol and place it in a forced-air oven at 80°C for 30 minutes to cure it, thus obtaining the silane coupling agent modified polyimide film layer A.

[0107] Step 2: Prepare nano-gold triangular sheets, mix them with the main component of polydimethylsiloxane, add a curing agent, stir evenly, and place in a 30℃ vacuum oven for 20 minutes for vacuum degassing. Take an appropriate amount of the degassed polydimethylsiloxane and use a 5μm doctor blade to evenly coat it onto the silane coupling agent modified polyimide film layer A after plasma activation. Place it in a forced-air oven at 70℃ for 50 minutes to cure, forming a nano-gold-polydimethylsiloxane composite layer D on the polyimide film layer A, obtaining an A / D structure. The main component of the mixed polydimethylsiloxane and the curing agent are in a mass ratio of 10:1.

[0108] Examples 19-30 all successfully prepared antigen-oxygen composite films with an A / C / B structure, with the antigen-oxygen composite film prepared in Example 19 being preferred. Examples 31-39 all successfully prepared antigen-oxygen composite films with an A / D structure, with the antigen-oxygen composite film prepared in Example 31 being preferred. Antigenic oxygen performance and ISO shedding level tests were performed on the composite films prepared in Comparative Examples 5-7, respectively. The test results are detailed in Table 2. Table 2 shows the performance comparison results of the composite films of Examples 19, 31 and Comparative Examples 1-7.

[0109] Table 2 compares the antigenic oxygen performance and ISO shedding grade of the composite films prepared in Examples 19, 31, and Comparative Examples 6-7 with the pure, unmodified polyimide film of Comparative Example 5. The difference between Comparative Example 6 and Example 17 is that MPTMS was not used to modify the metal catalyst layer at the interface. As shown in Table 2, the antigenic oxygen performance of Examples 31 and 19 is superior to that of the pure polyimide film. After the metal catalyst layer was modified with MPTMS, the ISO shedding grade of the organosilicon protective layer was 0, indicating no shedding. This demonstrates that regardless of whether it is an A / C / B type composite structure or an A / D type composite structure, the composite films obtained after establishing the metal catalyst layer and organosilicon protective layer not only have excellent antigenic oxygen performance, but also, after modification with a silane coupling agent, the interfacial interaction problem between layers is perfectly solved, with no shedding.

[0110] The preparation methods of polysiloxane protective layer B in Examples 10-15, Examples 22-27, and Examples 34-39 above are all based on the literature (Borisov et al., Materials Today Chemistry, 2021, 22, 100598, “Influence of side chains assembly on the structure and transport properties of comb-like polysiloxanes in hydrocarbon separation)). Experimental Test Figure 5 These are atomic force microscopy images of the A / B / C type composite thin film prepared in Example 1 before and after AO irradiation, wherein... Figure 5 The left image in the image is an atomic force microscopy photograph of the A / B / C type composite thin film before AO irradiation. Figure 5The right image in the image is an atomic force microscope photograph of the A / B / C type composite film after AO irradiation. By comparison, it can be seen that the surface of the A / B / C type composite film is slightly raised after AO irradiation.

[0111] Figure 6 The infrared spectra of the A / B / C type composite film prepared in Example 1 before and after AO irradiation are shown below. Figure 6 It can be seen that the structure of the A / B / C type composite film did not change significantly before and after irradiation.

[0112] Figure 7 The graphs show the cross-cut adhesion test results for six composite films: Example 1, Example 19, Comparative Examples 2-4, and Comparative Example 6. Figure 7 The top left image in the diagram is a cross-cut adhesion test result from Comparative Example 2. Figure 7 The lower left image in the figure shows the adhesion test results of the cross-cut adhesion test in Comparative Example 3. Figure 7 The upper middle image shows the adhesion test results of the cross-cut adhesion test in Comparative Example 4. Figure 7 The lower middle figure is a cross-cut adhesion test diagram of Example 1. Figure 7 The upper right image in the figure shows the adhesion test results of the cross-cut adhesion test in Comparative Example 6. Figure 7 The lower right figure shows the cross-cut adhesion test results of Example 19. As shown in the figure, after the composite film was modified at the interface with a silane coupling agent, the interlayer adhesion was enhanced, and the ISO peeling level was 0, indicating that no peeling occurred.

