阅读说明：本技术 基于仿生矿化技术的瓷砖修复方法 (Ceramic tile repairing method based on biomimetic mineralization technology ) 是由 严勇 韩凯 于 2021-06-30 设计创作，主要内容包括：本发明涉及瓷砖表面修复技术领域,具体公开一种基于仿生矿化技术的瓷砖修复方法,以无机硅酸盐及微量正硅酸乙酯作为前驱体,以不同分子量聚多胺作为诱导分子,以磷酸铝作为粘结剂,以水溶性氨基酸作为二氧化硅结晶的分子开关,形成复合溶胶。将此溶胶涂覆在经过预处理的瓷砖基底上,伯铵盐型阳离子聚合物分子富集于瓷砖破损处诱导二氧化硅前驱体水解结晶,并自组装形成二氧化硅与聚多胺复合多孔层。经此溶胶处理的瓷砖,不仅其釉面得到修复,且其局部摩擦系数亦得到较大提升,因此,本发明在高效修复地面瓷砖的同时,又可以解决地面瓷砖遇水湿滑的安全难题；其成本低廉、使用过程简易、组分绿色环保。(The invention relates to the technical field of ceramic tile surface repair, and particularly discloses a ceramic tile repair method based on a biomimetic mineralization technology. The sol is coated on a pretreated ceramic tile substrate, primary ammonium salt type cationic polymer molecules are enriched at the damaged part of the ceramic tile to induce silica precursor to be hydrolyzed and crystallized, and the silica and polyamine composite porous layer is formed through self-assembly. The ceramic tile treated by the sol not only has a repaired glaze surface, but also has a greatly improved local friction coefficient, so that the invention can solve the safety problem that the floor ceramic tile is wet and slippery when encountering water while efficiently repairing the floor ceramic tile; the cost is low, the using process is simple, and the components are green and environment-friendly.)

1. A tile repairing method based on a biomimetic mineralization technology is characterized by comprising the following steps: the method comprises the following steps:

s1: regulating and controlling the surface charge of the ceramic tile: uniformly coating the prepared pretreatment solution on the surface of a ceramic tile substrate to be repaired, standing for a certain time, and washing the surface of the ceramic tile substrate coated with the pretreatment solution at high pressure by using a sodium bicarbonate solution with the pH value of 10-11 to ensure that the Zeta potential at the damaged part of the ceramic tile substrate glaze is between-20 mV and-35 mV;

s2: coating sol: coating the prepared biomimetic mineralization sol on the surface of the ceramic tile substrate cleaned in the step S1, drying and standing for a certain time, cleaning the ceramic tile substrate by using purified water, and removing sol residues at the undamaged part of the ceramic tile substrate;

s3: and (3) crystallization: fully infiltrating the ceramic tile substrate treated by the biomimetic mineralization sol in the step S2 with a water-soluble amino acid solution, standing for a certain time, and crystallizing an amorphous silica precursor in the biomimetic mineralization sol to form a crystallized silica and polyamine composite porous layer with Mohs hardness of more than or equal to 2.0; and (5) washing the crystallized ceramic tile substrate by adopting purified water, drying at room temperature for a certain time, and finishing the ceramic tile repairing treatment.

2. The ceramic tile repair method based on biomimetic mineralization technology as claimed in claim 1, wherein: preparing the pretreatment solution in the step S1, wherein the pretreatment solution comprises the following raw materials in parts by mass:

5 to 20 portions of inorganic sylvite, 1 to 5 portions of surfactant, 10 to 20 portions of fruit acid, 10 to 20 portions of sodium bicarbonate, 0.1 to 0.5 portion of glycol, 100 to 150 portions of deionized water, 1 to 5 portions of anionic emulsifier and 0.1 to 0.5 portion of titanium sulfate.

3. The ceramic tile repair method based on biomimetic mineralization technology as claimed in claim 1, wherein: the biomimetic mineralization sol prepared in the step S2 comprises the following raw materials in parts by mass:

15 to 30 parts of inorganic silicate, 0.1 to 0.5 part of ethyl orthosilicate, 1 to 5 parts of nano aluminum phosphate, 1 to 5 parts of primary ammonium salt type cationic polymer, 1 to 5 parts of sodium bicarbonate and 80 to 120 parts of deionized water.

