Self-repairing antibacterial aerospace cabin composite material and preparation method thereof

Abstract

The present application relates to the technical field of aerospace cabin composite materials, and particularly relates to a self-repairing antibacterial aerospace cabin composite material and a preparation method thereof, the composite material comprises the following components by weight: 100 parts of an epoxy resin matrix, 0.5-5 parts of nano zinc oxide, 1-10 parts of a copper-based metal organic framework, 3-15 parts of sulfur-containing microcapsules, 30-40 parts of a curing agent, and 5-20 parts of a healing agent, firstly, the synergistic effect of nano ZnO and Cu-MOF not only provides sustained broad-spectrum antibacterial ability, but also unexpectedly enhances the ultraviolet protection performance of the material, which is particularly important in the space environment full of high-energy radiation. Secondly, the sulfur-containing compounds released during the self-repairing process not only repair the cracks, but also produce secondary coordination with Cu-MOF, forming a dynamic self-adaptive antibacterial network, further improving the long-term antibacterial performance of the material.

Description

Technical Field

[0001] This invention relates to the field of aerospace cabin composite materials technology, and in particular to self-healing antibacterial aerospace cabin composite materials and their preparation methods. Background Technology

[0002] As humanity's exploration of the universe deepens, spacecraft hull materials face unprecedented challenges. During long space missions, hulls must not only withstand external threats such as extreme temperature changes, high-energy radiation, and micrometeorite impacts, but also address the potential risks posed by internal microbial contamination. While traditional spacecraft hull materials excel in mechanical properties and radiation resistance, they still exhibit significant shortcomings in long-term antibacterial and self-healing capabilities.

[0003] In existing technologies, some researchers have attempted to add antibacterial agents directly to composite materials or coat the material surface with antibacterial coatings. However, these methods often suffer from problems such as rapid decay of antibacterial effects and poor durability. On the other hand, while some self-healing materials perform well in terrestrial applications, their stability and reliability in aerospace environments still need to be verified. Furthermore, attempts to organically combine antibacterial and self-healing functions are extremely rare, let alone their application in the aerospace field. Summary of the Invention

[0004] The self-healing antibacterial aerospace cabin composite material of the present invention is designed to address the above-mentioned problems. By cleverly combining functional components such as nano-zinc oxide, copper-based metal-organic framework, and sulfur-containing microcapsules, the present invention achieves synergistic enhancement of antibacterial properties and self-healing capabilities.

[0005] The purpose of this invention is to provide a thermally self-healing antibacterial aerospace cabin composite material, the composite material comprising the following components in parts by weight:

[0006] 100 parts epoxy resin matrix;

[0007] 0.5-5 parts of nano zinc oxide;

[0008] 1-10 parts of copper-based metal-organic framework;

[0009] 3-15 parts of sulfur-containing microcapsules;

[0010] 30-40 parts of curing agent;

[0011] 5-20 parts of healing agent.

[0012] Preferably, the epoxy resin matrix is ​​a bisphenol A type epoxy resin with an epoxy equivalent of 185-192 g / eq.

[0013] Preferably, the nano-zinc oxide has a particle size of 20-30 nm and a specific surface area of ​​30-50 m². 2 / g.

[0014] Preferably, the copper-based metal-organic framework is HKUST-1, with a specific surface area of ​​1500-2100 m². 2 / g, with a pore size of 0.9nm.

[0015] Preferably, the sulfur-containing microcapsules comprise a polymethyl methacrylate shell and a tetraethyl thiuram disulfide core.

[0016] Preferably, the curing agent is triethylenetetramine, with an amine value of 440-460 mg KOH / g.

[0017] Preferably, the healing agent is triglycidyl isocyanurate with an epoxy equivalent of 100-108 g / eq.

[0018] The preparation method of the self-healing antibacterial aerospace cabin composite material includes the following steps:

[0019] (1) First, heat the epoxy resin matrix at 60-70℃ and stir at 300-400 rpm.

[0020] (2) Next, slowly add nano zinc oxide and stir to disperse for 30-60 minutes;

[0021] (3) Then, add the copper-based metal-organic framework and continue stirring and dispersing for 30-60 minutes;

[0022] (4) Next, add the healing agent and stir well for 15-30 minutes;

[0023] (5) Next, add sulfur-containing microcapsules and stir gently for 10-15 minutes at a stirring speed of 100-200 rpm.

[0024] (6) Subsequently, vacuum degassing is performed at 70-80℃ for 15-30 minutes;

[0025] (7) Then, cool to 50-60℃, add curing agent, stir quickly for 3-5 minutes at a stirring speed of 400-500 rpm;

[0026] (8) Finally, pour the mixture into a preheated mold, cure it at 80-100℃ for 2-4 hours, then cure it at 120-140℃ for 2-4 hours, let it cool naturally to room temperature, and demold to obtain the composite material.

[0027] Preferably, the method further includes the step of preparing a copper-based metal-organic framework:

[0028] (1) First, mix 1.0-1.2 mol / L Cu(NO3)2·3H2O aqueous solution with 0.5-0.6 mol / L 1,3,5-benzenetricarboxylic acid ethanol solution at a volume ratio of 1:1;

[0029] (2) Next, stir the reaction at 60-70℃ for 8-12 hours;

[0030] (3) Then, the reaction product is cooled to room temperature and the precipitate is collected by centrifugation at a speed of 3000-4000 rpm for 10-15 minutes.

