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CN-122010596-A - Stone cultural relic protection material reinforcing agent of graphene composite nano aluminum phosphate, preparation and application

CN122010596ACN 122010596 ACN122010596 ACN 122010596ACN-122010596-A

Abstract

The invention discloses a stone cultural relic protection material reinforcing agent of graphene composite nano aluminum phosphate, and preparation and application thereof, and belongs to the field of cultural relic protection materials. The preparation method comprises the steps of dissolving diammonium hydrogen phosphate in deionized water, mixing graphene quantum dot aqueous solution with aluminum chloride hexahydrate to dissolve in deionized water after electromagnetic water bath stirring, slowly dripping the formed GQDs-AlCl 3 mixed solution into DAP solution, continuing electromagnetic water bath stirring to obtain graphene composite nano AlPO 4 precursor solution, moving the graphene composite nano AlPO 4 precursor solution to a high-pressure reaction kettle, after reaction in an oven, performing ultrasonic dispersion on a reaction product, alternately centrifuging and washing the deionized water and ethanol for a plurality of times, putting into the oven for drying, and grinding to obtain graphene composite nano AlPO 4 powder serving as an enhancer for protecting HAP materials of stone relics. The invention solves the problem that the prior HAP protective material is easy to crack.

Inventors

  • GU YAOQI
  • WEI SHUYA
  • ZHA JIANRUI
  • LI QING
  • LI DI
  • LU JIABING

Assignees

  • 北京科技大学
  • 北京石刻艺术博物馆

Dates

Publication Date
20260512
Application Date
20260126

Claims (10)

  1. 1. The preparation method of the graphene composite nano aluminum phosphate stone cultural relic protection material reinforcing agent is characterized by comprising the following steps of: Dissolving diammonium hydrogen phosphate in deionized water, mixing graphene quantum dot aqueous solution and aluminum chloride hexahydrate after electromagnetic water bath stirring, dissolving in deionized water, slowly dripping the formed GQDs-AlCl 3 mixed solution into DAP solution, and continuing electromagnetic water bath stirring to obtain graphene composite nano AlPO 4 precursor solution; and (2) transferring the graphene composite nano AlPO 4 precursor solution to a high-pressure reaction kettle, performing ultrasonic dispersion on a reaction product, performing centrifugal cleaning on deionized water and ethanol alternately for a plurality of times after the reaction in an oven, putting the reaction product into the oven for drying, and grinding to obtain graphene composite nano AlPO 4 powder serving as an enhancer of a stone cultural relic protection HAP material.
  2. 2. The method for preparing the graphene composite nano aluminum phosphate stone relic protection material reinforcing agent according to claim 1, wherein the lattice constant of the graphene composite nano AlPO 4 powder is between the stone relic and HAP.
  3. 3. The method for preparing the graphene composite nano aluminum phosphate stone relic protection material reinforcing agent according to claim 1, wherein the stone relic is a marble stone relic.
  4. 4. The method for preparing the graphene composite nano aluminum phosphate stone relic protection material reinforcing agent according to claim 1, wherein the step (1) is specifically: Dissolving 0.005-0.02mol of DAP in 10-40ml of deionized water, stirring in a 70-90 ℃ electromagnetic water bath for 10-30min, mixing 0.5-2ml of GQDs with 0.005-0.02mol of AlCl 3 ·6H 2 O, dissolving in 15-60ml of deionized water, slowly dripping the GQDs-AlCl 3 mixed solution into the DAP solution, and continuing stirring in the 70-90 ℃ electromagnetic water bath for 0.5-2h to obtain the graphene composite nano AlPO 4 precursor solution.
  5. 5. The method for preparing the graphene composite nano aluminum phosphate stone relic protection material reinforcing agent according to claim 1, wherein the step (2) is specifically: Transferring the obtained graphene composite nano AlPO 4 precursor solution to a high-pressure reaction kettle, reacting for 8-12 hours in a 170-180 ℃ oven, ultrasonically dispersing the reaction product, alternately centrifugally cleaning deionized water and ethanol for 2-4 times, putting into a 50-80 ℃ oven for drying for 10-15 hours, and grinding to obtain graphene composite nano AlPO 4 powder.
  6. 6. A graphene composite nano aluminum phosphate stone relic protective material reinforcing agent, wherein the stone relic protective material reinforcing agent is graphene composite nano AlPO 4 powder obtained by adopting the preparation method according to any one of claims 1 to 5; the lattice constant of the graphene composite nano AlPO 4 powder is between that of stone relics and HAP.
  7. 7. Use of a stone relic protection material enhancer employing the graphene composite nano aluminum phosphate according to claim 6 in relic protection.
  8. 8. The application of the graphene composite nano aluminum phosphate stone cultural relic protection material reinforcing agent in cultural relic protection according to claim 7, which is characterized by comprising the following steps: Preparing graphene composite nano AlPO 4 powder to obtain deionized water nano dispersion liquid, dripping the nano dispersion liquid on the surface of a stone cultural relic, and standing to obtain a graphene composite nano AlPO 4 deposition layer; And (22) soaking the stone relic with the graphene composite nano AlPO 4 deposition layer in DAP solution, taking out the stone relic after a plurality of hours, cleaning the stone relic with deionized water, and naturally drying the stone relic at room temperature to obtain a graphene composite nano AlPO 4 -HAP double-layer film structure, thereby realizing the protection of the stone relic.
  9. 9. The application of the graphene composite nano aluminum phosphate stone relic protection material reinforcing agent according to claim 8, wherein the step (21) is specifically: Preparing graphene composite nano AlPO 4 into 0.1-0.3g/L deionized water nano dispersion liquid, dripping the nano dispersion liquid on the surface of a stone cultural relic according to the volume of 0.2-0.8ml/cm 2 , and standing for more than 18 hours to obtain a graphene composite nano AlPO 4 deposition layer.
  10. 10. The application of the graphene composite nano aluminum phosphate stone relic protection material reinforcing agent according to claim 8, wherein the step (22) is specifically: Soaking a stone cultural relic with the graphene composite nano AlPO 4 deposition layer in 0.5-2mol/L DAP solution, taking out a sample after more than 18 hours, cleaning with deionized water, and naturally drying at room temperature to obtain the graphene composite nano AlPO 4 -HAP double-layer membrane structure.

