CN112225581A - Preparation method of durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating - Google Patents
Preparation method of durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention belongs to the technical field of preparation of novel light aging resistant coatings for stone cultural relics, and provides a preparation method of a durable hydrophobic light aging resistant stone cultural relic sealing and protecting coating, aiming at the defects of poor durability, easy pollution, poor light aging resistance, low strength and the like of the existing light aging resistant stone cultural relic sealing and protecting coating. Adding fluorosilane and nano TiO into isopropanol solution2Ultrasonic dispersion; preparing a mixed solution of PDMS and a curing agent; nano TiO to be grafted with fluorosilane2And drying, adding the dried mixture into PDMS mixed solution, performing ultrasonic dispersion, coating the mixture on the surface of the stone cultural relic, vacuumizing, and curing to obtain the durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating. Because the nano TiO with the light shielding performance is enriched on the surface2The light aging resistance is improved; fluorosilane-modified nano-T migrating to surfaceiO2The surface energy of the coating is reduced, and thus the hydrophobic property is improved. The preparation method is simple and easy to implement, has a short period, is suitable for large-scale production, and is applied to stone cultural relic protection.
Description
Technical Field
The invention belongs to the technical field of preparation of novel light aging resistant coatings for stone cultural relics, and particularly relates to a preparation method of a durable hydrophobic light aging resistant stone cultural relic sealing and protecting coating.
Background
The stone cultural relics are an important cultural relic form and are important carriers for recording the life, production and propagation civilizations of ancient people. However, the stone cultural relics receive serious wind, sand, rain, light, heat radiation and the like during the outdoor storage process,Serious damage such as microbial disease, severe weathering and corrosion. In addition, with the rapid development of human socioeconomic, a large amount of harmful exhaust gas is generated, such as a large amount of organic matters and SO discharged from the combustion process of coal2And NOx compounds, corrosion of stone cultural relics. In order to solve the problems of light radiation and pollutant corrosion of the stone cultural relics, the effective means for solving the problems is to coat a protective layer on the surfaces of the stone cultural relics. The polymer material has the characteristics of easy processing, simple method, easy modification, film formation and the like, and can effectively obstruct ultraviolet radiation and protect the stone cultural relics when being used in combination with the nano material with the ultraviolet absorption characteristic. In addition, the use of the nano material increases the surface roughness of the coating, enhances the wetting characteristic of the surface, realizes the super-hydrophobic self-cleaning characteristic by adjusting the surface energy, and prevents the adhesion pollution of pollutants.
At present, the common stone cultural relic protection coating is an acrylic resin-based silane/siloxane composite material, and the inorganic nano material is mainly SiO2，TiO2And the hydrophobic and anti-photoaging performances are realized through the increase of the surface roughness and the shielding effect of the nano material on ultraviolet rays, so that the stone cultural relics are protected. However, mixing inorganic nano-materials with macromolecules in a certain ratio results in brittleness, whitish color, crack initiation, and reduced durability of the coating. Therefore, the construction of the durable super-hydrophobic anti-photoaging stone cultural relic coating has very important significance for prolonging the service life of the stone cultural relic.
The prior art (patent No. ZL 201810008825.6, name: a preparation method of a durable PDMS bionic super-hydrophobic membrane) specifically discloses a preparation method of a durable super-hydrophobic membrane. The method is to form SiO by a mold2The nano particles are dispersed in the alcohol solution, loaded on a stainless steel net and then embedded into the surface of PDMS to obtain a micron/nano hierarchical structure, so that super-hydrophobicity is realized. However, the method has the defects that the film is thick, the appearance and the attractiveness of the stone cultural relic are influenced, and the operation on the surface of the stone cultural relic is not easy.
The prior art (application No. 201210565475.6, name: a stone cultural relic waterproof material and a preparation method thereof, published: 2014.10.01) specifically discloses titanium dioxide/polyethylene glycol octyl phenyl ether, aminopropyl triethoxysilane and a preparation method thereof. The method adopts ethanol and water as solvents to disperse polyethylene glycol octyl phenyl ether and aminopropyl triethoxysilane to prepare emulsion, then adds nano titanium dioxide to carry out ultrasonic dispersion, and carries out waterproof treatment by adopting means of spraying, brushing, soaking, pasting and the like. However, in the method, the hydrophobicity is in direct proportion to the content of titanium dioxide, and a large amount of titanium dioxide is often added for realizing the super-hydrophobic property, so that the brittleness of the coating is increased, the color is whitish, and the attractiveness of the stone cultural relic is influenced.