4. The ceramic tile repair method based on biomimetic mineralization technology as claimed in claim 3, wherein: after the preparation of the biomimetic mineralized sol is finished, the method also comprises the following steps: and shaking up the biomimetic mineralized sol by adopting ultrasonic mixing equipment.

5. The ceramic tile repair method based on biomimetic mineralization technology as claimed in claim 1, wherein: the water-soluble amino acid solution in the preparation step S3 comprises the following raw materials in parts by mass:

0.1 to 0.5 portion of water-soluble amino acid, 5 to 10 portions of sodium bicarbonate and 100 to 150 portions of purified water.

Technical Field

The invention relates to the technical field of ceramic tile repair, in particular to a ceramic tile repair method based on a biomimetic mineralization technology.

Background

Various ceramic tiles such as vitrified tiles, glazed tiles and the like are neat and attractive, and are one of the ground building materials with the widest application and the largest market share in China. Nevertheless, most tile glazes are prone to wear and depreciation, and the aesthetics of the tile can be greatly reduced after the tile is used for several years; in this case, the surface is more apt to store dirt and soil, and the indoor environment is seriously affected. According to the statistics of Chinese building material market data, the re-paving and renovating rate of the floor ceramic tile caused by the problems of abrasion and depreciation is as high as 25 percent, and the resource waste and the environmental problems caused by the re-paving and renovating rate are in urgent need of solving. Therefore, the development of the efficient and universal ground tile repairing technology has extremely high market demand and application prospect.

However, the most common tile repair technique at present is mainly by manual sanding and polishing of the breakage and application of a protective layer of epoxy (and its derivatives). The method has high cost (40-60% of the price of the ceramic tile), low efficiency (2-3 square meters per hour), obvious repair trace; on the other hand, the damage to the ceramic tile substrate caused by the grinding and polishing process is self-evident, and the harm to the human health caused by the volatilization of the organic solvent caused by the epoxy resin coating process is huge. According to relevant commodity inspection data, a rigid surface and an epoxy resin coating layer thereof generated by manual polishing are easy to wear, the repairing effect can be maintained for 3-6 months, and repeated cleaning and maintenance are needed. Therefore, the environmental protection property, the treatment effect and the durability of the ceramic tile repairing technology far do not meet the application requirement of universality.

In addition, foreign companies such as 3M have developed products such as floor repair materials, adhesives, floor coatings, etc., for the problem of repairing tiles. However, these products will cause new problems such as slippery ground, increased volatile organic compounds, etc., and are only suitable for application scenarios with low environmental requirements such as industrial plants, etc.; in addition, the product is expensive and has short service life (less than or equal to 6 months), and large-scale popularization and application are difficult to realize.

In nature, organisms can construct functional materials with multilevel ordered structures under mild conditions by inducing molecules, and the mechanical properties of the functional materials are quite excellent, such as teeth, bones and the like. By simulating the process (called as biomimetic mineralization process), researchers can realize the oriented nucleation, growth and self-assembly of materials such as silicon dioxide, hydroxyl phosphorus lime, titanium dioxide and the like at room temperature, and realize the traceless repair of a certain substrate interface.

In conclusion, the ceramic tile traceless repair technology with excellent performance and environmental protection is designed and constructed by growing the crystallized silicon dioxide and the induced molecular compound in situ at the damaged part of the ceramic tile glaze based on the biomimetic mineralization technology, and meanwhile, the porous film formed by the silicon dioxide and the induced molecular compound can improve the local friction coefficient of the ceramic tile to a certain extent. Therefore, the method for repairing the ceramic tile fundamentally solves the problems of potential safety hazards such as complexity, high cost, obvious trace, serious indoor pollution, easy wet and slippery and the like of the existing ceramic tile repairing technology.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: in order to overcome the defects in the prior art, the invention provides a ceramic tile repairing method based on a biomimetic mineralization technology, which takes inorganic silicate, Tetraethoxysilane (TEOS), primary ammonium salt type cationic polymers with different molecular weights, aluminum phosphate and the like as biomimetic mineralization sol raw materials; the selective adsorption of polyamine on the damaged surface of the ceramic tile can be realized by regulating and controlling the Zeta potential of the damaged part of the ceramic tile substrate, and firstly, a silicon dioxide precursor is induced to hydrolyze and is filled in the damaged part of the ceramic tile; and then, introducing water-soluble amino acid to promote the crystallization and solidification of amorphous silica to form a translucent silica and polyamine composite porous layer with Mohs hardness of more than or equal to 2.0, thereby completing traceless repair of the ceramic tile.