[0113] Figure 8 The cross-cut adhesion test chart for the composite film with the A / D type composite structure prepared in Example 31 is shown below. Figure 8 It can be seen that the ISO peeling level of the composite film is 0, indicating that no peeling occurred.

[0114] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. An antigen-oxygen composite thin film, characterized in that, The antigen-oxygen composite film is one of the following structures: A / B / C, A / C / B, or A / D. The A / B / C structure is formed by stacking a polyimide membrane substrate A, a polysiloxane protective layer B, and a metal catalytic layer C from bottom to top. The A / C / B structure is formed by stacking polyimide membrane substrate A, metal catalyst layer C and polysiloxane protective layer B from bottom to top. The A / D structure is formed by stacking a polyimide film substrate A and a nano-metal-polysiloxane composite functional layer D from bottom to top. In the A / B / C structure, the polyimide membrane substrate A and the polysiloxane protective layer B are modified at the interface by a silane coupling agent; in the A / C / B structure, the metal catalyst layer C is modified at the interface by a silane coupling agent; and in the A / D structure, the nano-metal-polysiloxane composite functional layer D is modified at the interface by a silane coupling agent.

2. The antigen-oxygen composite film according to claim 1, characterized in that, The silane coupling agent used for interface modification of the polyimide film substrate A is an aminosilane coupling agent; the silane coupling agent used for interface modification of the polysiloxane protective layer B is bis-[3-(triethoxysilane)propyl] disulfide; and the silane coupling agent used for interface modification of the metal catalyst layer C or the nano-metal-polysiloxane composite functional layer D is a mercaptosilane coupling agent.

3. The antigen-oxygen composite film according to claim 2, characterized in that, The silane coupling agent used for interface modification of the polyimide membrane substrate A is 3-aminopropyltriethoxysilane.

4. The antigen-oxygen composite film according to claim 2, characterized in that, The silane coupling agent used for interface modification of the metal catalyst layer C or the nano-metal-polysiloxane composite functional layer D is 3-mercaptopropyltrimethoxysilane.

5. The antigen-oxygen composite film according to claim 1, characterized in that, The metal catalyst layer C is made of one of gold, zinc, cobalt, manganese, copper, nickel or silver.

6. The antigen-oxygen composite film according to claim 1, characterized in that, The polysiloxane protective layer B is made of one of polydimethylsiloxane, comb-like alkyl polysiloxane, or plasma-polymerized hexamethyldisiloxane. The comb-shaped alkyl polysiloxane is obtained by crosslinking polymethylhydrosiloxane with terminal olefins via hydrosilylation reaction. The side chain of the comb-shaped alkyl polysiloxane is C6-C. 14 The straight-chain alkyl group; and the straight-chain alkyl group is one of hexyl, heptyl, octyl, decyl, dodecyl or tetradecyl.

7. The method for preparing the antigen-oxygen composite thin film according to claim 6, characterized in that, When the antigen-oxygen composite film has an A / B / C structure, the preparation method includes the following steps: After plasma activation, polyimide film layer A is immersed in a silane coupling agent hydrolysate solution with a concentration of 1% to 8% for 5 min to 10 min, then taken out, rinsed and cured at 50℃ to 100℃ for 10 min to 60 min to obtain silane coupling agent modified polyimide film layer A. The preparation steps for forming a polysiloxane protective layer B on a silane coupling agent modified polyimide film layer A to obtain product 1 are as follows: The main agent of polydimethylsiloxane and the curing agent are mixed at a mass ratio of 5~50:1, and after stirring, heating, and vacuum degassing, the mixture is coated onto the silane coupling agent modified polyimide film layer A, and cured at 60℃~80℃ for 10min~60min; or polymethylhydrosiloxane is mixed with C6~C 14 Terminal olefins undergo hydrosilylation reactions at 50°C–80°C in the presence of a platinum catalyst to obtain grafted polymers. Subsequently, a crosslinking agent is added to the reaction system to induce a crosslinking reaction, yielding a casting solution. This casting solution is then coated onto a silane coupling agent-modified polyimide film layer A and cured at 50°C–80°C to form the final film. Alternatively, hexamethyldisiloxane can be deposited onto the silane coupling agent-modified polyimide film layer A using plasma-enhanced chemical vapor deposition (PECVD), with the vacuum level of the vacuum chamber set to 4 × 10⁻⁶. −3 Pa, the hexamethyldisiloxane monomer is heated to 20℃~50℃ in a water bath and turned into steam. The monomer flow rate is set to 25sccm~60sccm. It is mixed with oxygen at a flow rate of 40sccm~70sccm and added to the vacuum chamber. The working pressure of the vacuum chamber is 5Pa. After plasma activation of product 1, a 1% to 8% silane coupling agent hydrolysate was sprayed onto the activated product 1 2 to 3 times. After natural drying at room temperature for 20 to 60 minutes, the product 2 was obtained by heating and curing at 50 to 100°C for 10 to 60 minutes. Product 2 was subjected to vacuum magnetron sputtering of metallic gold for 10s to 150s to obtain an A / B / C structure.