The prior art (application No. 201911115275.9, name: a scratch-resistant and light-aging-resistant polypropylene material and a preparation method thereof, published: 2020.03.27) specifically discloses a preparation method of a light-aging-resistant acrylic resin coating. The method uses polypropylene as film forming raw material, talcum powder, carbon black and scratch resistant agent as filler to improve durability, and uses light stabilizer and antioxidant to improve light aging resistance. However, the method uses carbon black to cause the coating to be changed from transparent to black and opaque, thereby affecting the original appearance and aesthetic degree of the stone cultural relic and not meeting the requirement of the coating of the stone cultural relic.
Disclosure of Invention
The invention provides a preparation method of a durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating, aiming at the defects of poor durability, easy pollution, poor photoaging resistance, low strength and the like of the traditional anti-photoaging stone cultural relic sealing and protecting coating.
The invention is realized by the following technical scheme: a durable hydrophobic and anti-photoaging stone cultural relic sealing and protecting coating is prepared by adding fluorosilane into isopropanol solution, and then adding nano TiO2Ultrasonic dispersing to obtain nano TiO2Uniformly grafting fluorosilane on the surface; preparing a mixed solution of polydimethylsiloxane PDMS and a curing agent; nano TiO to be grafted with fluorosilane2And drying, adding the dried mixture into a mixed solution of PDMS and a curing agent, performing ultrasonic dispersion, coating the mixed solution on the surface of the stone cultural relic, vacuumizing, and curing to obtain the durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating.
The method comprises the following specific steps:
(1) nano TiO modified by fluorosilane2Preparing a precursor: firstly, dispersing fluorosilane in isopropanol serving as a solvent, and performing ultrasonic dispersion; then adding nano TiO2And ultrasonically dispersing;
(2) preparing a mixed solution of polydimethylsiloxane PDMS and a curing agent: the mass ratio of PDMS to curing agent is 1: 1-10: 1, mixing PDMS with a curing agent;
(3) nano TiO modified by fluorosilane2Preparation of mixed precursor solution with PDMS: the nano TiO modified by the fluorosilane prepared in the step (1)2Adding the precursor into the mixed solution of polydimethylsiloxane PDMS and the curing agent prepared in the step (2), and performing ultrasonic dispersion for 5-30 min; nano TiO modified by fluorosilane2The mass fraction in PDMS is 0.01wt% -10.0 wt%;
(4) preparing a durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating: the fluorosilane modified nano TiO obtained in the step (3)2Spraying or dipping the mixed precursor solution with PDMS on the surface of the stone cultural relic, vacuumizing at room temperature until the solvent is completely volatilized, removing bubbles, and curing the nano TiO2And transferring to the surface of PDMS to obtain the durable hydrophobic light aging resistant stone cultural relic sealing and protecting coating.
The intermediate fluorosilane in the step (1) is silane or siloxane with low fluorine-containing surface energy and nano TiO2Is TiO2The nano particles, nano wires, nano fibers or nano blocks simultaneously comprise doped and modified nano materials; the solvent is isopropanol; the mass concentration of fluorosilane in isopropanol is 0.001-1.0 wt%, and nano TiO2The mass concentration in the isopropanol is 0.01wt% -10wt%, and the fluorosilane is nano TiO20.01wt% -1.0wt% of the amount of the active ingredient; the ultrasonic dispersion time of fluorosilane in isopropanol is 5-60 min; nano TiO22The ultrasonic dispersion time in the fluorosilane isopropanol is 5-30 min.