[0031] (4) Wash three times each with ethanol and deionized water.

[0032] (5) Finally, vacuum dry at 80-90℃ for 12-24 hours.

[0033] Preferably, the method further includes the step of preparing sulfur-containing microcapsules:

[0034] (1) First, 5-10 wt% of polymethyl methacrylate is dissolved in dichloromethane to form an oil phase;

[0035] (2) Next, tetraethylthiuram disulfide is dissolved in the oil phase at a concentration of 10-20 wt%.

[0036] (3) Then, 1-3 wt% of polyvinyl alcohol is dissolved in deionized water to form an aqueous phase;

[0037] (4) Again, while stirring at 500-800 rpm, the oil phase is slowly added dropwise to the aqueous phase at a rate of 2-5 mL / min to form an O / W emulsion.

[0038] (5) Next, stir continuously at room temperature for 6-8 hours to allow the solvent to evaporate and form microcapsules;

[0039] (6) Subsequently, the microcapsules were collected by centrifugation at a speed of 2000-3000 rpm for 5-10 minutes;

[0040] (7) Finally, wash three times with deionized water and vacuum dry at 40-50℃ for 12-24 hours.

[0041] At the molecular level, nano-zinc oxide can generate photogenerated electron-hole pairs under light irradiation, thereby generating superoxide radicals (·O). 2- The photocatalytic activity of copper-based metal-organic frameworks (Cu-MOFs) not only adsorbs and enriches bacteria, but also releases Cu2+ and hydroxyl radicals (·OH). These reactive free radicals can effectively disrupt bacterial cell membranes, achieving sustained photocatalytic antibacterial effects. Simultaneously, the porous structure of Cu-MOFs can not only adsorb and enrich bacteria, but also release Cu2+ through controlled release. 2+ Ions achieve targeted sterilization. (Cu)2+ Ions can bind to proteins on bacterial cell membranes, disrupting membrane integrity, or enter the cell to interfere with the active sites of enzymes.

[0042] More innovatively, the sulfur-containing microcapsules in this invention rupture when the material is damaged, releasing sulfur-containing compounds (such as tetraethylthiuram disulfide). The SS bonds in these compounds break to form highly reactive sulfur free radicals, which then react with triglycidyl isocyanate (TGIC) pre-dispersed in the matrix to form new covalent bonds, thereby achieving rapid self-repair of the material.

[0043] This multi-functional synergistic design not only solves the problem of rapid efficacy decay in traditional antibacterial materials, but also greatly extends the material's lifespan through its self-healing function. More importantly, this invention exhibits excellent stability in simulated aerospace environments, which may stem from the unique protective network structure formed between the functional components, mutually inhibiting the degradation process under extreme conditions.

[0044] The beneficial effects of this invention far exceed expectations. First, the synergistic effect of nano-ZnO and Cu-MOF not only provides sustained broad-spectrum antibacterial capabilities but also unexpectedly enhances the material's UV protection performance, which is particularly important in the high-energy radiation environment of space. Second, the sulfur-containing compounds released during the self-healing process not only repair cracks but also undergo secondary coordination with Cu-MOF, forming a dynamically adaptive antibacterial network, further improving the material's long-term antibacterial performance. Furthermore, although the addition of multiple functional components may affect the material's initial mechanical properties, the existence of the self-healing function ensures that the material maintains high mechanical property stability during long-term use, which is crucial for spacecraft cabins subjected to continuous stress.

[0045] In summary, this invention achieves multiple optimizations in antibacterial properties, self-healing capabilities, and environmental stability at the molecular and atomic levels through the ingenious combination of multiple components. This not only provides new ideas for the design of aerospace cabin materials but also has the potential for wide application in ground-based medical equipment, food packaging, marine engineering, and other fields, and has the potential to become the foundation for a new generation of intelligent protective materials. Detailed Implementation

[0046] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0047] Example 1: Preparation of self-healing antibacterial spacecraft cabin composite material

[0048] The self-healing antibacterial aerospace cabin composite material of this embodiment is composed of the following components: 100 parts by weight of bisphenol A type epoxy resin (DGEBA), 0.5 parts by weight of nano zinc oxide, 1 part by weight of copper-based metal-organic framework (Cu-MOF), 3 parts by weight of sulfur-containing microcapsules, 30 parts by weight of triethylenetetramine, and 5 parts by weight of triglycidyl isocyanurate (TGIC).

[0049] First, Cu-MOF was prepared. A 1.0 mol / L Cu(NO3)2·3H2O aqueous solution was mixed with a 0.5 mol / L 1,3,5-benzenetricarboxylic acid (BTC) ethanol solution at a 1:1 volume ratio. The mixture was then stirred at 60 °C for 8 hours. The reaction product was then cooled to room temperature, and the precipitate was collected by centrifugation (3000 rpm, 10 minutes). The precipitate was washed three times each with ethanol and deionized water. Finally, it was vacuum dried at 80 °C for 12 hours to obtain a specific surface area of ​​1500 m². 2 / g, Cu-MOF with a pore size of 0.9nm.

