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CN-121975353-A - Multistage nano SiO2Wind-proof reinforcing material for basic masonry cultural relics and preparation method thereof

CN121975353ACN 121975353 ACN121975353 ACN 121975353ACN-121975353-A

Abstract

The invention discloses a multistage nano SiO 2 -based masonry relic anti-weathering reinforcing material and a preparation method thereof, and relates to the technical field of relic protection materials. The method comprises the steps of preparing aqueous dispersion of a surfactant, adding an alkaline catalyst to prepare a water phase, dispersing a silicon source in an organic solvent to form an oil phase, preparing multi-level nano SiO 2 particles, carrying out surface activation on the multi-level nano SiO 2 particles by adopting a strong oxidant, then modifying the surfaces of the activated multi-level nano SiO 2 particles by adopting alkoxy silane or organosilicon quaternary ammonium salt to obtain super-hydrophobic nano SiO 2 particles with multi-level morphology, and dispersing the super-hydrophobic nano SiO 2 particles with multi-level morphology in the organic solvent according to the mass fraction of 1-5%, thus obtaining the multi-level nano SiO 2 -based masonry cultural relic wind-proof reinforcing material. The invention solves the problems that the existing masonry relic weather-proof material is complex in preparation process, single in function, poor in durability and the like, and is not suitable for large-scale production and application.

Inventors

  • CAO YIJIAN
  • Feng Wanqian
  • WANG CONG
  • DONG WENQIANG
  • Mara kamaidi

Assignees

  • 西北工业大学

Dates

Publication Date
20260505
Application Date
20260105

Claims (10)

  1. 1. The preparation method of the multistage nano SiO 2 -based masonry relic anti-wind-oxidation reinforcing material is characterized by comprising the following steps of: Preparing aqueous dispersion of a surfactant, adding an alkaline catalyst to prepare a water phase, dispersing a silicon source in an organic solvent to form an oil phase, adding the oil phase into the water phase, and stirring and reacting at 50-60 ℃ to prepare multi-level nano SiO 2 particles; Adopting a strong oxidant to perform surface activation on the multi-stage nano SiO 2 particles, and then adopting alkoxy silane or organosilicon quaternary ammonium salt to modify the surfaces of the activated multi-stage nano SiO 2 particles to obtain the super-hydrophobic nano SiO 2 particles with multi-stage morphology; Dispersing the super-hydrophobic nano SiO 2 particles with the multi-level morphology in an organic solvent with the mass fraction of 1-5%, and obtaining the multi-level nano SiO 2 -based masonry relic anti-weathering reinforcing material.
  2. 2. The preparation method of the multistage nano SiO 2 -based masonry relic anti-weathering reinforcement material according to claim 1, wherein the surface activation of the multistage nano SiO 2 particles is carried out by adopting a strong oxidant, and the preparation method comprises the steps of pretreating the surfaces of the multistage nano SiO 2 particles by adopting the strong oxidant in a water bath at 80-85 ℃ to activate hydroxyl groups on the surfaces of the particles, wherein the strong oxidant is HNO 3 .
  3. 3. The method for preparing the multistage nano SiO 2 -based masonry cultural relic anti-weathering reinforcing material according to claim 1, wherein the surface of activated SiO 2 particles is modified by adopting alkoxy silane or organosilicon quaternary ammonium salt, and the method comprises the steps of adding activated multistage nano SiO 2 particles into an organic solvent containing the alkoxy silane or organosilicon quaternary ammonium salt, and reacting for 6-12 hours at 40-50 ℃.
  4. 4. The method for preparing the multistage nano SiO 2 -based masonry relic anti-weathering reinforcement material according to claim 3, wherein the alkyl alkoxysilane has the following structural formula: wherein R 1 、R 2 、R 3 is methyl or ethyl; The structural formula of the organosilicon quaternary ammonium salt is as follows: Wherein R is methyl, ethyl or hydrogen atom.
  5. 5. The method for preparing the multistage nano SiO 2 -based masonry cultural relic anti-weathering reinforcing material according to claim 3, wherein all organic solvents are cyclohexane or absolute ethyl alcohol, and the alkaline catalyst is NaOH.
  6. 6. The method for preparing the multistage nano SiO 2 -based masonry cultural relic anti-weathering reinforcing material according to claim 1, wherein the multistage nano SiO 2 particles are sea urchin-shaped nano particles with the particle size of 30-100 nm, the sea urchin-shaped nano particles have three-dimensional multistage morphology, the inner core diameter is about 30-70 nm, and the surface needle or tubular bulge length is about 5-20 nm.
  7. 7. A multi-stage nano SiO 2 -based masonry relic weathered reinforcement material produced by the method of any one of claims 1 to 6.
  8. 8. The use of the multi-stage nano SiO 2 -based masonry relic weathered reinforcement material according to claim 7 in masonry relic protection and repair.
  9. 9. The windproof reinforcing layer is characterized in that the multistage nano SiO 2 -based windproof reinforcing material for masonry relics is adopted, the windproof reinforcing material is uniformly coated on the surface of the masonry relics by spraying or brushing, and the windproof reinforcing layer is prepared on the surface of the masonry relics after the solvent is completely volatilized; Wherein, the capillary hydrophobic efficiency of the wind-proof reinforcing layer prepared on the masonry substrate with the porosity of 2-45% is higher than 92%.
  10. 10. The weatherproof reinforcement layer of claim 9, wherein the weatherproof reinforcement layer has a water contact angle of 156 ° to 168 ° and a roll angle of 2.0 ° to 5.0 °; The mechanical strength of the anti-weathering reinforcing layer is improved by 26%; When the concentration of the nano composite material in the wind-proof reinforcing layer is 0.2-1.5 g/L, the antibacterial efficiency of the wind-proof reinforcing layer on gram positive/negative bacteria reaches more than 90%.