According to the above analysis, the specific technical solution to be adopted for solving the technical problems of the present invention is as follows: a tile repairing method based on a biomimetic mineralization technology comprises the following steps:

s1: regulating and controlling the surface charge of the ceramic tile:

firstly, preparing a pretreatment solution: the pretreatment solution comprises the following raw materials in parts by mass: 5 to 20 portions of inorganic sylvite, 1 to 5 portions of surfactant, 10 to 20 portions of fruit acid, 10 to 20 portions of sodium bicarbonate, 0.1 to 0.5 portion of glycol, 100 to 150 portions of deionized water, 1 to 5 portions of anionic emulsifier and 0.1 to 0.5 portion of titanium sulfate; the solution can be prepared at room temperature in a conventional manner.

Then, the prepared pretreatment solution is sprayed in an atomizing wayUniformly coating the mixture on the surface of a ceramic tile substrate to be repaired, wherein the spraying dosage of the pretreatment solution is related to the area and the damage degree of the ceramic tile, and preferably, the dosage of the pretreatment solution is about 100-120 mL/m²；

Then, standing the ceramic tile floor coated with the pretreatment solution for 10-30 min, and washing the surface of the ceramic tile substrate coated with the pretreatment solution at high pressure by using a sodium bicarbonate solution with the pH value of 10-11; then, monitoring the Zeta potential at the damaged part of the ceramic tile by adopting a Zeta potentiometer until the Zeta potential at the damaged part of the glaze surface of the ceramic tile substrate to be repaired is between-20 mV and-35 mV; if the Zeta potential requirement cannot be met by one coating and cleaning, cyclic coating and cyclic cleaning can be carried out until the potential requirement is met. The pretreatment solution of the invention has two functions: (1) cleaning the surface of the ceramic tile; (2) the damaged glaze surface of the ceramic tile substrate is negatively charged under an alkaline condition, so that a condition is provided for the subsequent positively charged polyamine induced molecular adsorption.

S2: coating sol:

firstly, preparing biomimetic mineralized sol: the biomimetic mineralization sol comprises the following raw materials in parts by mass: 15 to 30 parts of inorganic silicate, 0.1 to 0.5 part of tetraethyl orthosilicate (TEOS), 1 to 5 parts of nano aluminum phosphate, 1 to 5 parts of primary ammonium salt type cationic polymer, 1 to 5 parts of sodium bicarbonate and 80 to 120 parts of deionized water; wherein, the primary ammonium salt type cationic polymer can play a good mineralization role on the silicon dioxide.

And then, mixing the raw materials of the biomimetic mineralization sol, treating the mixture for 5-10min by adopting ultrasonic mixing equipment, and shaking up the biomimetic mineralization sol. The shaking time can be adjusted according to the amount of the raw materials.

Subsequently, coating: coating the prepared biomimetic mineralization sol on the surface of the ceramic tile substrate cleaned in the step S1, wherein the dosage is 50-100mL/m²Drying and standing for 30-90min under the air convection condition, and then cleaning the ceramic tile substrate by using purified water to remove sol residues at the undamaged part of the ceramic tile substrate;

s3: and (3) crystallization:

firstly, preparing a water-soluble amino acid solution: 0.1 to 0.5 part of water-soluble amino acid, 5 to 10 parts of sodium bicarbonate and 100 to 150 parts of purified water are prepared into a water-soluble amino acid solution, and the water-soluble amino acid is used as a molecular switch of the silicon dioxide crystal; the solution can be prepared at room temperature in a conventional manner.

Then, fully soaking the ceramic tile substrate subjected to biomimetic mineralization sol treatment in the step S2 by using a water-soluble amino acid solution, wherein the using amount is 50-100mL/m²Standing for 10-40 min, wherein the standing time is the infiltration time, and amorphous silica precursors in the biomimetic mineralized sol are crystallized to form a crystallized silica and polyamine composite porous layer with Mohs hardness of more than or equal to 2.0; and then, washing the crystallized ceramic tile substrate by using purified water, drying at room temperature for a certain time, and finishing the ceramic tile repairing treatment.