[0050] Next, sulfur-containing microcapsules were prepared. 5 wt% polymethyl methacrylate (PMMA) was dissolved in dichloromethane to form an oil phase. Tetraethylthiuram disulfide (TETD) was dissolved in the oil phase at a concentration of 10 wt%. Then, 1 wt% polyvinyl alcohol (PVA) was dissolved in deionized water to form an aqueous phase. The oil phase was slowly added dropwise to the aqueous phase at a rate of 2 mL / min while stirring at 500 rpm to form an O / W emulsion. The mixture was then stirred continuously at room temperature for 6 hours to allow the solvent to evaporate and form microcapsules. The microcapsules were then collected by centrifugation (2000 rpm, 5 min). Finally, the microcapsules were washed three times with deionized water and dried under vacuum at 40 °C for 12 hours.

[0051] The preparation method of composite materials includes the following steps:

[0052] (1) First, 100 parts by weight of DGEBA with an epoxy equivalent of 185 g / eq were heated at 60°C and stirred at 300 rpm.

[0053] (2) Next, slowly add 0.5 parts by weight of a particle size of 20 nm and a specific surface area of ​​30 m². 2 / g of nano-ZnO was stirred and dispersed for 30 minutes.

[0054] (3) Then, add 1 part by weight of Cu-MOF and continue to stir and disperse for 30 minutes.

[0055] (4) Next, add 5 parts by weight of TGIC healing agent with an epoxy equivalent of 100g / eq, and stir evenly for 15 minutes.

[0056] (5) Next, add 3 parts by weight of sulfur-containing microcapsules and stir lightly (100 rpm) for 10 minutes.

[0057] (6) Subsequently, vacuum degassing was performed at 70°C for 15 minutes.

[0058] (7) Then, cool to 50°C, add 30 parts by weight of triethylenetetramine with an amine value of 440 mg KOH / g, and stir rapidly (400 rpm) for 3 minutes.

[0059] (8) Finally, pour the mixture into a preheated mold, cure it at 80°C for 2 hours, then cure it at 120°C for 2 hours, and let it cool naturally to room temperature before demolding to obtain the composite material.

[0060] Preferably, in the embodiments of the present invention, nano-ZnO provides a sustained photocatalytic antibacterial effect. Its working principle is to generate photogenerated electron-hole pairs under light irradiation, thereby generating highly reactive free radicals that can effectively destroy bacterial cell membranes and oxidize internal cell components. Cu-MOF, on the other hand, releases Cu in a controlled manner. 2+ Ions achieve targeted sterilization, and their porous structure can also adsorb and enrich bacteria, enhancing the sterilization effect. Sulfur-containing microcapsules rupture when the material is damaged, releasing sulfur-containing compounds that react with a healing agent pre-dispersed in the matrix, achieving rapid self-repair. This synergistic effect of multiple antibacterial mechanisms and self-repair function ensures the material's long-lasting antibacterial properties and structural integrity in aerospace environments.

[0061] Example 2: Preparation of self-healing antibacterial spacecraft cabin composite material

[0062] The self-healing antibacterial aerospace cabin composite material of this embodiment is composed of the following components: 100 parts by weight of bisphenol A epoxy resin (DGEBA), 2.75 parts by weight of nano zinc oxide, 5.5 parts by weight of copper-based metal-organic framework (Cu-MOF), 9 parts by weight of sulfur-containing microcapsules, 35 parts by weight of triethylenetetramine, and 12.5 parts by weight of triglycidyl isocyanate (TGIC).

[0063] First, Cu-MOF was prepared. A 1.1 mol / L aqueous solution of Cu(NO3)2·3H2O was mixed with a 0.55 mol / L ethanol solution of 1,3,5-benzenetricarboxylic acid (BTC) at a 1:1 volume ratio. The mixture was then stirred at 65 °C for 10 hours. The reaction product was then cooled to room temperature, and the precipitate was collected by centrifugation (3500 rpm, 12.5 min). The precipitate was washed three times each with ethanol and deionized water. Finally, it was vacuum dried at 85 °C for 18 hours to obtain a specific surface area of ​​1800 m². 2 / g, Cu-MOF with a pore size of 0.9nm.

[0064] Next, sulfur-containing microcapsules were prepared. 7.5 wt% of polymethyl methacrylate (PMMA) was dissolved in dichloromethane to form an oil phase. Tetraethylthiuram disulfide (TETD) was dissolved in the oil phase at a concentration of 15 wt%. Then, 2 wt% of polyvinyl alcohol (PVA) was dissolved in deionized water to form an aqueous phase. The oil phase was slowly added dropwise to the aqueous phase at a rate of 3.5 mL / min while stirring at 650 rpm to form an O / W emulsion. The mixture was then stirred continuously at room temperature for 7 hours to allow the solvent to evaporate and form microcapsules. The microcapsules were then collected by centrifugation (2500 rpm, 7.5 min). Finally, the microcapsules were washed three times with deionized water and dried under vacuum at 45 °C for 18 hours.

[0065] The preparation method of composite materials includes the following steps:

[0066] (1) First, 100 parts by weight of DGEBA with an epoxy equivalent of 188.5 g / eq were heated at 65°C and stirred at 350 rpm.

[0067] (2) Next, slowly add 2.75 parts by weight of a material with a particle size of 25 nm and a specific surface area of ​​40 m². 2 / g of nano-ZnO was stirred and dispersed for 45 minutes.

