Novel anti-aging material for high-altitude shock insulation support and preparation method of novel anti-aging material

Abstract

The invention provides a novel anti-aging material for a high-altitude shock insulation support and a preparation method of the novel anti-aging material, and the novel anti-aging material is prepared from the following raw materials in percentage by mass: 85-90 wt% of silicon rubber, 1-2 wt% of nanoscale silicon dioxide, 3-5 wt% of micron-sized calcium carbonate, 0.5-1.5 wt% of anatase type titanium dioxide, 0.1-0.3 wt% of fluorosilicone modified nano aluminum oxide, 1-1.5 wt% of an oxide vulcanizing aid and 1-2 wt% of an anti-aging agent. Therefore, the prepared novel anti-aging material has excellent organic / inorganic pollutant adhesion and wear resistance in high-altitude strong ultraviolet, high sandstorm and extreme temperature change environments, the surface hydrophobicity effectively reduces moisture permeation and microcrack propagation, the thermo-oxidative aging resistance is synergistically improved through a stable cross-linked network and a composite anti-aging system, and the anti-aging performance of the material is greatly improved. And finally, excellent elasticity, good strength and stable shock insulation efficiency are realized, and the service life of the shock insulation support in a severe environment is prolonged.

Description

Technical Field

[0001] The present invention relates to the technical field of rubber products, and in particular to a new anti-aging material for high-altitude seismic isolation bearings and a preparation method thereof. Background Art

[0002] In high-altitude applications such as outdoor communication base stations, viewing platforms, and power transmission facility supports, isolation bearings face a complex aging problem caused by the combined effects of strong ultraviolet radiation, high wind and sand erosion, and organic and inorganic pollutants. These locations are constantly exposed to extreme environments, with UV intensity increasing by approximately 10% to 15% for every 1,000 meters of altitude increase, a temperature swing of 20 to 30°C between day and night, and an average of over 100 days of wind and sandstorms per year. Furthermore, due to the sparse surrounding vegetation but scattered distribution of cold-resistant shrubs (such as alpine rhododendrons and rhodiola rosea) and the frequent bird habitats, the surfaces of the isolation bearings are susceptible to organic pollutants such as bird droppings and resin exuded from cold-resistant plants, as well as inorganic particles such as grit and salt.

[0003] During long-term service, these pollutants and high-altitude environmental factors work together to accelerate the degradation of material performance:

[0004] 1. Uric acid and fatty acids in bird droppings and sticky organic matter in plant resins generate active free radicals under strong ultraviolet radiation, which attack the rubber molecular chains and cause thermal oxidative aging. At the same time, organic pollutants and gravel rub against the surface together, destroying the material's protective layer and exacerbating wear.

[0005] 2. Salts (such as sodium sulfate and magnesium chloride) carried by wind-blown sand penetrate into the material along with water. The freeze-thaw cycle caused by the temperature difference between day and night induces the growth of internal microcracks.

[0006] Therefore, a solution is urgently needed to solve the problems in the prior art. Summary of the Invention

[0007] The main purpose of the present invention is to provide a new anti-aging material for high-altitude seismic isolation bearings and its preparation method, so as to at least solve the problem in the prior art that in the high-altitude strong ultraviolet radiation and wind and sand environment, the synergistic effect of organic pollutants and inorganic particles leads to accelerated thermal oxidation aging, surface wear and internal microcrack expansion of seismic isolation bearing materials.

[0008] In order to achieve the above-mentioned objectives, the first aspect of the present invention provides a new anti-aging material for high-altitude seismic isolation bearings, which includes the following raw materials, calculated by mass fraction: 85~90 wt% silicone rubber, 1~2 wt% nano-scale silica, 3~5wt% micron-scale calcium carbonate, 0.5~1.5 wt% anatase titanium dioxide, 0.1~0.3 wt% fluorine-silicon modified nano-alumina, 1~1.5 wt% oxide vulcanization aid, and 1~2 wt% antioxidant.

[0009] Optionally, the mass ratio of the nano-sized silicon dioxide to the micron-sized calcium carbonate is (0.3-0.5):1.

[0010] Optionally, the antioxidant is a mixture of an amine compound and a phenol compound.

[0011] A second aspect of the present invention provides a method for preparing a novel anti-aging material for high-altitude seismic isolation bearings. The novel anti-aging material for high-altitude seismic isolation bearings of the present invention comprises:

[0012] Step 1: Put the silicone rubber into an internal mixer for plasticization, then add micron-sized calcium carbonate and nano-sized silicon dioxide in sequence, and perform the first mixing to disperse the micron-sized calcium carbonate in the rubber continuous phase and allow the nano-sized silicon dioxide to be initially adsorbed on the surface of the micron-sized calcium carbonate;

[0013] Step 2: adding fluorine-silicon modified nano-alumina and anatase titanium dioxide to the product of step 1, performing a second mixing, and simultaneously performing ultrasonic treatment, so that the anatase titanium dioxide and the fluorine-silicon modified nano-alumina are uniformly embedded between the silicone rubber molecular chains;

[0014] Step 3: adding a peroxide curing agent and an antioxidant to the product of step 2, performing a third mixing and aging process to obtain an aged rubber composite material;

[0015] Step 4: placing the aged rubber composite material into a mold cavity of a vulcanization device for vulcanization to obtain a vulcanized rubber composite material;

[0016] Step 5: placing the rubber composite material in a radio frequency plasma device, and performing plasma treatment on the surface of the vulcanized rubber composite material using a treatment gas containing argon and oxygen to obtain a new anti-aging material.

[0017] Optionally, in step 1, the first mixing condition is: mixing at a rotation speed of 30-50 rpm for 8 minutes.

[0018] Optionally, in step 2, the second mixing condition is: mixing at 50-60° C. for 5 minutes.

[0019] Optionally, in step 2, the conditions for the ultrasonic treatment are:

[0020] Before 3 minutes, set the main frequency to 20kHz, power to 100W, the auxiliary frequency to 40kHz, power to 50W;

[0021] After 3 minutes, set the main frequency to 20kHz, power to 60W, and the auxiliary frequency to 40kHz, power to 30W.

[0022] Optionally, in step 3, the third mixing and aging specifically includes: mixing at a rotation speed of 30-50 rpm for 3 minutes, and aging for 12 hours after the mixing is completed.

[0023] Optionally, in step 4, the step of placing the matured rubber composite material into a mold cavity of a vulcanization device for vulcanization specifically includes:

[0024] The cured rubber composite material is added to the mold cavity of the vulcanization equipment, and the temperature is increased to 150° C. at a rate of 2-3° C. / min, and a pressure of 15 MPa is applied during the heating process;

[0025] After heating to 150°C, continue heating to 170-180°C at a rate of 2-4°C / min under a pressure of 15 MPa;

[0026] At 170-180°C, gradually reduce the pressure from 15 MPa to 12 MPa and maintain for 10-20 minutes;

[0027] Then the temperature is lowered to below 80°C at a rate of 1-2°C / min, and after pressure relief, the mold is opened to take out the vulcanized rubber composite material.

[0028] Optionally, before step 4, the method further includes pre-processing the mold cavity, including:

[0029] Polish the mold cavity to a surface roughness of Ra5~10nm, and spray the release agent after cleaning.