Description

Multistage nano SiO 2 -based masonry relic anti-wind-aging reinforcing material and preparation method thereof Technical Field The invention relates to the technical field of cultural relic protection materials, in particular to a multistage nano SiO 2 -based masonry cultural relic anti-wind-break reinforcing material and a preparation method thereof. Background Masonry relics such as stone cave temple, cliff carving, stone carving and various stone ancient architectures are widely distributed in China and remain in a large number. The masonry cultural relics have higher historic, cultural and artistic values, are important components of historic cultural heritage of China, and are witnessed by thousands of years of bright culture of Chinese nationality. However, due to exposure to the open natural environment, the surface layer of masonry cultural relics is severely weathered under the long-term actions of natural power and artificial activities, and diseases such as cracks, chalking, flaking, salt, biological growth and the like are quite common. The disease not only seriously jeopardizes the stability of the cultural relics, but also causes the loss of the value contained in the cultural relics. Therefore, in order to slow down the surface layer weathering of masonry cultural relics and prevent the weathering from developing from the outside to the inside, development of a weather-proof reinforcing material which is good in compatibility, outstanding in performance and durable is urgent. In recent years, the super-hydrophobic material has strong application potential in the weather resistance of the surface layer of the cultural relics. Compared with the traditional organic and inorganic materials, the super-hydrophobic material can prevent the attachment and penetration of rainwater, surface water and condensed water and protect the cultural relic body, and can automatically clean the atmospheric pollutants, bird feces and the like attached to the surface by utilizing the self-cleaning function to maintain the artistic characteristics （Adv. Colloid Interface Sci., 2025, 335, 103343;Constr. Build. Mater., 2025, 467,140412; Constr. Build. Mater., 2022, 320, 126175）. of the surface of the cultural relic, however, as the intensive research and preliminary application find, the super-hydrophobic material generally has no reinforcing performance and cannot meet the application requirements of remodelling and deteriorating the cohesive force of the cultural relic body and improving the mechanical strength as an interface material, and the surface micro-nano multi-stage structure is fragile and easy to damage due to the structural and composition characteristics of the super-hydrophobic material, and meanwhile, low-surface energy substances are easy to consume, so that the durability of the super-hydrophobic material is poor. At present, the prior art discloses an inorganic-organic super-hydrophobic nano composite material for preventing stone cultural relics from being weathered. The material component comprises hydrophobic organic silicon liquid phase, and the weight percentage is 0.2-4 percent of nano ZnO/SiO 2 (ZnO coated SiO 2, and the average grain diameter is 20-200 nm). The material can form a layer of micron-nanometer double-layer structure layer with low surface energy on the surface of sandstone stone cultural relics, and has the functions of super-hydrophobicity and self-cleaning. The preparation process of nano ZnO/SiO 2 is more in the method, and the material does not show reinforcing performance and excellent durability. The prior art discloses a preparation method of a self-cleaning coating for protecting stone relics. The method comprises the steps of ① dispersing nano SiO 2、TiO2 and ZnO to obtain a mixed dispersion liquid, ② dispersing nano SiO 2 in the mixed dispersion liquid, ultrasonically purifying the SiO 2 dispersion liquid, ③ respectively adding a silane coupling agent and hydrochloric acid into the mixed dispersion liquid and the SiO 2 dispersion liquid to obtain a solution A and a solution B, ④ adding an aqueous emulsion diluted by water into the solution B to obtain a bonding layer solution for spraying, ⑤ ultrasonically spraying the bonding layer solution on a sample, naturally curing, ⑥ ultrasonically spraying the solution A on the sample, and drying the sample sprayed by ⑦ at room temperature to obtain the transparent self-cleaning super-hydrophobic coating. The preparation process of the method is complex, and the prepared anti-oxidation layer has single function. The prior art discloses a durable super-hydrophobic weather-proof material for masonry cultural relics and a preparation method thereof. The raw materials include partially fluorinated siloxane and solvent. The partially fluorinated siloxane is prepared by reacting an aminoalkyl silane coupling agent with fluorinated propylene oxide (the molar ratio of the aminoalkyl silane coupling agent to the fluorinated propylene ox