[0068] (3) Then, add 5.5 parts by weight of Cu-MOF and continue to stir and disperse for 45 minutes.

[0069] (4) Next, add 12.5 parts by weight of TGIC healing agent with an epoxy equivalent of 104 g / eq, and stir evenly for 22.5 minutes.

[0070] (5) Next, add 9 parts by weight of sulfur-containing microcapsules and stir gently (150 rpm) for 12.5 minutes.

[0071] (6) Subsequently, the sample was degassed under vacuum at 75°C for 22.5 minutes.

[0072] (7) Then, cool to 55°C, add 35 parts by weight of triethylenetetramine with an amine value of 450 mg KOH / g, and stir rapidly (450 rpm) for 4 minutes.

[0073] (8) Finally, pour the mixture into a preheated mold, cure it at 90°C for 3 hours, then cure it at 130°C for 3 hours, and let it cool naturally to room temperature before demolding to obtain the composite material.

[0074] In this embodiment, the content of nano-ZnO and Cu-MOF was increased to enhance the antibacterial properties of the material. Simultaneously, the amount of sulfur-containing microcapsules and healing agents was increased to improve self-healing effects. This formulation adjustment aims to balance antibacterial properties and self-healing capabilities, making the material more suitable for the needs of long-term space missions.

[0075] Example 3: Preparation of self-healing antibacterial spacecraft cabin composite material

[0076] The self-healing antibacterial aerospace cabin composite material of this embodiment is composed of the following components: 100 parts by weight of bisphenol A type epoxy resin (DGEBA), 5 parts by weight of nano zinc oxide, 10 parts by weight of copper-based metal-organic framework (Cu-MOF), 15 parts by weight of sulfur-containing microcapsules, 40 parts by weight of triethylenetetramine, and 20 parts by weight of triglycidyl isocyanurate (TGIC).

[0077] First, Cu-MOF was prepared. A 1.2 mol / L aqueous solution of Cu(NO3)2·3H2O was mixed with a 0.6 mol / L ethanol solution of 1,3,5-benzenetricarboxylic acid (BTC) at a 1:1 volume ratio. The mixture was then stirred at 70 °C for 12 hours. The reaction product was then cooled to room temperature, and the precipitate was collected by centrifugation (4000 rpm, 15 minutes). The precipitate was washed three times each with ethanol and deionized water. Finally, it was vacuum dried at 90 °C for 24 hours to obtain a specific surface area of ​​2100 m². 2 / g, Cu-MOF with a pore size of 0.9nm.

[0078] Next, sulfur-containing microcapsules were prepared. 10 wt% of polymethyl methacrylate (PMMA) was dissolved in dichloromethane to form an oil phase. Tetraethylthiuram disulfide (TETD) was dissolved in the oil phase at a concentration of 20 wt%. Then, 3 wt% of polyvinyl alcohol (PVA) was dissolved in deionized water to form an aqueous phase. The oil phase was slowly added dropwise to the aqueous phase at a rate of 5 mL / min while stirring at 800 rpm to form an O / W emulsion. The mixture was then stirred continuously at room temperature for 8 hours to allow the solvent to evaporate and form microcapsules. The microcapsules were then collected by centrifugation (3000 rpm, 10 min). Finally, the microcapsules were washed three times with deionized water and dried under vacuum at 50 °C for 24 hours.

[0079] The preparation method of composite materials includes the following steps:

[0080] (1) First, 100 parts by weight of DGEBA with an epoxy equivalent of 192 g / eq were heated at 70°C and stirred at 400 rpm.

[0081] (2) Next, slowly add 5 parts by weight of particles with a diameter of 30 nm and a specific surface area of ​​50 m². 2 / g of nano-ZnO was stirred and dispersed for 60 minutes.

[0082] (3) Then, add 10 parts by weight of Cu-MOF and continue to stir and disperse for 60 minutes.

[0083] (4) Next, add 20 parts by weight of TGIC healing agent with an epoxy equivalent of 108g / eq, and stir evenly for 30 minutes.

[0084] (5) Next, add 15 parts by weight of sulfur-containing microcapsules and stir lightly (200 rpm) for 15 minutes.

[0085] (6) Subsequently, vacuum degassing was performed at 80°C for 30 minutes.

[0086] (7) Then, cool to 60°C, add 40 parts by weight of triethylenetetramine with an amine value of 460 mg KOH / g, and stir rapidly (500 rpm) for 5 minutes.

[0087] (8) Finally, pour the mixture into a preheated mold, cure it at 100°C for 4 hours, then cure it at 140°C for 4 hours, and let it cool naturally to room temperature before demolding to obtain the composite material.

[0088] In this embodiment, all functional components were present at their maximum content to maximize the material's antibacterial and self-healing properties. Notably, the content of nano-ZnO reached 5 parts by weight, which not only provides the strongest photocatalytic antibacterial effect but may also enhance the material's UV protection capability. The content of Cu-MOF reached 10 parts by weight, significantly increasing the material's antibacterial ability and controlled release characteristics. Simultaneously, the content of sulfur-containing microcapsules and healing agents was also maximized, greatly improving the material's self-healing efficiency and making it more suitable for handling extreme situations such as potential micrometeorite impacts.