The invention takes inorganic silicate and trace tetraethyl orthosilicate (TEOS) as precursors, primary ammonium salt type cationic polymers with different molecular weights as inducing molecules, aluminum phosphate as a binder and water-soluble amino acid as a molecular switch of silicon dioxide crystallization to form composite sol on a ceramic tile substrate. Primary ammonium salt type cationic polymer molecules are enriched at the damaged part of the ceramic tile to induce the hydrolysis and crystallization of a silicon dioxide precursor, and self-assembly is carried out to form a translucent silicon dioxide and polyamine composite porous layer. The ceramic tile which is repaired by the pretreatment cleaning and the biomimetic mineralization technology has the advantages that the absorption characteristics of visible light at the damaged part and the undamaged part of the ceramic tile are close, no obvious color difference exists, the macroscopic scale has no obvious shape change, the glaze surface of the ceramic tile is repaired, the local friction coefficient of the ceramic tile is greatly improved, the ceramic tile has an obvious anti-skid effect under the wetting condition of strong polar liquid such as water, ethanol and the like, and the friction coefficient is higher than the national safety standard (0.50), so that the technology can efficiently and intelligently repair the ground ceramic tile and can solve the safety problem that the ground ceramic tile is wet and slippery when meeting water; the ceramic tile repairing technology has the advantages of low cost, simple use process and green and environment-friendly components, and is a next-generation ceramic tile repairing technology far superior to manual polishing and grinding.

The invention has the beneficial effects that:

(1) high-efficiency general application: compared with the traditional technology of manually polishing the damaged part and coating epoxy resin at present, the method directionally forms a layer of highly ordered crystallized silicon dioxide and polyamine composite porous layer with good mechanical property on the damaged surface of the base material by the biomimetic mineralization technology, and has the advantages of high efficiency, universality and environmental protection;

(2) traceless repair property: the traditional technology of manually polishing the damaged part and coating epoxy resin at present has obvious repair traces on the ceramic tile; in contrast, the broken part of the ceramic tile repaired by the technology has no obvious color difference and appearance change on a macroscopic scale, and can be called traceless repair to a certain extent.

(3) The technical performance of the product is as follows: according to the technology, the traceless repair of the ceramic tile is realized, and the introduced crystallized silicon dioxide and polyamine composite porous layer enables the friction coefficient of the local area of the surface of the ceramic tile to be remarkably improved, so that a good anti-skid effect is achieved.

(4) Technical reliability: the related technology is tested and applied on more than 20 ceramic tile substrates at present, the repairing effect is very excellent, and the durability is good (more than or equal to 24 months).

(5) The cost advantage is realized: the repair treatment cost of the technology is about 20-30 yuan/square meter; compared with the prior art, the cost of manual grinding and polishing is about 70-120 yuan/square meter, and the cost of products such as repair mucilage glue produced by large-scale transnational enterprises such as 3M is about 50-80 yuan/square meter, so the cost advantage of the technology is very outstanding.

Drawings

The invention is further illustrated by the following figures and examples.

FIG. 1 is a flow chart of components and application of a bionic mineralized ceramic tile repair sol.

FIG. 2 is a schematic diagram of the in-situ preparation process of the silica and polyamine composite porous layer on the surface of the ceramic tile.

FIG. 3 is a scanning electron microscope image of a porous silica/polyamine composite layer.

FIG. 4 is a comparison graph of the effect of a biomimetic mineralization technology before and after repairing a tile.

Detailed Description

The present invention will now be described in detail with reference to the accompanying drawings. This figure is a simplified schematic diagram, and merely illustrates the basic structure of the present invention in a schematic manner, and therefore it shows only the constitution related to the present invention.

According to the ceramic tile repair method based on the biomimetic mineralization technology, the high-silicon dioxide and polyamine composite porous layer is constructed at the damaged part of the ceramic tile glaze surface by adopting a pretreatment process, biomimetic mineralization, silicon dioxide crystallization and other segmentation methods, so that the damaged part of the ceramic tile is repaired. The repair method is described in detail below with reference to specific data.