The curing agent in the step (2) is a conventional commercially available product, in particular a Sygard 184 silicon resin curing agent sold by Dow Corning company; the mass ratio of PDMS to curing agent is 10: 1.
vacuumizing for 1-120min in the step (4); the curing time of the composite coating is 5-120min, and the curing temperature is60-120 ℃; the coating process of the stone cultural relic coating is dip coating or pressure spray gun spraying; the method specifically comprises the following steps: dip coating: completely dipping the massive stone cultural relics into fluorosilane modified nano TiO2Soaking in the mixed precursor solution of PDMS for 30s, taking out, repeating for 3-5 times, placing in a vacuum glove box, vacuumizing to remove bubbles, and curing; the spraying process of the pressure spray gun has the following requirements: caliber of a spray gun nozzle: 0.05mm-0.3 mm; pressure: 0.1MPa to 0.6 MPa; frequency: 10HZ-50 HZ; the addition amount is as follows: 0.1g to 2.0 g.
The intermediate fluorosilane in the step (1) is tridecafluorooctyl trimethoxysilane, perfluorooctyl trichlorosilane, heptadecafluorodecyl trimethoxysilane or trifluoromethyl trimethylsilane; the concentration of fluorosilane in isopropanol is 0.1wt%, 0.5wt% or 1.0 wt%; nano TiO22The mass concentration in isopropanol is 0.1wt%, 2.0wt% or 10 wt%.
The thickness of the prepared mixed coating is 1-1000 mu m, and the nano TiO migrates to the surface2The thickness is 10nm-500 nm.
Vacuumizing for 10min, 30min or 1h in the step (4); the curing time of the composite coating is 30min or 1 h; the curing temperature is 75 ℃ or 90 ℃.
Nano TiO22The dosage of the nano TiO ensures the use of nano TiO2The transparency of PDMS is not affected. Nano TiO modified by fluorosilane2The dosage of the nano TiO compound ensures enough chemical potential difference and promotes the nano TiO2Migration to the surface of the coating.
The invention utilizes fluorosilane with lower surface energy to modify nano TiO2Surface, driven by chemical potential difference, nano TiO2Migration to the surface of PDMS, resulting in increased surface roughness without nano TiO inside2. By adding nano TiO2The surface is grafted with fluorosilane with lower surface energy, and the nano TiO with lower surface energy is promoted by the difference of chemical potential (surface energy)2Directionally migrate to the surface of PDMS without nano TiO inside2And the surface roughness follows nanometer TiO2The migration from the interior of PDMS to the surface is improved, a rough surface is formed, and nano TiO2Hydrophobic property is realized under the combined action of the surface fluorosilane.
The invention can realize the nano TiO without the help of external force2The method has the advantages of simple operation, low cost, strong operability, easy coating on the surface of the stone cultural relic and formation of a sealing and protecting coating with high film forming degree. Nano TiO22Under the promotion of chemical potential, the nano TiO is transferred to the surface of PDMS, so that the nano TiO is greatly reduced2The usage amount of the inorganic nano material reduces the manufacturing cost, and effectively solves the problem that the brittleness of the polymer material is increased due to the use of the inorganic nano material; nano TiO22The composite material is firmly combined with a PDMS substrate through physical action, and the durability is improved, so that the composite material has lasting hydrophobicity.
The contact angle of the coating prepared by the method of the invention to water is 100-120 degrees. Nano TiO22The ultraviolet light is promoted to migrate to the surface of the coating from the inside of the coating under the promotion of chemical potential, so that the ultraviolet light shielding and absorbing capacity is improved, ultraviolet rays are effectively prevented from entering the inside of the PDMS coating, bond breakage is caused, and the aging of macromolecules is caused, and the light aging resistance is improved. Furthermore, nano TiO2After the polymer is transferred to the surface of the coating, the polymer is crosslinked with the substrate, so that the bonding strength is high, the polymer is not easy to fall off from the surface, and the durability is improved.
The method has the characteristics of simplicity, rapidness and high efficiency. Meanwhile, the durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating skillfully utilizes the action of chemical potential to ensure that the nano TiO is coated on the surface of the cultural relic2The nano-material migrates to the surface, and the dosage of the nano-material and the negative influence on the high-molecular material are greatly reduced on the premise of ensuring the same light aging resistance. The method can coat the PDMS/titanium dioxide dispersion liquid on the surface of the stone cultural relic through various ways, and has wide practicability.