[0089] Example 4: Preparation of self-healing antibacterial spacecraft cabin composite material

[0090] The self-healing antibacterial aerospace cabin composite material of this embodiment is composed of the following components: 100 parts by weight of bisphenol A epoxy resin (DGEBA), 1.625 parts by weight of nano zinc oxide, 3.25 parts by weight of copper-based metal-organic framework (Cu-MOF), 6 parts by weight of sulfur-containing microcapsules, 32.5 parts by weight of triethylenetetramine, and 8.75 parts by weight of triglycidyl isocyanate (TGIC).

[0091] First, Cu-MOF was prepared. A 1.05 mol / L aqueous solution of Cu(NO3)2·3H2O was mixed with a 0.525 mol / L ethanol solution of 1,3,5-benzenetricarboxylic acid (BTC) at a 1:1 volume ratio. The mixture was then stirred at 62.5 °C for 9 hours. The reaction product was then cooled to room temperature, and the precipitate was collected by centrifugation (3250 rpm, 11.25 min). The precipitate was then washed three times each with ethanol and deionized water. Example 4 was then completed.

[0092] Finally, after vacuum drying at 82.5℃ for 15 hours, a specific surface area of ​​1650 m² was obtained.2 / g, Cu-MOF with a pore size of 0.9nm.

[0093] Next, sulfur-containing microcapsules were prepared. 6.25 wt% of polymethyl methacrylate (PMMA) was dissolved in dichloromethane to form an oil phase. Tetraethylthiuram disulfide (TETD) was dissolved in the oil phase at a concentration of 12.5 wt%. Then, 1.5 wt% of polyvinyl alcohol (PVA) was dissolved in deionized water to form an aqueous phase. The oil phase was slowly added dropwise to the aqueous phase at a rate of 2.75 mL / min while stirring at 575 rpm to form an O / W emulsion. The mixture was then stirred continuously at room temperature for 6.5 hours to allow the solvent to evaporate and form microcapsules. The microcapsules were then collected by centrifugation (2250 rpm, 6.25 min). Finally, the microcapsules were washed three times with deionized water and dried under vacuum at 42.5 °C for 15 hours.

[0094] The preparation method of composite materials includes the following steps:

[0095] (1) First, 100 parts by weight of DGEBA with an epoxy equivalent of 186.75 g / eq were heated at 62.5°C and stirred at 325 rpm.

[0096] (2) Next, slowly add 1.625 parts by weight of a material with a particle size of 22.5 nm and a specific surface area of ​​35 m². 2 / g of nano-ZnO was stirred and dispersed for 37.5 minutes.

[0097] (3) Then, add 3.25 parts by weight of Cu-MOF and continue to stir and disperse for 37.5 minutes.

[0098] (4) Next, add 8.75 parts by weight of TGIC healing agent with an epoxy equivalent of 102 g / eq, and stir evenly for 18.75 minutes.

[0099] (5) Next, add 6 parts by weight of sulfur-containing microcapsules and stir gently (125 rpm) for 11.25 minutes.

[0100] (6) Subsequently, vacuum degassing was performed at 72.5°C for 18.75 minutes.

[0101] (7) Then, cool to 52.5°C, add 32.5 parts by weight of triethylenetetramine with an amine value of 445 mg KOH / g, and stir rapidly (425 rpm) for 3.5 minutes.

[0102] (8) Finally, pour the mixture into a preheated mold, cure at 85°C for 2.5 hours, then cure at 125°C for 2.5 hours, cool naturally to room temperature, and demold to obtain the composite material.

[0103] In this embodiment, the content of each component was chosen to be at an intermediate value, aiming to achieve a balance between antibacterial properties and self-healing capabilities. This formulation design may be more suitable for routine aerospace missions, providing sufficient antibacterial and self-healing capabilities while maintaining the overall performance balance of the material.

[0104] Preferably, in this embodiment, the moderate content of nano-ZnO and Cu-MOF ensures sustained photocatalytic antibacterial activity and controllable copper ion release, providing dual antibacterial protection for the material. Simultaneously, the appropriate dosage of sulfur-containing microcapsules and TGIC healing agent guarantees good self-healing capabilities, enabling the material to cope with minor damage that may occur in the aerospace environment. This balanced formulation not only meets the antibacterial and self-healing requirements of aerospace cabin materials but also achieves a good balance in maintaining other physical properties of the material (such as mechanical strength and thermal stability).

[0105] Comparative Example 1: Self-healing antibacterial spacecraft cabin composite material lacking nano-zinc oxide

[0106] This comparative example aims to verify the importance of nano-zinc oxide in composite materials, corresponding to Example 1. Its composition is: 100 parts by weight of bisphenol A type epoxy resin (DGEBA), 1 part by weight of copper-based metal-organic framework (Cu-MOF), 3 parts by weight of sulfur-containing microcapsules, 30 parts by weight of triethylenetetramine, and 5 parts by weight of triglycidyl isocyanate (TGIC).

[0107] The preparation method is basically the same as in Example 1, but the step of adding nano-ZnO is omitted. The preparation methods of Cu-MOF and sulfur-containing microcapsules are completely consistent with those in Example 1.

[0108] Preferably, in this comparative example, the material loses its sustained photocatalytic antibacterial effect due to the lack of nano-ZnO. This may lead to a decline in the antibacterial performance of the material during long-term space missions, especially in areas exposed to light. By comparing with Example 1, the present invention clearly demonstrates the important role of nano-ZnO in providing sustained antibacterial performance, thus proving the innovation and necessity of the present invention in the design of multiple antibacterial mechanisms.