[0030] The present invention discloses a novel anti-aging material for high-altitude seismic isolation bearings and its preparation method. The material comprises, by mass fraction, 85-90 wt% silicone rubber, 1-2 wt% nano-silicon dioxide, 3-5 wt% micron-sized calcium carbonate, 0.5-1.5 wt% anatase titanium dioxide, 0.1-0.3 wt% fluorosilicon-modified nano-alumina, 1-1.5 wt% oxide vulcanization aid, and 1-2 wt% antioxidant. The resulting novel anti-aging material exhibits excellent resistance to adhesion and wear of organic / inorganic pollutants in high-altitude environments with strong ultraviolet rays, high winds and sandstorms, and extreme temperature fluctuations. Its surface hydrophobicity effectively reduces water penetration and microcrack propagation. Its stable cross-linked network and composite anti-aging system synergistically enhance its resistance to thermal oxidative aging, ultimately maintaining excellent elasticity, good strength, and stable seismic isolation efficiency, thereby extending the service life of the seismic isolation bearing in harsh environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The accompanying drawings, which constitute part of this application, are intended to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0032] Figure 1 This is a flow chart of a method for preparing a new anti-aging material for high-altitude seismic isolation bearings that can be selected according to an embodiment of the present invention. DETAILED DESCRIPTION

[0033] It should be noted that, in the absence of conflict, the embodiments and features of the embodiments in this application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0034] The present application provides a new anti-aging material for high-altitude seismic isolation bearings, which includes the following raw materials, calculated by mass fraction: 85~90 wt% silicone rubber, 1~2 wt% nano-scale silicon dioxide, 3~5 wt% micron-scale calcium carbonate, 0.5~1.5 wt% anatase titanium dioxide, 0.1~0.3 wt% fluorine-silicon modified nano-alumina, 1~1.5 wt% oxide vulcanization aid, and 1~2 wt% antioxidant.

[0035] Specifically, the new anti-aging material for high-altitude seismic isolation bearings of the present application uses 85~90 wt% silicone rubber as a matrix, and combines 1~2 wt% nano-silicon dioxide and 3~5 wt% micron-sized calcium carbonate to construct a micro-nano structure foundation, introduces 0.5~1.5 wt% rutile titanium dioxide to enhance surface protection, adds 0.1~0.3 wt% fluorosilicon-modified nano-alumina to reduce surface energy, combines 1~1.5 wt% oxide vulcanization aid to form a stable cross-linked network, and 1~2 wt% antioxidant to inhibit free radical aging reactions. The material has excellent resistance to adhesion and wear of organic / inorganic pollutants (such as bird droppings, resin, gravel, and salt) under high-altitude strong ultraviolet rays, high winds and extreme temperature changes. The surface hydrophobicity effectively reduces moisture penetration and microcrack propagation. The stable cross-linked network and composite anti-aging system synergistically improve the resistance to thermal oxidative aging, ultimately achieving excellent elasticity, good strength, and stable seismic isolation efficiency, thereby extending the service life of the seismic isolation bearing in harsh environments. The nano-silica is nano-silica modified with a silane coupling agent, and the anatase titanium dioxide is an anatase titanium dioxide modified with a silane coupling agent. Methods for modifying nano-silica and anatase titanium dioxide with silane coupling agents are prior art and are not further described here. Furthermore, the whiteness of the micron-sized calcium carbonate is ≥95%, and the purity of the anatase titanium dioxide is ≥99.5%.

[0036] In one possible embodiment, the mass ratio of the nano-sized silicon dioxide to the micron-sized calcium carbonate is (0.3-0.5):1.

[0037] Specifically, micron-sized calcium carbonate, as the main filler, provides the overall rigidity, structural stability and compression resistance of the material. However, its high content when used alone can easily lead to filler agglomeration or uneven distribution, causing local stress concentration; while nano-sized silica is evenly dispersed in the rubber matrix, filling the gaps between fillers and between molecular chains, enhancing the interaction between rubber molecular chains, while dispersing the local stress of the micron filler and avoiding agglomeration defects; thus forming a "macro support-micro reinforcement" composite structure, while improving the overall strength and wear resistance of the material, maintaining the flexibility and processing fluidity of the rubber matrix, avoiding mechanical property imbalance caused by excessive amount of a certain component (such as excessive agglomeration of nanometers or insufficient micrometers to weaken support), thereby achieving the optimal balance of comprehensive mechanical properties.

[0038] In one possible implementation, the antioxidant is a mixture of an amine compound and a phenol compound.

[0039] Specifically, the active hydrogen atoms in the molecules of amine compounds (such as N-phenyl-α-naphthylamine and diphenylamine derivatives) can directly react with the alkyl radicals (R·) and peroxy radicals (ROO·) generated during the thermal oxidative aging of rubber, quickly terminating the free radical chain reaction, and are particularly effective in inhibiting the breakage and cross-linking of rubber molecular chains; phenolic compounds (such as 2,6-di-tert-butyl-p-cresol and hydroquinone derivatives) preferentially react with peroxy radicals (ROO·) through the phenolic hydroxyl group to generate relatively stable phenoloxy radicals (RO·), blocking the transmission of the oxidation reaction chain and reducing the concentration of active free radicals in the system.

[0040] After the two are compounded, the amine compound can quickly capture highly active free radicals and inhibit the chain initiation reaction in the early stage of aging, while the phenolic compound can specifically block the chain transfer initiated by peroxy radicals, reduce the total amount of free radicals in the system, and thus reduce the oxidation reaction rate. This synergistic effect can not only improve the protection efficiency of the rubber molecular chain, but also avoid the problem of insufficient protection time or material discoloration caused by excessive consumption of a single amine antioxidant. The compounded system has a more comprehensive protective effect against complex oxidative aging caused by strong ultraviolet radiation, large temperature difference between day and night, and changes in oxygen concentration in high-altitude areas. It can effectively delay the decline in material elasticity, increase in hardness, and surface cracking, thereby enhancing the anti-aging stability and service life of the seismic isolation bearing prepared by the new material prepared in this application in a long-term complex environment.

[0041] like Figure 1 As shown, the present application also provides a method for preparing a novel anti-aging material for high-altitude seismic isolation bearings, and the novel anti-aging material for high-altitude seismic isolation bearings described in the present application comprises:

[0042] Step 1: Put the silicone rubber into an internal mixer for plasticization, then add micron-sized calcium carbonate and nano-sized silicon dioxide in sequence, and perform the first mixing to disperse the micron-sized calcium carbonate in the rubber continuous phase and allow the nano-sized silicon dioxide to be initially adsorbed on the surface of the micron-sized calcium carbonate;

[0043] Step 2: adding fluorine-silicon modified nano-alumina and anatase titanium dioxide to the product of step 1, performing a second mixing, and simultaneously performing ultrasonic treatment, so that the anatase titanium dioxide and the fluorine-silicon modified nano-alumina are uniformly embedded between the silicone rubber molecular chains;

[0044] Step 3: adding a peroxide curing agent and an antioxidant to the product of step 2, performing a third mixing and aging process to obtain an aged rubber composite material;

[0045] Step 4: placing the aged rubber composite material into a mold cavity of a vulcanization device for vulcanization to obtain a vulcanized rubber composite material;

[0046] Step 5: placing the rubber composite material in a radio frequency plasma device, and performing plasma treatment on the surface of the vulcanized rubber composite material using a treatment gas containing argon and oxygen to obtain a new anti-aging material.

