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CN-122011469-A - Antigen-oxygen composite film, preparation method and application

CN122011469ACN 122011469 ACN122011469 ACN 122011469ACN-122011469-A

Abstract

The invention belongs to the technical field of aerospace materials, and particularly relates to an antigen sub-oxygen composite film, a preparation method and application thereof. Wherein A is a polymer substrate, B is an organosilicon protective layer, C is a metal catalytic layer, and D is a composite functional layer formed by dispersing nano metal particles in an organosilicon matrix. The antigenic oxygen composite film prepared by the invention can reform and convert high-energy AO into O 2 in time and release energy to reduce the strong oxidation of the surface high-energy AO to the coating, further slow down or even stop the chain degradation reaction of the organosilicon polymer, and cooperate with the flexible organosilicon coating to limit the diffusion rate of AO, thereby being hopeful to inhibit the oxidation and the ablation of AO to the polymer substrate. Through triple optimization of the structure, the material and the interface, the excellent and durable antigen oxygen capability is obtained, and the method is suitable for protecting the surface of a spacecraft.

Inventors

  • GAO WENSHENG
  • SHI JIAOJIAO
  • LIU CAN

Assignees

  • 兰州大学

Dates

Publication Date
20260512
Application Date
20260326

Claims (10)

  1. 1. An atomic oxygen resistant composite film is characterized in that the atomic oxygen resistant composite film is one of an A/B/C structure, an A/C/B structure or an A/D structure; The A/B/C structure is formed by sequentially laminating a polyimide film 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 sequentially laminating a polyimide film substrate A, a metal catalytic layer C and a polysiloxane protective layer B from bottom to top; The A/D structure is formed by sequentially laminating 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 film substrate A and the polysiloxane protective layer B are subjected to interface modification through a silane coupling agent, in the A/C/B structure, the metal catalytic layer C is subjected to interface modification through the silane coupling agent, and in the A/D structure, the nano metal-polysiloxane composite functional layer D is subjected to interface modification through the silane coupling agent.
  2. 2. The atomic oxygen resistant composite film according to claim 1, wherein the silane coupling agent for interface modification of the polyimide film substrate a is an aminosilane coupling agent, the silane coupling agent for interface modification of the polysiloxane protecting layer B is bis- [3- (triethoxysilane) propyl ] disulfide, and the silane coupling agent for interface modification of the metal catalytic layer C or the nano metal-polysiloxane composite functional layer D is a mercapto silane coupling agent.
  3. 3. The protoxide composite film according to claim 2, wherein the silane coupling agent for interface modification of the polyimide film substrate a is 3-aminopropyl triethoxysilane.
  4. 4. The atomic oxygen resisting composite film according to claim 2, wherein the silane coupling agent for interface modification of the metal catalytic layer C or the nano metal-polysiloxane composite functional layer D is 3-mercaptopropyl trimethoxy silane.
  5. 5. The atomic oxygen composite film according to claim 1, wherein the metal catalyst layer C is made of one of gold, zinc, cobalt, manganese, copper, nickel or silver.
  6. 6. The atomic oxygen composite film according to claim 1, wherein the polysiloxane protective layer B is made of one of polydimethylsiloxane, pectinate alkyl polysiloxane or plasma polymerized hexamethyldisiloxane; The comb-shaped alkyl polysiloxane is obtained by crosslinking polymethyl hydrosiloxane and terminal olefin through hydrosilylation reaction, the side chain of the comb-shaped alkyl polysiloxane is linear alkyl of C 6 -C 14 , and the linear alkyl is one of hexyl, heptyl, octyl, decyl, dodecyl or tetradecyl.
  7. 7. The method for producing an atomic oxygen resistant composite film according to claim 6, wherein when the atomic oxygen resistant composite film has an a/B/C structure, the method comprises the steps of: after plasma activation is carried out on the polyimide film layer A, the polyimide film layer A is soaked in silane coupling agent hydrolysate with the concentration of 1% -8% for 5 min-10 min, and is taken out to be washed and cured at 50 ℃ -100 ℃ for 10 min-60 min, so that the silane coupling agent modified polyimide film layer A is obtained; The preparation method comprises the steps of mixing a main agent of polydimethylsiloxane with a curing agent according to a mass ratio of 5-50:1, stirring, heating and vacuum defoamating, then scraping and coating the mixture on the polyimide film layer A modified by the silane coupling agent, heating and curing the mixture for 10-60 min at 60-80 ℃, or performing hydrosilylation reaction on the polymethylhydrosiloxane and terminal olefin of C 6 ~C 14 at 50-80 ℃ in the presence of a platinum catalyst to obtain a grafted polymer, then adding a cross-linking agent into a reaction