Drawings
FIG. 1 shows the results obtained in example 1 without adding TiO2Scanning electron microscope images of the microstructure of the PDMS coating surface of the particles;
FIG. 2 is a scanning electron microscope image of the microstructure of the surface and cross section of the composite coating after the anti-photoaging fluorosilane prepared in example 1 of the present invention is modified and mixed with PDMS;
FIG. 3 is a graph showing the effect of contact angle of water drops on a composite coating after mixing PDMS after being modified with durable fluorosilane prepared according to the present invention;
figure 4 is a digital photograph of sandstone and its coated TiO2 nanoparticle-PDMS composite coating, according to an example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: a preparation method of a durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating specifically comprises the following steps:
(1) preparing a fluorosilane dilute solution: adding fluorosilane into isopropanol in a vacuum glove box, performing ultrasonic dispersion for 5min, wherein the mass fraction of fluorosilane is 1.0wt%, sealing with a sealing film, and placing in the glove box for later use;
(2) nano TiO modified by fluorosilane2: in a vacuum and glove box, nanometer TiO is added2Adding into diluted fluorosilane solution, and ultrasonically dispersing for 5 min; and (3) placing the mixture in a vacuum drying oven for drying, and removing the organic solvent, wherein the drying temperature is 25 ℃, and the drying time is 8 h.
(3) Preparing a durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating: nano TiO modified by fluorosilane2Adding into PDMS solution, and ultrasonically dispersing for 30min, wherein the nano TiO is2Is 10.0 wt%. Spraying the uniformly dispersed dispersion liquid onto the surface of the stone cultural relic, wherein the spraying amount is 0.5g, the spraying pressure is 0.3MPa, the diameter of a spray gun opening is 0.2mm, and the distance between a spray gun and the stone cultural relic is 20 cm; or soaking the blocky stone cultural relic in the solution, waiting for 30s, taking out, repeating for 3 times, and forming a coating layer on the surface; vacuumizing for 10min, and curing at 60 deg.C for 60 min.
(4) And spraying the uniformly mixed PDMS and curing agent precursor liquid onto the surface of the stone cultural relic, wherein the spraying amount is 0.5g, the spraying pressure is 0.3MPa, the diameter of a spray gun opening is 0.2mm, and the distance between a spray gun and the stone cultural relic is 20cm, and the comparison sample is prepared.
Example 2: a preparation method of a durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating specifically comprises the following steps:
(1) preparing a fluorosilane dilute solution: adding fluorosilane into isopropanol in a vacuum glove box, performing ultrasonic dispersion for 5min, wherein the mass fraction of fluorosilane is 0.5wt%, sealing with a sealing film, and placing in the glove box for later use;
(2) nano TiO modified by fluorosilane2: in a vacuum and glove box, nanometer TiO is added2Adding the mixture into diluted fluorosilane solution, and carrying out ultrasonic dispersion for 5 min; and (3) placing the mixture in a vacuum drying oven for drying, and removing the organic solvent, wherein the drying temperature is 25 ℃, and the drying time is 8 h.
(3) Preparing a durable hydrophobic anti-photoaging coating: nano TiO modified by fluorosilane2Adding into PDMS solution, and ultrasonically dispersing for 30min, wherein the nano TiO is2Is 2.0 wt%. Spraying the uniformly dispersed dispersion liquid onto the surface of the stone cultural relic, wherein the spraying amount is 1.5g, the spraying pressure is 0.6MPa, the diameter of a spray gun opening is 0.5 mm, and the distance between a spray gun and the stone cultural relic is 30 cm; or soaking the blocky stone cultural relic in the solution, waiting for 30s, taking out, repeating for 5 times, and forming a coating layer on the surface; after 20min after evacuation, curing was carried out at 75 ℃ for 10 min.
Example 3: a preparation method of a durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating specifically comprises the following steps:
(1) preparing a fluorosilane dilute solution: adding fluorosilane into isopropanol in a vacuum glove box, performing ultrasonic dispersion for 5min, wherein the mass fraction of fluorosilane is 0.1wt%, sealing with a sealing film, and placing in the glove box for later use;
(2) nano TiO modified by fluorosilane2: in a vacuum and glove box, nanometer TiO is added2Adding into diluted fluorosilane solution, and ultrasonically dispersing for 10 min; placing it in a vacuum drierDrying in a drying oven, removing the organic solvent, wherein the drying temperature is 25 ℃, and the drying time is 8 h.