[0047] Specifically, step 1 is to put the raw silicone rubber into an internal mixer for plasticization, reduce the degree of entanglement between the raw rubber molecular chains through mechanical shearing, improve its fluidity and plasticity, and facilitate the uniform dispersion of subsequent fillers; then, micron-sized calcium carbonate and nano-sized silica are added in sequence for the first mixing, and the shear force of the internal mixer is used to uniformly disperse the micron-sized calcium carbonate in the rubber continuous phase to form a physical support skeleton, thereby improving the overall strength and rigidity of the material. At the same time, nano-sized silica is initially adsorbed on the surface of the micron-sized calcium carbonate due to its large specific surface area, thereby constructing the basis of the micro-nano composite structure, enhancing the synergistic dispersion effect of subsequent fillers, and providing uniform mechanical support and interface bonding basis for the material.

[0048] Step 2: Add fluorine-silicon modified nano-alumina and anatase titanium dioxide to the product of step 1 for a second mixing, and simultaneously perform ultrasonic treatment. The ultrasonic cavitation effect and the shear force of the internal mixer work synergistically to promote the uniform embedding of anatase titanium dioxide and fluorine-silicon modified nano-alumina between the silicone rubber molecular chains. Fluorine-silicon modified nano-alumina can be subsequently enriched on the surface of the material to reduce the adhesion of pollutants due to its low surface energy characteristics. Anatase titanium dioxide enhances the scattering and absorption capacity of ultraviolet rays by dispersed embedding, thereby improving the internal light aging protection of the material. The uniform dispersion of the two effectively reduces local stress concentration and enhances the overall anti-aging performance and structural stability of the material.

[0049] Step 3: Add a peroxide curative and antioxidant to the product from Step 2 for a third mixing process. The shearing action of the internal mixer evenly disperses the curative and antioxidant throughout the rubber matrix, ensuring full contact between the vulcanization reaction sites and uniform distribution of the antioxidant molecules, laying the foundation for subsequent crosslinking network construction and anti-aging protection. The mixture is then left to mature under static conditions to achieve uniform component distribution and a stable state, avoiding local concentration variations and ensuring uniform vulcanization and long-lasting antioxidant protection. Fluorosilicon-modified nano-alumina, with a significantly lower surface energy than the rubber matrix and other fillers, gradually migrates from the matrix interior to the surface and accumulates during the subsequent high-temperature vulcanization process, driven by both thermodynamics (minimizing the system's surface energy) and kinetics (enhancing the mobility of the rubber molecular chains). This ultimately forms a low-surface-energy functional layer on the material surface, laying the foundation for reducing contaminant adhesion and providing the material with stable anti-adhesion and wear resistance.

[0050] Step 4: Place the matured rubber composite material into the mold cavity of the vulcanization equipment. Under the vulcanization conditions, the peroxide vulcanizer decomposes to produce free radicals, which trigger a cross-linking reaction between the rubber molecular chains to form a three-dimensional network structure, significantly improving the strength, elasticity and dimensional stability of the material, and enhancing the energy dissipation capacity and structural integrity of the seismic isolation bearing under dynamic loads. At the same time, the cross-linked network fixes the dispersed state of the filler, maintains the effectiveness of the micro-nano structure and functional components, and ensures the long-term service performance and stability of the material.

[0051] Step 5: Place the vulcanized rubber composite material in a radio frequency plasma device, introduce a treatment gas containing argon and oxygen, use the high-energy particles in the plasma to bombard the material surface, and slightly etch the surface through argon ion sputtering to remove the weak boundary layer, thereby improving the surface cleanliness and activity. At the same time, polar groups are introduced through the reaction of oxygen plasma with surface rubber molecules to enhance the surface energy regulation ability, and the low surface energy characteristics of fluorine-silicon modified nano-alumina are enriched on the surface, synergistically reducing the surface energy of the material and optimizing the micro-nano structure, significantly reducing the adhesion of water, dust and organic pollutants (such as bird droppings and resins), improving the material's anti-adhesion and wear resistance, and extending the service life of the seismic isolation bearing in harsh environments.

[0052] Among them, fluorine-silicon modified nano-alumina is prepared according to the following process:

[0053] Select nano-alumina powder with a particle size of 20-40 nm, use anhydrous ethanol: deionized water = 3:1 (volume ratio) as a mixed solvent, add 0.1%-1% of the mass of the nano-alumina powder as a dispersant (sodium hexametaphosphate or polycarboxylate), first use intermittent ultrasonic dispersion (power 400-500W, ultrasonic 5 minutes pause 2 minutes, total time 60 minutes), and then low-speed mechanical stirring for 30 minutes to ensure that the nanoparticles are fully dispersed and no hard agglomerates are formed.

[0054] The dispersed suspension is then heated to 50-60°C and continuously stirred at 800-1000 rpm. A fluorosilane coupling agent (perfluorodecyltriethoxysilane) at a concentration of 1% to 3% of the mass of the nano-alumina powder is added dropwise. At the same time, the pH of the system is adjusted to 4.5-5.5 with a 0.01 mol / L hydrochloric acid solution. The mixture is reacted at a constant temperature for 3-4 hours to allow the fluorosilane to fully condense with the hydroxyl groups on the surface of the nano-alumina.

[0055] After the reaction is completed, 0.2-0.5 g of polyethylene glycol 400 is added as an anti-agglomeration agent, and stirring is continued at 800-1000 rpm for 60 min to inhibit secondary agglomeration of the particles through the steric hindrance effect.

[0056] Centrifuge at 6000-7000 rpm for 10-12 minutes, then collect the precipitate, wash twice with deionized water, and then wash twice with anhydrous ethanol.

[0057] The washed precipitate is pre-frozen to -40°C to -60°C and maintained for 2-4 hours, then placed in a vacuum freeze drying oven and sublimated and dried for 5 hours at a vacuum degree of 1-10 Pa and a temperature of 40-50°C to obtain nano-scale fluorine-silicon modified nano-alumina.

[0058] In a possible implementation, in step 1, the first mixing condition is: mixing at a rotation speed of 30-50 rpm for 8 minutes.

[0059] Specifically, the shear force generated by 30~50rpm is moderate, which can not only effectively break up the initial agglomerates of micron-sized calcium carbonate and promote their uniform dispersion in the silicone rubber continuous phase, but also avoid local overheating caused by too high a speed, excessive breakage of rubber molecular chains, or excessive aggregation of nano-silica due to severe shearing; the 8-minute mixing time ensures that the micron filler is fully dispersed and the nano-silica can form a stable adsorption layer on the surface of calcium carbonate, forming an ideal "micron skeleton + nano-node" basic structure, providing good interface conditions for the subsequent dispersion of nano-functional fillers, and preventing filler agglomeration caused by insufficient mixing or weakening of the filler-rubber interface caused by excessive mixing, thereby laying the foundation for the material to ultimately obtain balanced mechanical properties and functional characteristics while ensuring processing efficiency.

[0060] In a possible implementation, in step 2, the second mixing is performed at 50-60° C. for 5 minutes.