8. The method for preparing the antigen-oxygen composite thin film according to claim 6, characterized in that, When the antigen-oxygen composite film has an A / C / B structure, the preparation method includes the following steps: The polyimide thin film layer A was subjected to ultra-vacuum magnetron sputtering of metallic gold for 10s to 150s to form a metal catalyst layer C on the polyimide thin film layer A, resulting in product 3. After activating product 3 with plasma, it is immersed in a 1% to 8% silane coupling agent hydrolysate for 5 to 10 minutes. After being removed, it is rinsed and cured at 50°C to 100°C for 10 to 60 minutes to obtain product 4. The steps for forming a polysiloxane protective layer B on product 4 are as follows: The main agent of polydimethylsiloxane and the curing agent are mixed at a mass ratio of 5~50:

1. After stirring, heating, and vacuum degassing, the mixture is applied to product 4 and cured at 60℃~80℃ for 10min~60min to obtain an A / C / B structure; or polymethylhydrosiloxane is combined with C6~C 14 The terminal olefins underwent a hydrosilylation reaction at 50℃~80℃ in the presence of a platinum catalyst to obtain a grafted polymer; subsequently, a crosslinking agent was added to the reaction system to carry out a crosslinking reaction, yielding a casting solution; the casting solution was then coated onto product 4 and cured at 50℃~80℃ to obtain an A / C / B structure; or hexamethyldisiloxane was deposited onto product 4 using plasma-enhanced chemical vapor deposition equipment, with the vacuum degree of the equipment vacuum chamber being 4×10⁻⁶. −3 Pa, hexamethyldisiloxane monomer is heated to 20℃~50℃ in a water bath to become steam, the monomer flow rate is set to 25~60 sccm, mixed with oxygen at a flow rate of 40~70 sccm, and added to a vacuum chamber with a working pressure of 5 Pa, to form a polysiloxane protective layer B on the metal catalyst layer C, thus obtaining the A / C / B structure.

9. The method for preparing the antigen-oxygen composite thin film according to claim 6, characterized in that, When the antigen-oxygen composite film has an A / D structure, the preparation method includes the following steps: After plasma activation, polyimide film layer A is immersed in a 1% to 8% silane coupling agent hydrolysate for 5 to 10 minutes. After rinsing, it is cured at 50°C to 100°C for 10 to 60 minutes to obtain silane coupling agent modified polyimide film layer A. The surface of the nano-gold triangle sheet was modified by a 2%–8% silane coupling agent / ethanol solution. After stirring overnight, it was mixed with the main agent of polydimethylsiloxane and a curing agent was added. After stirring, the mixture was degassed and coated onto a plasma-activated and silane coupling agent-modified polyimide film layer A. After curing at 60℃–80℃ for 10 min–60 min, a nano-metal-polysiloxane composite functional layer D was formed on the polyimide film layer A, resulting in an A / D structure. The mass ratio of the main agent of polydimethylsiloxane to the curing agent was 5–50:

1. Or combine polymethylhydrosiloxane with C6-C 14 Terminal olefins undergo hydrosilylation in the presence of a platinum catalyst at 50°C–80°C to obtain a grafted polymer. Subsequently, nano-gold triangular sheets modified with a 2%–8% silane coupling agent / ethanol solution and stirred overnight are added to the reaction system and stirred until homogeneous. Then, a crosslinking agent is added to carry out a crosslinking reaction to obtain a casting solution. The casting solution is coated onto a silane coupling agent modified polyimide film layer A after plasma activation. After curing at 50°C–80°C, a nano-metal-polysiloxane composite functional layer D is formed on the polyimide film layer A, resulting in an A / D structure.

10. The application of the antigen-oxygen composite film according to claim 1 in spacecraft surface protection.

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