[0109] Comparative Example 2: Self-healing antibacterial spacecraft cabin composite material lacking a copper-based metal-organic framework

[0110] This comparative example corresponds to Example 2 and aims to verify the key role of Cu-MOF in the composite material. Its composition is: 100 parts by weight of bisphenol A epoxy resin (DGEBA), 2.75 parts by weight of nano zinc oxide, 9 parts by weight of sulfur-containing microcapsules, 35 parts by weight of triethylenetetramine, and 12.5 parts by weight of triglycidyl isocyanate (TGIC).

[0111] The preparation method basically follows Example 2, but the preparation and addition steps of Cu-MOF are omitted. The preparation methods of other components are consistent with those in Example 2.

[0112] In this comparative example, the lack of Cu-MOF caused the material to lose its controllable release of Cu. 2+ Ions achieve targeted sterilization. This may significantly reduce the antibacterial performance of the material in areas without or with insufficient light. By comparing with Example 2, this invention clearly demonstrates the importance of Cu-MOF in providing comprehensive antibacterial protection, further proving the innovation and completeness of the antibacterial mechanism design of this invention.

[0113] Comparative Example 3: Self-healing antibacterial spacecraft cabin composite material lacking sulfur-containing microcapsules

[0114] This comparative example corresponds to Example 3, and its purpose is to verify the key role of sulfur-containing microcapsules in the self-healing function of materials. Its composition is: 100 parts by weight of bisphenol A type epoxy resin (DGEBA), 5 parts by weight of nano zinc oxide, 10 parts by weight of copper-based metal-organic framework (Cu-MOF), 40 parts by weight of triethylenetetramine, and 20 parts by weight of triglycidyl isocyanate (TGIC).

[0115] The preparation method basically follows Example 3, but the preparation and addition steps of sulfur-containing microcapsules are omitted. The preparation methods of other components are completely consistent with Example 3.

[0116] Preferably, in this comparative example, the material loses its self-healing ability due to the lack of sulfur-containing microcapsules. This may result in the material being unable to self-repair when subjected to minor damage, thus affecting long-term performance. By comparing with Example 3, the present invention clearly demonstrates the importance of sulfur-containing microcapsules in providing self-healing functionality, proving the innovation and necessity of the present invention in its multifunctional synergistic design.

[0117] Comparative Example 4: Self-healing antibacterial spacecraft cabin composite material using traditional organic antibacterial agents to replace nano-zinc oxide and copper-based metal-organic frameworks

[0118] This comparative example corresponds to Example 4, and aims to verify the superiority of the synergistic antibacterial mechanism of nano-ZnO and Cu-MOF in this invention. Its composition is: 100 parts by weight of bisphenol A type epoxy resin (DGEBA), 4.875 parts by weight of organic antibacterial agent (such as triclosan), 6 parts by weight of sulfur-containing microcapsules, 32.5 parts by weight of triethylenetetramine, and 8.75 parts by weight of triglycidyl isocyanate (TGIC).

[0119] The preparation method basically follows Example 4, but the steps of adding nano-ZnO and Cu-MOF are replaced with adding an organic antibacterial agent. The preparation method of sulfur-containing microcapsules is consistent with Example 4.

[0120] In this comparative example, conventional organic antibacterial agents were used instead of nano-ZnO and Cu-MOF. While this may provide initial antibacterial effects, it lacks sustained photocatalytic antibacterial activity and controlled release characteristics. This may lead to a decline in the long-term antibacterial performance of the material, and the organic antibacterial agents may gradually leach out. By comparing with Example 4, the superiority of the synergistic antibacterial mechanism of nano-ZnO and Cu-MOF in this invention can be clearly seen, especially in terms of long-term antibacterial effect and environmental friendliness.

[0121] Comparative Example 5: Self-healing antibacterial spacecraft cabin composite material using conventional self-healing resin instead of sulfur-containing microcapsules and triglycidyl isocyanurate.

[0122] This comparative example combines the features of Examples 1 and 2, aiming to verify the superiority of the microcapsule self-healing system of the present invention. Its composition is: 100 parts by weight of bisphenol A type epoxy resin (DGEBA), 1.625 parts by weight of nano zinc oxide, 3.25 parts by weight of copper-based metal-organic framework (Cu-MOF), 32.5 parts by weight of triethylenetetramine, and 14.75 parts by weight of conventional self-healing resin (such as epoxy resin containing Diels-Alder adducts).

[0123] The preparation method basically follows a combination of Examples 1 and 2, but the addition steps of sulfur-containing microcapsules and TGIC are replaced with the addition of traditional self-healing resin. The preparation methods of nano-ZnO and Cu-MOF remain unchanged.

[0124] Preferably, in this comparative example, a conventional self-healing resin was used instead of the combination of sulfur-containing microcapsules and TGIC. While this may provide some self-healing capability, it may lack rapid response and efficient repair properties. By comparing with Examples 1 and 2, the advantages of the microcapsule self-healing system in terms of repair speed and efficiency can be clearly seen, further demonstrating the innovation of the self-healing mechanism design of this invention.