[0061] Specifically, a temperature range of 50-60°C ensures moderate fluidity in the rubber molecular chains, allowing the newly added fluorine-silicon-modified nano-alumina and anatase-type titanium dioxide in the second mixing step to be efficiently dispersed and initially embedded between the rubber molecular chains, thereby avoiding insufficient fluidity caused by low temperatures or molecular chain degradation / filler inactivation caused by high temperatures. A short mixing time of 5 minutes controls processing intensity, preventing excessive shearing from causing secondary filler aggregation or rubber molecular chain breakage. Ultrasonic treatment breaks down filler agglomerates through the cavitation effect, promoting a more uniform dispersion state of the fluorine-silicon-modified nano-alumina and anatase-type titanium dioxide in the second mixing stage, ultimately laying the foundation for the stable embedding and functional performance of the fillers in subsequent steps. This not only improves the dispersion efficiency of the second mixing step itself and the filler-rubber interface bonding quality, but also optimizes the overall anti-aging properties and mechanical stability of the material.

[0062] In one possible embodiment, in step 2, the conditions for the ultrasonic treatment are:

[0063] Before 3 minutes, set the main frequency to 20kHz, power to 100W, the auxiliary frequency to 40kHz, power to 50W;

[0064] After 3 minutes, set the main frequency to 20kHz, power to 60W, and the auxiliary frequency to 40kHz, power to 30W.

[0065] Specifically, in the early stage, high-intensity ultrasound produces strong microjets and shock waves through the violent collapse of high-frequency cavitation bubbles, which quickly break up the agglomerates of fluorosilicone-modified nano-alumina and anatase-type titanium dioxide, and promote their initial dispersion in the rubber matrix; in the later stage, the power is reduced to avoid long-term high-intensity ultrasound causing thermal damage to the rubber molecular chains or destruction of the surface active groups of the filler, and it switches to mild cavitation to maintain the dispersed state and promote the stable combination of the filler and the rubber molecular chain, which not only ensures the efficient and uniform dispersion of the filler in the mixing stage, but also protects the intrinsic properties of the rubber matrix and the filler, and ultimately lays the foundation for the stable embedding and functional performance of the filler in the rubber.

[0066] In a possible embodiment, in step 3, the third mixing and aging specifically includes: mixing at a rotation speed of 30-50 rpm for 3 minutes, and aging for 12 hours after the mixing is completed.

[0067] Specifically, the third mixing speed is consistent with the first mixing speed. The low-speed mixing avoids excessive damage to the rubber molecular chain caused by high-intensity shearing and secondary agglomeration of nano / micro fillers such as fluorosilicone-modified nano-alumina and anatase-type titanium dioxide. Only sufficient shear force is provided to make the peroxide vulcanizer and antioxidant uniformly dispersed in the rubber matrix and make initial contact with the filler, while retaining the stable embedded structure of the filler and the rubber molecular chain formed in the early mixing; after the mixing is completed, it is parked for 12 hours for aging, and the slow relaxation and diffusion movement of the rubber molecular chain is utilized to promote the vulcanizer, antioxidant and filler to further diffuse between the rubber molecular chains and achieve a more uniform distribution state. At the same time, the filler-rubber interface and the vulcanizer active point gradually form a stable bond through intermolecular forces, avoiding local performance defects caused by uneven distribution of components when vulcanization is immediately performed after mixing.

[0068] In a possible embodiment, in step 4, the step of placing the matured rubber composite material into a mold cavity of a vulcanization device for vulcanization specifically includes:

[0069] The cured rubber composite material is added to the mold cavity of the vulcanization equipment, and the temperature is increased to 150° C. at a rate of 2-3° C. / min, and a pressure of 15 MPa is applied during the heating process;

[0070] After heating to 150°C, continue heating to 170-180°C at a rate of 2-4°C / min under a pressure of 15 MPa;

[0071] At 170-180°C, gradually reduce the pressure from 15 MPa to 12 MPa and maintain for 10-20 minutes;

[0072] Then the temperature is lowered to below 80°C at a rate of 1-2°C / min, and after pressure relief, the mold is opened to take out the vulcanized rubber composite material.

[0073] Specifically, the first stage: rapid heating from low temperature (2~3℃ / min to 150℃, constant pressure 15MPa)

[0074] The mold temperature is raised from room temperature to 150°C at a rate of 2-3°C / min to prevent the rubber matrix from being heated too quickly, leading to internal stress concentration and uneven local expansion, which can cause deformation, or agglomeration of the nano-alumina and titanium dioxide due to thermal shock. The peroxide curing agent in this application is dicumyl peroxide, which is stable at low temperatures to prevent premature decomposition.

[0075] During the heating process, a high pressure of 15MPa is continuously applied to compress the rubber composite material through external mechanical force, expel air, moisture, low-molecular residues and other volatile substances in the cavity, and reduce the pore defects inside the material after vulcanization; at the same time, the pressure causes the rubber molecular chains to fit closely with the filler, pre-filling the gaps between the molecular chains and providing a uniform initial structural foundation for the subsequent cross-linking network construction.

[0076] The second stage: high temperature gradient heating (2~4℃ / min to 170~180℃, constant pressure 15MPa)

[0077] After entering the high-temperature range, the heating rate is appropriately relaxed to 2-4°C / min to uniformly heat the rubber matrix and the vulcanizer, accelerate the decomposition of the peroxide vulcanizer, and initiate crosslinking reactions between the rubber molecular chains, forming a three-dimensional network structure. Using a gradient heating method can avoid excessive local movement of the rubber molecular chains (such as breakage or disordered entanglement) caused by sudden temperature changes.

[0078] Maintaining high pressure in the high temperature range of 150~180℃ further compacts the rubber matrix, promotes the close bonding of fillers such as nano-silica and fluorosilicone-modified nano-alumina with the rubber molecular chains, and at the same time inhibits excessive flow of rubber at high temperatures, ensuring that the cross-linked network evenly wraps the filler to form a stable structure.

[0079] The third stage: dynamic pressure control and pressure maintenance (pressure drops to 12MPa at 170-180℃, pressure maintenance for 10-20min)

[0080] After reaching 170-180°C, the pressure is gradually reduced from 15MPa to 12MPa. Because the mobility of rubber molecular chains is already high at high temperatures, excessive pressure may lead to excessive compression of the crosslinked network (restricting the free movement of the molecular chains), which in turn affects the crosslink density and elastic recovery properties. Reducing the pressure to 12MPa maintains close contact between the materials in the cavity while avoiding excessive constraint, allowing the crosslinking reaction to proceed under a more balanced mechanical environment. Maintaining the pressure at 170-180°C and 12MPa for 10-20 minutes provides ample time for the free radicals generated by the decomposition of the peroxide curative to fully crosslink the rubber molecular chains (forming a dense three-dimensional network). This also promotes the uniform anchoring of fillers (such as nanoparticles) within the network nodes, enhancing the material's mechanical strength (such as tensile strength and elastic modulus), thermal stability (resistance to high-temperature softening), and dimensional stability (reducing vulcanization shrinkage). The holding time needs to balance crosslinking adequacy with production efficiency.