Description

Stone cultural relic protection material reinforcing agent of graphene composite nano aluminum phosphate, preparation and application Technical Field The invention belongs to the field of cultural relic protection materials, and particularly relates to a graphene composite nano aluminum phosphate stone cultural relic protection material reinforcing agent, preparation and application. Background The stone relics are used as a representation form of cultural heritage, are witness and carrier of ancient human civilization, and have the value of inheriting cultural root and pulse and promoting the soul of ethnicity, so the stone relics are of great significance in protecting the stone relics. However, most open-air stone relics suffer from various physical, chemical and biological efflorescence all the year round under the influence of natural climate and human activity, and diseases such as cracks, chalking, flaking, disintegration, crusting, erosion, defect, pollution, biological damage, improper repair and the like appear. The corrosion and pulverization are the most apparent and common diseases in the rock cultural relics of the open sky, and a large number of stone-engraved surface pictures and characters are blurred, so that the surface morphology of the cultural relics is destroyed, the explanation of the historical cultural value is influenced, the combination among stone particles is destroyed, and development conditions are provided for more other diseases, so that a safe and effective protection scheme is needed. The bionic inorganic mineralized material has special structure and function, wherein Hydroxyapatite (HAP) is a main component of natural bone inorganic matters, has compact structure, strong matching property and good corrosion resistance, and is used as a novel bionic material in the field of stone cultural relics protection for more than ten years. In the field of cultural relic protection, most of the HAP is prepared directly on the stone surface in situ by using a chemical method, for example, ammonium phosphate salt solution with a certain concentration is used for directly reacting with calcium ions dissolved out of marble. However, the protective film prepared at present has defects such as cracks, gaps and the like, so that the film forming effect is greatly reduced. Disclosure of Invention In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art and provides a stone cultural relic protection material reinforcing agent of graphene composite nano aluminum phosphate, and preparation and application thereof. The graphene composite nano AlPO 4 particles with lattice constants between marble and HAP are obtained through a hydrothermal method, a novel process for preparing the graphene composite nano AlPO 4 is provided, the compatibility with a marble substrate is good, the graphene composite nano AlPO 4 -HAP composite reinforced protective coating with uniform film formation is prepared through a chemical method, and the problem that an existing HAP protective material is easy to crack is solved. According to a first aspect of the technical scheme of the invention, the preparation method of the stone cultural relic protection material reinforcing agent of the graphene composite nano aluminum phosphate is provided, and comprises the following steps: Dissolving diammonium hydrogen phosphate (DAP) in deionized water, mixing a graphene quantum dot aqueous solution with aluminum chloride hexahydrate to dissolve in the deionized water after electromagnetic water bath stirring, slowly dripping the formed GQDs-AlCl 3 mixed solution into the DAP solution, and continuing electromagnetic water bath stirring to obtain a graphene composite nano AlPO 4 precursor solution; and (2) transferring the graphene composite nano AlPO 4 precursor solution to a high-pressure reaction kettle, performing ultrasonic dispersion on a reaction product, performing centrifugal cleaning on deionized water and ethanol alternately for a plurality of times after the reaction in an oven, putting the reaction product into the oven for drying, and grinding to obtain graphene composite nano AlPO 4 powder serving as an enhancer of a stone cultural relic protection HAP material. Further, the lattice constant of the graphene composite nano AlPO 4 powder is between that of stone relics and HAP. Further, the stone relic is a marble stone relic. Further, the step (1) specifically comprises the following steps: Dissolving 0.005-0.02mol of DAP in 10-40ml of deionized water, stirring in a 70-90 ℃ electromagnetic water bath for 10-30min, mixing 0.5-2ml of GQDs with 0.005-0.02mol of AlCl 3·6H2 O, dissolving in 15-60ml of deionized water, slowly dripping the GQDs-AlCl 3 mixed solution into the DAP solution, and continuing stirring in the 70-90 ℃ electromagnetic water bath for 0.5-2h to obtain the graphene composite nano AlPO 4 precursor solution. Further, in the step (1): Dissolving 0.01m