system to perform cross-linking reaction to obtain a casting film liquid, scraping and coating the casting film liquid on the polyimide film layer A modified by the silane coupling agent, curing the polyimide film layer A at 50-80 ℃, or using plasma enhanced chemical vapor deposition equipment to deposit hexamethyldisiloxane on the polyimide film layer A modified by the silane coupling agent, wherein the vacuum degree of a vacuum chamber of the equipment is 4 x 10 Pa −3 , heating the hexamethyldisiloxane monomer to 20-50 ℃ in a water bath, setting the vacuum chamber to be in a vacuum chamber with the vacuum flow of 60-70 Pa, and setting the vacuum flow of the polyimide monomer to be 60-70 cm; After the product 1 is subjected to plasma activation, spraying a silane coupling agent hydrolysate with the concentration of 1% -8% on the activated product 1 for 2-3 times, naturally drying at room temperature for 20-60 min, and heating and curing at 50-100 ℃ for 10-60 min to obtain a product 2; and carrying out vacuum magnetron sputtering on the product 2 for 10-150 s of metal gold to obtain an A/B/C structure.
  8. 8. The method for preparing an atomic oxygen resistant composite film according to claim 6, wherein when the atomic oxygen resistant composite film has an a/C/B structure, the method comprises the steps of: Performing super-vacuum magnetron sputtering on the polyimide film layer A for 10-150 s of metal gold, and forming a metal catalytic layer C on the polyimide film layer A to obtain a product 3; After the product 3 is activated by using plasma, soaking the product in a silane coupling agent hydrolysate with the concentration of 1% -8% for 5 min-10 min, taking out the product, and then washing and curing the product at 50 ℃ -100 ℃ for 10 min-60 min to obtain a product 4; The method for forming the polysiloxane protective layer B on the product 4 comprises the steps of mixing a main agent of polydimethylsiloxane and a curing agent according to a mass ratio of 5-50:1, stirring, heating and vacuum defoamating, then scraping and coating the mixture on the product 4, heating and curing the mixture for 10-60 min at 60-80 ℃ to obtain an A/C/B structure, or carrying out hydrosilylation reaction on the polymethylhydrosiloxane and terminal olefin of C 6 ~C 14 at 50-80 ℃ in the presence of a platinum catalyst to obtain a grafted polymer, then adding a cross-linking agent into a reaction system to carry out cross-linking reaction to obtain a casting solution, scraping and coating the casting solution on the product 4 at 50-80 ℃ to obtain an A/C/B structure, or depositing hexamethyldisiloxane on the product 4 by using plasma enhanced chemical vapor deposition equipment, heating a hexamethyldisiloxane monomer to 70-5 Pa in a water bath to obtain a vacuum degree of 4X 10 −3 Pa, changing the hexamethyldisiloxane monomer into steam, setting the monomer flow to 25-60 cm, adding the monomer flow to the polysiloxane at 70-60 cm, and forming the metal protective layer on the vacuum protective layer at 70-5 Pa.
  9. 9. The method for preparing an atomic oxygen resistant composite film according to claim 6, wherein when the atomic oxygen resistant composite film has an a/D structure, the method comprises the steps of: After plasma activation is carried out on the polyimide film layer A, the polyimide film layer A is soaked in silane coupling agent hydrolysate with the concentration of 1% -8% for 5 min-10 min, and is taken out, washed and cured at 50 ℃ -100 ℃ for 10 min-60 min, so that the silane coupling agent modified polyimide film layer A is obtained; Carrying out surface modification on the nano gold triangular plate by using a silane coupling agent/ethanol solution with the concentration of 2% -8%, mixing the nano gold triangular plate with a main agent of polydimethylsiloxane after stirring overnight, adding a curing agent, uniformly stirring, carrying out defoamation, then spreading the mixture on a polyimide film layer A which is activated by plasma and modified by the silane coupling agent, and carrying out heating and curing for 10-60 min at 60-80 ℃ to form a nano metal-polysiloxane composite functional layer D on the polyimide film layer A, thereby obtaining an A/D structure, wherein the mass ratio of the main agent of polydimethylsiloxane to the curing agent is 5-50:1; Or carrying out hydrosilylation reaction on polymethyl hydrosiloxane and C 6 -C 14 terminal olefin at 50-80 ℃ in the presence of a platinum catalyst to obtain a graft polymer, then adding a nano gold triangular plate which is subjected to surface modification by a silane coupling agent/ethanol solution with concentration of 2-8% after being stirred overnight into a reaction system, uniformly stirring, then adding a cross-linking agent to carry out cross-linking reaction to obtain casting solution, carrying out knife coating on the casting solution on a polyimide film layer A modified by the silane coupling agent after plasma activation, and forming a nano metal-polysiloxane composite functional layer D on the polyimide film layer A after curing at 50-80 ℃ to obtain an A/D structure.
  10. 10. The use of the atomic oxygen resistant composite film according to claim 1 in the surface protection of a spacecraft.