[0081] After the pressure holding is completed, the temperature is lowered to below 80°C at a rate of 1~2°C / min. After the pressure is released, the mold is opened and the vulcanized rubber composite material is taken out.

[0082] In a possible implementation, before step 4, the step further includes pre-processing the mold cavity, including:

[0083] Polish the mold cavity to a surface roughness of Ra5~10 nanometers, and spray the release agent after cleaning.

[0084] Specifically, a conventional polishing machine was first used with 800-3000 mesh diamond abrasive paste (particle size 5-20 μm) and a polyurethane polishing pad to pre-rough polish the mold cavity at a speed of 250-350 rpm and a pressure of 0.2-0.4 MPa for 8-15 minutes, effectively removing obvious tool marks and scratches caused by machining, and initially reducing the surface roughness from the original Ra>100 nm to Ra 30-50 nm; then, a 15000 mesh diamond abrasive paste (particle size of about 1 μm) and a polyurethane polishing pad of the same type were used to perform rough polishing for 5-10 minutes at a speed of 200-300 rpm and a pressure of 0.1-0.3 MPa, refining the surface texture and eliminating residual traces of pre-rough polishing, further reducing the roughness to Ra≤100 nm (submicron level); then, a cerium oxide polishing liquid (particle size 0.5-1 μm) and a polyurethane polishing pad were used to perform low-speed polishing at 100-150 rpm for 3-5 minutes. The surface of the cavity is polished evenly for 2 to 5 minutes per area, and the roughness of the entire area is monitored and controlled in real time to stabilize at Ra 3~8nm (Ra≤5nm is preferred) to ensure a smooth surface close to mirror level. The polished mold cavity is immersed in anhydrous ethanol (analytical grade, ≥99.7%) and cleaned with a 40kHz ultrasonic cleaner (power 100W) for 5 minutes to effectively remove the nano-abrasive particles and organic additives in the polishing liquid through the cavitation effect; the mold is then transferred to a deionized water high-pressure spray cleaner (water resistivity ≥18.2MΩ·cm) and the cavity surface is flushed at a pressure of 0.3~0.5MPa for 2~3 minutes, focusing on grooves, edges and corners and other areas prone to residue, to completely remove ethanol and particulate impurities; then high-purity nitrogen (purity ≥99.99%) is used to vertically purge the cavity for 3~5 minutes at a flow rate of 5~8L / min to ensure that there is no liquid residue or water stains on the surface.

[0085] Use electrostatic spraying equipment or ultra-fine atomizing nozzles to evenly spray special rubber release agents (such as silicone-based release agents, fluorine-based release agents or high-molecular polymer coatings) onto the cavity surface, and precisely control the coating thickness to 100-200nm to avoid local excessive thickness that may cause white spots or adhesion on the vulcanized rubber surface. After spraying, place the mold at 50-60°C for 5-10 minutes to allow the release agent solvent to fully evaporate and form a stable low-surface-energy isolation film (if it is a thermosetting release agent, it should be cured according to the instructions). This isolation film can effectively reduce the adhesion between the mold and the vulcanized rubber, ensuring that the rubber composite material can easily be separated from the mold after vulcanization, avoiding tearing, residue or surface damage, while protecting the nano-smooth surface of the mold cavity from damage.

[0086] The present application is further illustrated by the following examples.

[0087] Example 1

[0088] Raw material ratio:

[0089] Calculated by mass fraction, the raw material composition is as follows: 88wt% silicone rubber, 1.5wt% nano-sized silica, 4wt% micron-sized calcium carbonate, 1wt% anatase-type titanium dioxide, 0.2wt% fluorine-silicon-modified nano-alumina, 1.3wt% diisopropylbenzene peroxide, and 1.5wt% antioxidant (N-phenyl-α-naphthylamine and 2,6-di-tert-butyl-p-cresol are compounded in a mass ratio of 1:1), wherein the mass ratio of nano-sized silica to micron-sized calcium carbonate is 3:8.

[0090] Preparation process:

[0091] The silicone rubber was put into an internal mixer for plastication, followed by the addition of micronized calcium carbonate and nano-silicon dioxide, and the mixing was completed at 40 rpm for 8 minutes. Fluorosilicon-modified nano-alumina and anatase titanium dioxide were added to the product and mixed at 55°C for 5 minutes. Ultrasonic treatment was also performed (the main frequency was set at 20 kHz, power 100 W, and the auxiliary frequency was set at 40 kHz, power 50 W for the first 3 minutes, and the main frequency was adjusted to 20 kHz, power 60 W, and the auxiliary frequency was adjusted to 40 kHz, power 30 W for the next 2 minutes). Complete the second mixing; then add the oxide vulcanization aid and antioxidant, mix at 40 rpm for 3 minutes, and let it stand for 12 hours to mature after mixing; put the matured rubber composite material into the pretreated mold cavity, heat it to 150°C at a rate of 2.5°C / min, and maintain a pressure of 15MPa, then heat it to 175°C at a rate of 3°C / min and still maintain a pressure of 15MPa, finally reduce the pressure to 12MPa at 175°C, and maintain it at 12MPa for 15 minutes to complete the vulcanization, then cool it to below 80°C at a rate of 1°C / min, release the pressure, open the mold and take out the vulcanized rubber composite material; finally, place the vulcanized material in a radio frequency plasma equipment, pass a mixed gas of argon and oxygen (volume ratio 3:1), and treat it at a power of 50W for 2 minutes to obtain a new anti-aging material.

[0092] Example 2

[0093] Raw material ratio:

[0094] Calculated by mass fraction, the raw material composition is as follows: 85wt% silicone rubber, 2wt% nano-silicon dioxide, 5wt% micron-sized calcium carbonate, 1.5wt% anatase-type titanium dioxide, 0.3wt% fluorine-silicon modified nano-alumina, 1.5wt% oxide vulcanization aid, 2wt% antioxidant (compounded N-phenyl-α-naphthylamine and 2,6-di-tert-butyl-p-cresol in a mass ratio of 1:1), among which the mass ratio of nano-silicon dioxide to micron-sized calcium carbonate is 2:5.

[0095] Preparation process:

[0096] The silicone rubber was put into an internal mixer for plastication; micron-sized calcium carbonate and nano-sized silicon dioxide were then added in sequence, and the first mixing was completed at a speed of 50 rpm for 8 minutes; fluorine-silicon-modified nano-alumina and anatase-type titanium dioxide were added to the product, and the mixture was mixed at 60°C for 5 minutes, and ultrasonic treatment was performed at the same time (the main frequency was set to 20 kHz, power to 100 W, the auxiliary frequency to 40 kHz, power to 50 W for the first 3 minutes, and the main frequency was adjusted to 20 kHz, power to 60 W, the auxiliary frequency to 40 kHz, power to 30 W for the next 2 minutes) to complete the second mixing; then the oxide vulcanization aid and antioxidant were added, and the mixture was mixed at a speed of 50 rpm for 3 minutes, and then the mixture was left to mature for 12 hours after mixing; the matured material was put into the pretreated mold cavity, and the temperature was raised to 180°C at a pressure of 15 MPa at a rate of 4°C / min, and then the pressure was reduced to 12 MPa at 180°C and the pressure was maintained for 18 minutes to complete the vulcanization; then the temperature was increased at a rate of 2°C / min The temperature was rapidly reduced to below 80°C, and after the pressure was released, the mold was opened to take out the vulcanized rubber composite material. Finally, the vulcanized material was placed in a radio frequency plasma device, and a mixed gas of argon and oxygen (volume ratio 3:1) was introduced. The material was treated at a power of 50W for 2 minutes to obtain a new anti-aging material and the target material.