(3) Preparing a durable hydrophobic anti-photoaging coating: nano TiO modified by fluorosilane2Adding into PDMS solution, and ultrasonically dispersing for 45min, wherein the nano TiO is2Is 1.0 wt%. Spraying the uniformly dispersed dispersion liquid onto the surface of the stone cultural relic, wherein the spraying amount is 1.5g, the spraying pressure is 0.6MPa, the diameter of a spray gun opening is 0.5 mm, and the distance between a spray gun and the stone cultural relic is 30 cm; or soaking the blocky stone cultural relic in the solution, waiting for 30s, taking out, repeating for 5 times, and forming a coating layer on the surface; after 20min after evacuation, curing at 90 ℃ for 10 min.
Fig. 1 and 2 are the results in example 1, respectively: without addition of TiO2PDMS coated surface of nanoparticles (fig. 1); TiO modified by fluorosilane2The coating surface and cross-sectional micro-topography after mixing the nanoparticles into PDMS (fig. 2). As can be seen from FIG. 2, TiO was modified with fluorosilane2The nano particles migrate to the surface of the coating under the driving of chemical potential without the modification of fluorine silane on the inner part and the bottom part of the coating2And (3) nanoparticles. Proves that the directional migration of the nano material can be regulated and controlled by the action of chemical potential to obtain the surface-enriched TiO2The light shielding of the nanoparticles, with the interior still being PDMS, demonstrates the feasibility of this approach.
FIG. 3 shows TiO modified with fluorosilane2Contact angle of PDMS composite coating, TiO modified by fluorosilane2The nanoparticles, which do not significantly reduce PDMS bonding to the thick foot, still maintain high hydrophobicity, prove the feasibility of the method.
FIG. 4 depicts sandstone and its coated TiO selected for use in embodiments of the present invention2Digital photo of nanoparticle-PDMS composite coating.
In the application example of the invention, fluorosilane is used for modifying TiO2The nano particle-PDMS composite coating is sprayed on the sandstone surface and is irradiated under UV (254 nm) for different time (0-240 h). Particularly, after 240 hours of irradiation, the contact angle is still 100 degrees, the coating layer shows better transmittance, and the surface has no obvious aging phenomenon. Demonstration of TiO modification by Fluorosilane2Nano particles to make it becomeThe surface is reached under the promotion of the chemical potential, and the light aging resistance is improved.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A preparation method of a durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating is characterized by comprising the following steps: adding fluorosilane into isopropyl alcohol solution, and then adding nano TiO2Ultrasonic dispersing to obtain nano TiO2Uniformly grafting fluorosilane on the surface; preparing a mixed solution of polydimethylsiloxane PDMS and a curing agent; nano TiO to be grafted with fluorosilane2And drying, adding the dried mixture into a mixed solution of PDMS and a curing agent, performing ultrasonic dispersion, coating the mixed solution on the surface of the stone cultural relic, vacuumizing, and curing to obtain the durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating.
2. The method of claim 1 for preparing a durable hydrophobic photoaging-resistant stone cultural relic sealing and protecting coating, which is characterized in that: the method comprises the following specific steps:
(1) nano TiO modified by fluorosilane2Preparing a precursor: firstly, dispersing fluorosilane in isopropanol serving as a solvent, and performing ultrasonic dispersion; then adding nano TiO2And ultrasonically dispersing;
(2) preparing a mixed solution of polydimethylsiloxane PDMS and a curing agent: the mass ratio of PDMS to curing agent is 1: 1-10: 1, mixing PDMS with a curing agent;
(3) nano TiO modified by fluorosilane2Preparation of mixed precursor solution with PDMS: the nano TiO modified by the fluorosilane prepared in the step (1)2Adding the precursor into the polydiene prepared in the step (2)Ultrasonically dispersing for 5-30min in a mixed solution of methyl siloxane PDMS and a curing agent; nano TiO modified by fluorosilane2The mass fraction in PDMS is 0.01wt% -1.0 wt%;
(4) preparing a durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating: the fluorosilane modified nano TiO obtained in the step (3)2Spraying or dipping the mixed precursor solution with PDMS on the surface of the stone cultural relic, vacuumizing at room temperature until the solvent is completely volatilized, removing bubbles, and curing the nano TiO2And transferring to the surface of PDMS to obtain the durable hydrophobic light aging resistant stone cultural relic sealing and protecting coating.