Description

Antigen-oxygen composite film, preparation method and application Technical Field The invention belongs to the technical field of aerospace materials, and particularly relates to an atomic oxygen antigen composite film, a preparation method and application thereof. Background Polymer materials represented by Polyimide (PI) have been widely used in various types of spacecraft by virtue of excellent properties such as excellent flexibility, optical properties, mechanical strength, thermal stability, and light weight. In the service process of the spacecraft, severe space environments such as various charged particle irradiation, space ultraviolet radiation, high-low temperature alternation, high vacuum deflation, space debris impact, high-energy Atomic Oxygen (AO) corrosion and the like need to be dealt with, so that extremely high requirements are placed on the tolerance of various structural and functional materials in the spacecraft. The AO is mainly distributed in Low Earth Orbit environment (LEO, 200-700 km) of space station and other spacecrafts, and the particles have non-negligible corrosion damage effect on the spacecrafts. AO is caused by ultraviolet light dissociating O 2 molecules at the top of the atmosphere, and because the environment is in a relatively high vacuum condition, the average free path of AO is large (108 m), so that O 2 or O 3 molecules are difficult to recombine. This allows the AO density to reach up to 10 9atoms/cm2. When a low orbit spacecraft (space station, etc.) is flown at a speed of about 8km/s, the AO beam density impinging on the spacecraft increases to 2.0 x 10 15atoms/cm2 s. Unlike other ray particles, AO is a high-energy (4.2-5.1 eV) atom with high oxidation activity, and when the AO impacts a polymer material at a high speed, covalent bonds of polymer molecular chains are rapidly broken to cause breakage of the polymer molecular chains and decomposition of fragment molecules, and the change of the quality, the surface morphology, the strength and the photoelectric performance of the polymer material is represented as AO effect. When a spacecraft is in such a high-energy, high-oxidability AO-gas layer for a long period of time, the performance and in-orbit service life of each main technical subsystem of the spacecraft are directly affected. The simulation of the ground experiment of the American aviation and aerospace agency (NASA) and the space flight experiment show that the degradation rate of AO to PI is as high as 3.0 multiplied by 10 -24cm3/atom in 300 km-400 km space station orbit height, and PI material with the thickness of 25 μm can be degraded by AO in half a year, so that the failure of the lower layer load can be caused, and the design requirement of resisting 7.83 multiplied by 10 22atom/cm2 irradiation flux (namely equivalent 15 years) can not be met. Significant effects caused by the AO effect draw great attention in the aerospace scientific research and aerospace industry, and especially for development and research of long-life low-earth orbit spacecrafts and manned aerospace stations in aerospace engineering, the AO effect is an important scientific and engineering problem which must be fully recognized and studied and solved. How to further improve the AO resistance of a PI-based protective layer on a low-orbit spacecraft is an important challenge for the development of aerospace technology. The high-flexibility organosilicon/PI composite film is one of the most efficient AO protective coatings reported at home and abroad at present. The protective coating has strong interfacial adhesion, high transparency and high flexibility, has strong AO protective performance and self-repairing characteristic, and more importantly, the model of a certain type of coating meets the design requirement of the protection of the prior low-orbit aircraft, is successfully applied to a plurality of aircraft tasks and realizes commercialization. However, the protective film has a failure induction period with a certain period of time, when the AO flux exceeds 2.5X10 22atom/cm2 (namely after 5 years of equivalent) or the irradiation dose is continuously increased, the surface flexible organosilicon component is further converted into silicon dioxide with high modulus or even completely converted into silicon dioxide, so that interface separation and surface tortoise cracks are generated under the action of interface stress, and finally the effective protection of a bottom substrate is lost, thus hidden danger is buried for the safe operation of a long-service-life aircraft. Therefore, developing a new protection strategy further improves the AO resistance of the organic silicon flexible protection coating and has great practical value. Disclosure of Invention Aiming at the defects of the prior art, the invention aims to provide an antigen-oxygen composite film, a preparation method and application thereof, and the prepared antigen-oxygen composite film is hope