[0097] Example 3

[0098] Raw material ratio:

[0099] Calculated by mass fraction, the raw material composition is as follows: 90wt% silicone rubber, 1wt% nano-silicon dioxide, 3wt% micron-sized calcium carbonate, 0.5wt% anatase-type titanium dioxide, 0.1wt% fluorine-silicon modified nano-alumina, 1wt% oxide vulcanization aid, 1wt% antioxidant (N-phenyl-α-naphthylamine and 2,6-di-tert-butyl-p-cresol are compounded in a mass ratio of 1:1), among which the mass ratio of nano-silicon dioxide to micron-sized calcium carbonate is 1:3.

[0100] Preparation process:

[0101] The silicone rubber was put into an internal mixer for plastication; micronized calcium carbonate and nano-silicon dioxide were then added in sequence, and the first mixing was completed at a speed of 30 rpm for 8 minutes; fluorine-silicon modified nano-alumina and anatase titanium dioxide were added to the product, mixed at 50 ° C for 5 minutes, and ultrasonic treatment was performed at the same time (the main frequency was set to 20 kHz, power 100 W, the auxiliary frequency was 40 kHz, and power 50 W for the first 3 minutes, and the main frequency was adjusted to 20 kHz, power 60 W, and the auxiliary frequency was 40 kHz, and power 30 W for the next 2 minutes) to complete the second mixing; then the oxide vulcanization aid and antioxidant were added, mixed at a speed of 30 rpm for 3 minutes, and then allowed to mature for 12 hours after mixing; the matured material was put into the pretreated mold cavity, and the temperature was raised to 150 ° C at a pressure of 15 MPa at a rate of 2 ° C / min, and then raised to 170 ° C at a rate of 2 ° C / min, and then the pressure was reduced to 12 MPa at 170 ° C and the pressure was maintained for 12 minutes to complete the vulcanization, and then the temperature was increased to 170 ° C at a rate of 170 ° C. The temperature was then rapidly cooled to below 80°C, and after decompression, the mold was opened and the vulcanized rubber composite material was removed. Finally, the vulcanized material was placed in a radio frequency plasma device, where a mixture of argon and oxygen (3:1 by volume) was introduced at 50W for 2 minutes to produce a new anti-aging material.

[0102] Comparative Example 1

[0103] Raw material ratio:

[0104] On the basis of Example 1, the fluorine-silicon modified nano-alumina was removed, and the proportions of other raw materials were exactly the same as those in Example 1.

[0105] Preparation process:

[0106] Except that fluorine-silicon-modified nano-alumina was not added during the second mixing, the remaining steps were exactly the same as in Example 1: after the silicone rubber was plasticized, micron-sized calcium carbonate and nano-sized silicon dioxide were added and mixed at 40 rpm for 8 minutes; anatase-type titanium dioxide was then added, mixed at 55°C for 5 minutes, and ultrasonically treated according to the parameters of Example 1; a vulcanizing agent and an antioxidant were then added, mixed at 40 rpm for 3 minutes, and then allowed to mature for 12 hours; the matured material was put into a mold cavity pretreated in the same manner as in Example 1, heated to 150°C (15 MPa) at a rate of 2.5°C / min, then heated to 175°C (15 MPa) at 3°C / min, and vulcanized at 175°C under a pressure of 12 MPa for 15 minutes. After the pressure holding period, the material was cooled to below 80°C at a rate of 1°C / min, and the mold was opened after the pressure was released to remove the vulcanized rubber composite material; finally, the material was subjected to plasma treatment to obtain a comparative material.

[0107] Comparative Example 2

[0108] Raw material ratio:

[0109] On the basis of Example 1, anatase titanium dioxide was removed, and the proportions of other raw materials were exactly the same as those in Example 1.

[0110] Preparation process:

[0111] Except that anatase titanium dioxide was not added during the second mixing, the remaining steps were exactly the same as in Example 1: after the silicone rubber was plasticized, micron-sized calcium carbonate and nano-sized silicon dioxide were added and mixed at 40 rpm for 8 minutes; fluorine-silicon-modified nano-alumina was then added, mixed at 55°C for 5 minutes, and ultrasonically treated according to the parameters of Example 1; a vulcanizing agent and an antioxidant were then added, mixed at 40 rpm for 3 minutes, and then left to mature for 12 hours; the matured material was placed into a mold cavity pretreated in the same manner as in Example 1, and vulcanized according to the same parameters. After the pressure holding period, the temperature was then lowered to below 80°C at a rate of 1°C / min. After the pressure was released, the mold was opened and the vulcanized rubber composite material was removed; and finally, it was subjected to plasma treatment to obtain a comparative material.

[0112] Comparative Example 3

[0113] Raw material ratio

[0114] On the basis of Example 1, "1.5 wt % of compound antioxidant" was replaced by "1.5 wt % of N-phenyl-α-naphthylamine)", and the proportions of other raw materials were exactly the same as those in Example 1.

[0115] Preparation process

[0116] Consistent with Example 1: after the silicone rubber was plasticized, micron-sized calcium carbonate and nano-sized silicon dioxide were added and mixed at 40 rpm for 8 minutes; fluorine-silicon-modified nano-alumina and anatase-type titanium dioxide were then added, mixed at 55°C for 5 minutes, and ultrasonically treated according to the parameters of Example 1; then, a vulcanizing agent and N-phenyl-α-naphthylamine were added, mixed at 40 rpm for 3 minutes, and then left to mature for 12 hours; the matured material was placed into a mold cavity pretreated in the same manner as in Example 1, and vulcanized according to the same parameters. After the pressure holding period was completed, the temperature was then lowered to below 80°C at a rate of 1°C / min. After the pressure was released, the mold was opened and the vulcanized rubber composite material was removed; finally, it was treated with plasma to obtain a comparative material.

[0117] Performance testing

[0118] 1. Anti-ultraviolet aging performance test

[0119] Equipment: UVB-313 ultraviolet aging test chamber with a temperature control accuracy of ±2°C and an irradiation intensity accuracy of ±0.02W / m² is used to simulate the strong ultraviolet environment in high altitude areas.

[0120] Sample Preparation: Cut standard specimens measuring 100 mm × 25 mm × 2 mm from each Example and Comparative Example. Set up three replicates per group to ensure the reliability of the test results. After cutting, carefully wipe the surface with anhydrous ethanol to remove oil and impurities, then air dry.

[0121] Test parameter settings: UVB-313 lamps were used as the UV light source, with an irradiance setting of 0.71W / m² to simulate high-intensity UV radiation at high altitudes. The blackboard temperature was maintained at 60°C, the humidity was controlled at 50%, and the aging time was continued for 1000 hours to accelerate the material's aging process and simulate the long-term exposure to UV radiation at high altitudes.

[0122] Performance Testing: After the aging test, the specimens were subjected to a tensile strength test using an electronic universal tensile testing machine. The material's UV aging resistance was determined by calculating "tensile strength retention = (strength after aging / initial strength) × 100%." ​​The average of three replicate samples was used as the final result.