3. The method of claim 2, wherein the durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating comprises the following steps: the intermediate fluorosilane in the step (1) is silane or siloxane with low fluorine-containing surface energy and nano TiO2Is TiO2The nano particles, nano wires, nano fibers or nano blocks simultaneously comprise doped and modified nano materials; the solvent is isopropanol; the mass concentration of fluorosilane in isopropanol is 0.001-1.0 wt%, and nano TiO2The mass concentration in the isopropanol is 0.01-10.0 wt%, and the fluorosilane accounts for 0.01-1.0 wt% of the dosage of the nano TiO 2; the ultrasonic dispersion time of fluorosilane in isopropanol is 5-60 min; nano TiO22The ultrasonic dispersion time in the fluorosilane isopropanol is 5-30 min.
4. The method of claim 2, wherein the durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating comprises the following steps: the curing agent in the step (2) is Sygard 184 silicon resin curing agent; the mass ratio of PDMS to curing agent is 10: 1.
5. the method of claim 2, wherein the durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating comprises the following steps: vacuumizing for 1-120min in the step (4); the curing time of the composite coating is 5-120min, and the curing temperature is 60-120 ℃; the coating process of the stone cultural relic coating is dip coating or pressure spray gun spraying; utensil for cleaning buttockThe body is as follows: dip coating: completely dipping the massive stone cultural relics into fluorosilane modified nano TiO2Soaking in the mixed precursor solution of PDMS for 30s, taking out, repeating for 3-5 times, placing in a vacuum glove box, vacuumizing to remove bubbles, and curing; the spraying process of the pressure spray gun has the following requirements: caliber of a spray gun nozzle: 0.05mm-0.3 mm; pressure: 0.1MPa to 0.6 MPa; frequency: 10HZ-50 HZ; the addition amount is as follows: 0.1g to 2.0 g.
6. The method of claim 3 for preparing a durable hydrophobic photoaging-resistant stone cultural relic sealing and protecting coating, which is characterized in that: the intermediate fluorosilane in the step (1) is tridecafluorooctyl trimethoxysilane, perfluorooctyl trichlorosilane, heptadecafluorodecyl trimethoxysilane or trifluoromethyl trimethylsilane; the concentration of fluorosilane in isopropanol is 0.1wt%, 0.5wt% or 1.0 wt%; nano TiO22The mass concentration in isopropanol is 0.1wt%, 2.0wt%, or 10.0 wt%.
7. The method of claim 2, wherein the durable hydrophobic anti-photoaging stone cultural relic sealing and protecting coating comprises the following steps: the thickness of the prepared mixed coating is 1-1000 mu m, and the nano TiO migrates to the surface2The thickness is 10nm-500 nm.
8. The method of claim 5 for preparing a durable hydrophobic photoaging-resistant stone cultural relic sealing and protecting coating, which is characterized in that: vacuumizing for 10min, 30min or 1h in the step (4); the curing time of the composite coating is 30min or 1 h; the curing temperature is 75 ℃ or 90 ℃.
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Cited By (3)
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| CN115572539A (en) * | 2022-09-22 | 2023-01-06 | 西北工业大学 | Durable super-hydrophobic anti-weathering material for masonry cultural relics, preparation method and coating preparation method |
| CN115991942A (en) * | 2022-11-29 | 2023-04-21 | 西北工业大学 | Weather-proof material for surface of open-air masonry cultural relics and preparation method thereof |
| CN116004114A (en) * | 2022-04-29 | 2023-04-25 | 重庆深盟新材料科技有限公司 | Light reflection heat-preservation weather-resistant coating and preparation method and application thereof |
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| CN115572539B (en) * | 2022-09-22 | 2024-01-16 | 西北工业大学 | Durable superhydrophobic weather-proof material for masonry cultural relics, preparation method and coating preparation method |
| CN115991942A (en) * | 2022-11-29 | 2023-04-21 | 西北工业大学 | Weather-proof material for surface of open-air masonry cultural relics and preparation method thereof |
| CN115991942B (en) * | 2022-11-29 | 2024-03-29 | 西北工业大学 | Weather-proof material for surface of open-air masonry cultural relics and preparation method thereof |
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