[0125] Comparative Example 6: Self-healing antibacterial spacecraft cabin composite material with component contents exceeding the scope of this invention.

[0126] This comparative example aims to verify the rationality and necessity of the content range of each component in this invention, combining the characteristics of Examples 3 and 4. Its composition is: 100 parts by weight of bisphenol A type epoxy resin (DGEBA), 7 parts by weight of nano zinc oxide, 15 parts by weight of copper-based metal-organic framework (Cu-MOF), 20 parts by weight of sulfur-containing microcapsules, 50 parts by weight of triethylenetetramine, and 25 parts by weight of triglycidyl isocyanate (TGIC).

[0127] The preparation method basically follows a combination of Examples 3 and 4, but the amount of each component added exceeds the limits of this invention. The preparation methods of Cu-MOF and sulfur-containing microcapsules are consistent with the previous examples.

[0128] In this comparative example, the content of each functional component exceeded the limits defined in this invention. This may lead to an imbalance in material properties, such as decreased mechanical strength, incomplete curing, or biocompatibility issues caused by excessive antibacterial components. By comparing with Examples 3 and 4, the rationality and necessity of the component content range design in this invention can be clearly seen, demonstrating the innovation of this invention in terms of formulation optimization and performance balance.

[0129] Through these six comparative examples, this invention comprehensively verifies the necessity of each key component, the superiority of their synergistic effects, and the rationality of the formulation design. These comparisons not only highlight the innovations of this invention in terms of multiple antibacterial mechanisms, intelligent self-healing, and long-lasting performance, but also demonstrate its unique value and potential application prospects in aerospace cabin material design.

[0130] To comprehensively evaluate the performance and effectiveness of the self-healing antibacterial aerospace cabin composite material, this invention designed a series of tests covering the material's antibacterial properties, self-healing ability, mechanical properties, and stability under simulated aerospace conditions. These tests not only verified the core innovations of this invention but also revealed some unexpected technical effects.

[0131] 1. Antibacterial performance test

[0132] Experimental conditions: Escherichia coli and Staphylococcus aureus were selected as representative bacteria.

[0133] Experimental steps:

[0134] First, cut the material sample into 2cm x 2cm cubes. Second, prepare the bacterial suspension (10... 6 The sample was uniformly coated with CFU / mL. Then, the sample was subjected to both dark conditions and simulated sunlight (AM 1.5G sunlight simulator, 100mW / cm²). 2 Incubate for 24 hours. Finally, determine the number of surviving bacteria using the plate count method.

[0135] The results are shown in Table 1: Antibacterial performance test results.

[0136] Table 1: Antibacterial Performance Test Results (Survival Rate %)

[0137]

[0138] 2. Self-healing performance test

[0139] Experimental conditions: Use a sharp blade to create scratches 10 mm long and 0.5 mm deep on the sample surface.

[0140] Experimental steps:

[0141] First, scratches were created on the sample surface. Second, the sample was placed in an environment of 25°C and 50% relative humidity. Then, the scratch healing was observed using scanning electron microscopy (SEM) after 0, 12, 24, and 48 hours. Finally, the scratch healing rate was calculated.

[0142] The results are shown in Table 2: Self-healing performance test results.

[0143] Table 2: Self-healing performance test results (healing rate %)

[0144]

[0145]

[0146] 3. Mechanical property testing

[0147] Experimental conditions: Dumbbell-shaped specimens were prepared according to ASTM D638 standard.

[0148] Experimental steps:

[0149] First, tensile tests were performed using a universal testing machine at a tensile rate of 5 mm / min. Second, the tensile strength, elastic modulus, and elongation at break of the samples were recorded. Then, the samples were scratched and allowed to self-heal for 48 hours before being subjected to tensile tests again. Finally, the recovery rate of mechanical properties after self-healing was calculated.

[0150] The results are shown in Table 3: Mechanical property test results

[0151] Table 3: Mechanical Performance Test Results

[0152]

[0153] 4. Simulated aerospace environment stability test

[0154] Experimental conditions: A space environment simulation chamber was used to simulate the low Earth orbit environment.

[0155] Experimental steps:

[0156] First, the sample was placed in the simulation chamber and exposed to the following conditions: vacuum level 10. -6 Pa, temperature cycling from -100℃ to +100℃ (cycle 90 minutes), ultraviolet radiation intensity 1000W / m 2Secondly, after 1000 hours of continuous exposure, the samples were removed for antibacterial and self-healing performance tests. Then, the performance changes before and after exposure were compared. Finally, X-ray photoelectron spectroscopy (XPS) was used to analyze changes in the sample surface composition.

[0157] The results are shown in Table 4: Stability Test Results in Simulated Aerospace Environment

[0158] Table 4: Results of Simulated Space Environment Stability Tests (Performance Retention Rate %)

[0159]

[0160] Based on the above test results, the present invention can draw the following conclusions:

[0161] 1. Best Practice Example: Example 3 exhibits the best overall performance, demonstrating excellent performance in antibacterial properties, self-healing ability, mechanical properties and environmental stability.

[0162] 2. Unexpected technical effects:

[0163] a) Synergistic enhancement effect: The combination of nano-ZnO and Cu-MOF not only provides excellent antibacterial properties, but also unexpectedly enhances the material's UV protection capability, which is particularly important in aerospace environments.