[0123] 2. Hot and cold cycle resistance test

[0124] Equipment: Utilizing a high-low temperature alternating test chamber with a temperature range of -60°C to 150°C, this chamber can simulate extreme temperature fluctuations at high altitudes, with a temperature control accuracy of ±1°C. Paired with an electronic universal testing machine, this chamber is used to test changes in the mechanical properties of materials after thermal cycling.

[0125] Sample preparation: Cut specimens with a size of 80 mm × 10 mm × 2 mm. Prepare three parallel specimens for each group and clearly mark the initial length of the specimens.

[0126] Cyclic test parameters: The test was set up with the following hot and cold cycling program: first, maintain the temperature at -40°C for 8 hours to simulate the low temperatures of high altitudes; then, increase the temperature to 25°C over 2 hours at a rate of 5°C / min; then maintain the temperature at 80°C for 8 hours to simulate a high temperature; and finally, decrease the temperature to 25°C over 2 hours at a rate of 5°C / min. This cycle was repeated 50 times to fully simulate the frequent temperature changes caused by the alternation of day and night and the seasons at high altitudes.

[0127] Performance testing: After 50 hot and cold cycles, use an electronic universal testing machine to test the tensile elongation at break of the specimens. Calculate "tensile elongation at break retention = (elongation at break after cycle / initial elongation at break) × 100%" to evaluate the material's elasticity and toughness retention after hot and cold cycles, and take the average value of the parallel samples.

[0128] 3. Anti-wind and sand wear performance test

[0129] Equipment: A sand and dust abrasion test chamber equipped with a wind speed adjustment system allows for precise wind speed control. 80-mesh quartz sand is used to simulate dust particles found at high altitudes.

[0130] Sample preparation: Prepare square samples measuring 50 mm × 50 mm × 3 mm, with three replicates per group. Before testing, weigh the initial mass of the sample using an analytical balance with an accuracy of 0.1 mg and record the mass.

[0131] Test parameters: A dust concentration of 10g / m³ was set to simulate the dust content found in a high-altitude, windy, and sandy environment. The wind speed was adjusted to 8m / s, and the angle between the sample and the airflow was set at 30°, ensuring that the dust effectively abraded the sample surface. The abrasion test lasted 200 hours to simulate the long-term erosion of the material by wind and sand at high altitudes.

[0132] Performance testing: After the wear test, the sample mass was weighed again using an analytical balance. The material's resistance to wind and sand wear was evaluated by calculating "mass loss rate = (initial mass - mass after wear) / initial mass × 100%". The average value of three parallel samples was taken as the mass loss rate of this group of materials.

[0133] 4. Hydrophobicity test

[0134] Equipment: Using a contact angle meter with a measurement accuracy of ±0.1° and a 5μL water droplet volume for testing, it can accurately measure the water contact angle on the material surface to evaluate the hydrophobicity of the material.

[0135] Sample preparation: Prepare flat samples of 50 mm × 50 mm × 2 mm, with three replicates per group. Before testing, purge the sample surface with nitrogen to ensure that there are no impurities on the surface, which may interfere with the hydrophobicity test results.

[0136] Test parameters: At room temperature (25°C) and humidity (45%), three locations were randomly selected on each sample surface. Deionized water was added using a contact angle meter. The water droplet was allowed to sit for 10 seconds, and the water contact angle was measured using the instrument's built-in image analysis software.

[0137] Performance testing: Calculate the average of the water contact angles at three locations as the sample's initial water contact angle. A larger water contact angle indicates a more hydrophobic material and better resistance to water erosion.

[0138] 5. Hardness change test after aging

[0139] Equipment: Use Shore A hardness tester with an accuracy of ±1°, which can accurately measure the hardness of the material.

[0140] Sample preparation: Prepare 100 mm × 100 mm × 6 mm thick samples, with 3 parallel samples in each group.

[0141] Testing steps: First, the initial hardness of each sample was measured using a Shore A durometer at five evenly spaced locations. The data was then recorded. The sample was then subjected to a 1000-hour UV aging test. After aging, the hardness was measured again at the same locations as previously measured.

[0142] Performance testing: By calculating "hardness change after aging = average hardness after aging - initial average hardness", the hardness change value of the material before and after aging is obtained, and the impact of aging on the hardness of the material is evaluated.

[0143] 6. Seismic isolation efficiency test

[0144] Equipment: Use a small vibration table with a frequency range of 0~50Hz and a maximum amplitude of 10mm, which can simulate vibration environments of different frequencies and amplitudes. The matching accuracy is ±0.01m / s 2 Accelerometers are used to measure input and output acceleration.

[0145] Sample preparation: Process cylindrical seismic isolation pad samples with a diameter of 50 mm and a height of 20 mm, with 2 parallel samples in each group, and paste metal connectors on the surface of the samples to ensure a stable connection with the vibration table and sensor.

[0146] Test parameters: The vibration table frequency was set to vary within the range of 1-5 Hz, with an amplitude of 5 mm. Acceleration sensors were installed at the input end of the vibration table and the output end of the isolation pad sample to collect acceleration data during the vibration process.

[0147] Performance testing: The material's seismic isolation efficiency is calculated based on the formula "isolation efficiency η = (mean input acceleration - mean output acceleration) / mean input acceleration × 100%). The material's isolation performance in a simulated vibration environment is evaluated, and the average value of two parallel samples is taken as the final isolation efficiency result.

[0148] 7. Bird droppings resistance and cleaning performance test

[0149] equipment

[0150] Artificial bird droppings are prepared with a composition of "40% uric acid, 30% fecal residue, and 30% water," with a viscosity controlled at 500 mPa·s to mimic the adhesion characteristics of real bird droppings. A constant temperature and humidity chamber, model HD-E702-225K40 / 60, a rain test chamber, model HD-E710-3, is used to simulate a rainy environment. An analytical balance with an accuracy of 0.1 mg is also required for weighing the droppings.

[0151] Sample preparation

[0152] Prepare flat samples of 50 mm × 50 mm × 2 mm, with 3 parallel samples in each group. Purge the sample surface with nitrogen before testing to ensure that there is no interference from impurities.

[0153] Test steps

[0154] Artificial coating of bird droppings: Use a pipette to evenly coat the surface of each sample with 0.2 g of simulated bird droppings (the initial coating mass is recorded as m0). The coating area is controlled to 20 mm × 20 mm. The sample is then placed in a constant temperature and humidity chamber for 24 hours to simulate the drying and adhesion process of bird droppings in the natural environment.

[0155] Simulated rainfall cleaning: After 24 hours, take out the sample and start the spray device for cleaning. The parameters are set as water temperature 25℃, water pressure 0.1MPa, spray angle 45°, spray distance 20cm from the sample, and continue spraying for 3 minutes to simulate the intensity of moderate rain in high altitude areas.

[0156] Performance testing

[0157] After the spraying is completed, the mass of residual bird droppings on the sample surface is weighed using an analytical balance (recorded as m1), and the final result is calculated according to the formula "Guano cleaning efficiency = (m0-m1) / m0×100%". The average value of 3 parallel samples is taken as the final result.