[0164] b) Enhanced antibacterial properties triggered by self-healing: During the self-healing process, the rupture of sulfur-containing microcapsules not only repairs the cracks but also releases sulfur-containing compounds with antibacterial activity, further enhancing the antibacterial ability of the material.

[0165] c) Dynamic balance of mechanical properties: Although the addition of functional components may reduce the initial mechanical properties of the material, the existence of self-healing function enables the material to maintain high mechanical property stability during long-term use.

[0166] d) Environmental adaptability: In simulated aerospace environments, the material exhibits stability beyond expectations, which may be due to the formation of a protective network structure among the components, which mutually inhibits the degradation process.

[0167] 3. Mechanism Explanation: The synergistic effect of nano-ZnO and Cu-MOF creates a continuous reactive oxygen species (ROS) generation environment, which not only provides broad-spectrum antibacterial capabilities but may also slow down the material's aging process through free radical scavenging. Simultaneously, compounds released from the sulfur-containing microcapsules during the repair process may undergo secondary coordination with Cu-MOF, forming a dynamically adaptive antibacterial network. This dynamic network not only enhances the material's antibacterial properties but also improves its stability under extreme environments.

[0168] 4. Potential Applications: Based on the test results, this material is not only suitable for spacecraft hulls, but may also find applications in ground-based medical equipment, food packaging, and marine engineering. Its excellent self-healing capabilities and environmental adaptability make it a potential foundation for next-generation smart protective materials.

[0169] In summary, this invention achieves multiple optimizations in antibacterial properties, self-healing capabilities, and environmental stability through the synergistic effect of multiple components, providing new ideas and possibilities for the development of aerospace materials.

[0170] The above description is merely an embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principle of the present invention should be included within the scope of the claims of the present invention.

Claims

1. A self-healing, antibacterial aerospace cabin composite material, characterized in that, The composite material comprises the following components in parts by weight: 100 parts epoxy resin matrix; 0.5-5 parts of nano zinc oxide; 1-10 parts of copper-based metal-organic framework; 3-15 parts of sulfur-containing microcapsules; 30-40 parts of curing agent; 5-20 parts of healing agent; The healing agent is triglycidyl isocyanurate, with an epoxy equivalent of 100-108 g / eq; The steps for preparing copper-based metal-organic frameworks are as follows: (1) First, mix 1.0-1.2 mol / L Cu(NO3)2·3H2O aqueous solution with 0.5-0.6 mol / L 1,3,5-benzenetricarboxylic acid ethanol solution at a volume ratio of 1:1; (2) Next, stir the reaction at 60-70°C for 8-12 hours; (3) Then, the reaction product is cooled to room temperature and the precipitate is collected by centrifugation at a speed of 3000-4000 rpm for 10-15 minutes. (4) Wash three times each with ethanol and deionized water. (5) Finally, vacuum dry at 80-90°C for 12-24 hours; The steps for preparing sulfur-containing microcapsules are as follows: (1) First, 5-10 wt% of polymethyl methacrylate is dissolved in dichloromethane to form an oil phase; (2) Next, tetraethylthiuram disulfide is dissolved in the oil phase at a concentration of 10-20 wt%; (3) Then, 1-3 wt% of polyvinyl alcohol is dissolved in deionized water to form an aqueous phase; (4) Next, while stirring at 500-800 rpm, the oil phase is slowly added dropwise to the aqueous phase at a rate of 2-5 mL / min to form an O / W emulsion; (5) Next, stir continuously at room temperature for 6-8 hours to allow the solvent to evaporate and form microcapsules; (6) Subsequently, the microcapsules were collected by centrifugation at a speed of 2000-3000 rpm for 5-10 minutes; (7) Finally, wash with deionized water three times and vacuum dry at 40-50°C for 12-24 hours.

2. The composite material according to claim 1, characterized in that, The epoxy resin matrix is ​​a bisphenol A type epoxy resin with an epoxy equivalent of 185-192 g / eq.

3. The composite material according to claim 1, characterized in that, The nano-zinc oxide has a particle size of 20-30 nm and a specific surface area of ​​30-50 m². 2 / g.

4. The composite material according to claim 1, characterized in that, The curing agent is triethylenetetramine, with an amine value of 440-460 mg KOH / g.

5. The method for preparing the self-healing antibacterial aerospace cabin composite material according to any one of claims 1-4, characterized in that, Includes the following steps: (1) First, heat the epoxy resin matrix at 60-70°C and stir at 300-400 rpm; (2) Next, slowly add nano zinc oxide and stir to disperse for 30-60 minutes; (3) Then, add the copper-based metal-organic framework and continue stirring and dispersing for 30-60 minutes; (4) Next, add the healing agent and stir well for 15-30 minutes; (5) Next, add sulfur-containing microcapsules and stir gently for 10-15 minutes at a stirring speed of 100-200 rpm; (6) Subsequently, vacuum degassing was performed at 70-80°C for 15-30 minutes; (7) Then, cool to 50-60°C, add curing agent, and stir quickly for 3-5 minutes at a stirring speed of 400-500 rpm; (8) Finally, pour the mixture into a preheated mold, cure at 80-100°C for 2-4 hours, then cure at 120-140°C for 2-4 hours, cool naturally to room temperature, and demold to obtain the composite material.

Images