[0158] This indicator directly reflects the material's actual ability to remove bird droppings under natural rainfall conditions. It strongly matches the core requirements of high-altitude seismic isolation bearings, namely "easy to clean and reduce long-term adhesion of pollutants", and is a key indicator for evaluating bird droppings resistance.

[0159] The performance tests are shown in Table 1:

[0160] Table 1 Performance test data

[0161] Example / Comparative Example Initial water contact angle (°) Tensile strength retention rate (%) Retention rate of elongation at break (%) Mass loss rate (%) Shore A hardness change (°) Isolation efficiency (%) Guano cleaning efficiency (%) Example 1 118 89 92 0.35 +3 88 90 Example 2 122 92 94 0.32 +2 90 93 Example 3 115 87 90 0.38 +4 86 88 Comparative Example 1 (Fluorine-deficient silicon-modified nano-alumina) 82 88 86 0.82 +4 75 62 Comparative Example 2 (lacking anatase-type titanium dioxide) 116 78 91 0.43 +5 79 89 Comparative Example 3 (single antioxidant) 117 86 83 0.37 +7 77 91

[0162] As can be seen from Table 1, the initial water contact angles of Examples 1 to 3 are 115°~122°, indicating that the surface of the material has good hydrophobic properties; the tensile strength retention rate after 1000h of UV aging is 87%~92%, therefore, the material prepared in this application has excellent resistance to UV aging and is suitable for use in scenarios with strong ultraviolet rays in high-altitude areas; the elongation at break retention rate after 50 hot and cold cycles is greater than or equal to 90%, indicating that it can withstand extreme temperature changes; and the mass loss rate after 200h of wind and sand wear is 0.32%~0.38%, therefore, it also has good resistance to wind and sand wear; the Shore A hardness increase after aging does not exceed 4°, which can stably maintain the flexibility required for seismic isolation; the seismic isolation efficiency after 1000h of aging is 86%~90%, and the core seismic isolation function is stable; the bird droppings cleaning efficiency is 88%~93%, and combined with the hydrophobic properties, bird droppings can be efficiently removed through natural rainfall, reducing the long-term adhesion of pollutants.

[0163] In addition, compared with the examples, the hydrophobicity, wind and sand wear resistance, and bird droppings cleaning ability of Comparative Example 1 were significantly reduced due to the lack of fluorine-silicon modified nano-alumina, and its anti-fouling and anti-damage performance were poor. Comparative Example 2 did not add anatase titanium dioxide. Compared with the examples, its tensile strength retention rate after UV aging was significantly reduced, and the material's resistance to ultraviolet aging was significantly weakened, resulting in poor anti-ultraviolet performance. Comparative Example 3, in which the compound antioxidant was replaced with a single antioxidant, showed a significantly lower retention rate of elongation at break after hot and cold cycles, an increase in the hardness change after aging, and a decline in the material's resistance to temperature-induced aging.

[0164] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A new anti-aging material for high-altitude seismic isolation bearings, characterized in that: Calculated by mass fraction, the raw materials include: 85-90 wt% silicone rubber, 1-2 wt% nano-sized silicon dioxide, 3-5 wt% micron-sized calcium carbonate, 0.5-1.5 wt% anatase titanium dioxide, 0.1-0.3 wt% fluorine-silicon modified nano-alumina, 1-1.5 wt% oxide vulcanization aid, and 1-2 wt% antioxidant.

2. The new anti-aging material for high-altitude seismic isolation bearings according to claim 1 is characterized in that: The mass ratio of the nano-sized silicon dioxide to the micron-sized calcium carbonate is (0.3-0.5):

1.

3. The new anti-aging material for high-altitude seismic isolation bearings according to claim 1 is characterized in that: The antioxidant is a mixture of amine compounds and phenolic compounds.

4. A method for preparing a novel anti-aging material for high-altitude seismic isolation bearings, characterized in that: The new anti-aging material used in the high-altitude seismic isolation bearing according to any one of claims 1 to 3 comprises: Step 1: Put the silicone rubber into an internal mixer for plasticization, then add micron-sized calcium carbonate and nano-sized silicon dioxide in sequence, and perform the first mixing to disperse the micron-sized calcium carbonate in the rubber continuous phase and allow the nano-sized silicon dioxide to be initially adsorbed on the surface of the micron-sized calcium carbonate; Step 2: adding fluorine-silicon modified nano-alumina and anatase titanium dioxide to the product of step 1, performing a second mixing, and simultaneously performing ultrasonic treatment, so that the anatase titanium dioxide and the fluorine-silicon modified nano-alumina are uniformly embedded between the silicone rubber molecular chains; Step 3: adding a peroxide curing agent and an antioxidant to the product of step 2, performing a third mixing and aging process to obtain an aged rubber composite material; Step 4: placing the aged rubber composite material into a mold cavity of a vulcanization device for vulcanization to obtain a vulcanized rubber composite material; Step 5: placing the rubber composite material in a radio frequency plasma device, and performing plasma treatment on the surface of the vulcanized rubber composite material using a treatment gas containing argon and oxygen to obtain a new anti-aging material.

5. The method for preparing the new anti-aging material for high-altitude seismic isolation bearings according to claim 4, characterized in that: In the step 1, the first mixing condition is: mixing at a rotation speed of 30-50 rpm for 8 minutes.

6. The method for preparing the new anti-aging material for high-altitude seismic isolation bearings according to claim 4, characterized in that: In step 2, the second mixing condition is: mixing at 50-60° C. for 5 minutes.

7. The method for preparing the new anti-aging material for high-altitude seismic isolation bearings according to claim 6, characterized in that: In step 2, the conditions for the ultrasonic treatment are: Before 3 minutes, set the main frequency to 20kHz, power to 100W, the auxiliary frequency to 40kHz, power to 50W; After 3 minutes, set the main frequency to 20kHz, power to 60W, and the auxiliary frequency to 40kHz, power to 30W.

8. The method for preparing the new anti-aging material for high-altitude seismic isolation bearings according to claim 5, characterized in that: In step 3, the third mixing and aging specifically includes: mixing at a rotation speed of 30-50 rpm for 3 minutes, and aging for 12 hours after the mixing is completed.

9. The method for preparing the new anti-aging material for high-altitude seismic isolation bearings according to claim 4, characterized in that: In step 4, the step of placing the matured rubber composite material into a mold cavity of a vulcanization device for vulcanization specifically includes: The cured rubber composite material is added to the mold cavity of the vulcanization equipment, and the temperature is increased to 150° C. at a rate of 2-3° C. / min, and a pressure of 15 MPa is applied during the heating process; After heating to 150°C, continue heating to 170-180°C at a rate of 2-4°C / min under a pressure of 15 MPa; At 170-180°C, gradually reduce the pressure from 15 MPa to 12 MPa and maintain for 10-20 minutes; Then the temperature is lowered to below 80°C at a rate of 1-2°C / min, and after pressure relief, the mold is opened to take out the vulcanized rubber composite material.

10. The method for preparing the new anti-aging material for high-altitude seismic isolation bearings according to claim 4, characterized in that: Before step 4, the method further includes pre-processing the mold cavity, including: Polish the mold cavity to a surface roughness of Ra 5~10nm, and spray the release agent after cleaning.

Images