Example 1:

as shown in fig. 1 and 2, the tile repairing method based on the biomimetic mineralization technology comprises the following steps:

s1: regulating and controlling the surface charge of the ceramic tile:

firstly, preparing a pretreatment solution, wherein the raw materials comprise the following components in parts by weight:

5 parts of inorganic sylvite, 1 part of surfactant, 10 parts of fruit acid, 10 parts of sodium bicarbonate, 0.1 part of ethylene glycol, 100 parts of deionized water, 1 part of anionic emulsifier and 0.1 part of titanium sulfate;

then, the prepared pretreatment solution is uniformly coated on the surface of the ceramic tile substrate to be repaired in an atomizing and spraying manner, the spraying amount of the pretreatment solution is related to the area and the damage degree of the ceramic tile, and the consumption amount of the pretreatment solution in the embodiment is about 100mL/m²；

Then, standing the ceramic tile floor coated with the pretreatment solution for 10 min; and then, carrying out high-pressure washing on the surface of the ceramic tile substrate coated with the pretreatment solution by using a sodium bicarbonate solution with the pH value of 10, then monitoring the Zeta potential at the damaged part of the ceramic tile by using a Zeta potential meter, and judging whether the Zeta potential at the damaged part of the glaze of the ceramic tile substrate is between-20 mV and-35 mV, wherein the pretreatment process is finished when the Zeta potential value at the damaged part of the glaze of the ceramic tile substrate to be repaired reaches-20 mV. At this time, the tile surface with high density negative charges can selectively adsorb the polyamine induced molecules with positive charges and generate strong interaction with the polyamine induced molecules.

S2: coating sol:

firstly, preparing biomimetic mineralization sol, wherein the biomimetic mineralization sol comprises the following raw materials in parts by mass:

15 parts of inorganic silicate, 0.1 part of tetraethyl orthosilicate (TEOS), 1 part of nano aluminum phosphate, 1 part of primary ammonium salt type cationic polymer, 1 part of sodium bicarbonate and 80 parts of deionized water;

and then, mixing the raw materials of the biomimetic mineralization sol, treating the mixture for 5min by adopting ultrasonic mixing equipment, and shaking up the biomimetic mineralization sol.

Then, uniformly coating the evenly shaken biomimetic mineralization sol on the surface of the ceramic tile substrate, wherein the dosage is 50mL/m²And drying and standing for 30min under the air convection condition, and then cleaning the ceramic tile substrate by using purified water to remove sol residues at the undamaged part of the ceramic tile.

S3: and (3) crystallization:

firstly, preparing a water-soluble amino acid solution, wherein the water-soluble amino acid solution comprises the following raw materials in parts by mass:

0.1 part of water-soluble amino acid, 5 parts of sodium bicarbonate and 100 parts of purified water are prepared into a water-soluble amino acid solution which is used as a molecular switch of silicon dioxide crystals;

then, the ceramic tile substrate treated by the biomimetic mineralization sol in the step S2 is fully soaked by a water-soluble amino acid solution, and the dosage is 50mL/m²Standing for 10min, crystallizing the amorphous silica precursor in the biomimetic mineralized sol to form a highly ordered crystallized silica and polyamine composite porous layer with Mohs hardness of more than or equal to 2.0. And finally, washing the ceramic tile substrate by using purified water, drying at room temperature for 2-4 hours, and finishing the ceramic tile repairing treatment.

Observing the repair area by using an electron microscope, wherein the left side image is the display state of the front surface of the repaired ceramic tile under the electron microscope as shown in figure 3 (the ruler is 5 microns), and the repair area on the surface of the ceramic tile is of a porous structure; the right side of the figure shows the repaired tile in the state of its side under an electron microscope, from which it can be seen that the upper side of the tile is a porous repair layer with a thickness of about 20-30 μm and the lower side is a relatively compact tile substrate. For example, as shown in fig. 4, the left photo is in a state before repair, and the right photo is in a state after repair, so that the surface of the repaired tile has no obvious color difference or trace, and the repairing effect is good.

Example 2

The tile repairing method based on the biomimetic mineralization technology comprises the following steps:

s1: regulating and controlling the surface charge of the ceramic tile:

firstly, preparing a pretreatment solution, wherein the raw materials comprise the following components in parts by weight:

15 parts of inorganic sylvite, 3 parts of surfactant, 15 parts of fruit acid, 15 parts of sodium bicarbonate, 0.3 part of ethylene glycol, 125 parts of deionized water, 3 parts of anionic emulsifier and 0.3 part of titanium sulfate; the raw materials were mixed in the same manner as in example 1.

Then, the prepared pretreatment solution is uniformly coated on the surface of the ceramic tile substrate to be repaired in an atomizing and spraying manner, the spraying amount of the pretreatment solution is related to the area and the damage degree of the ceramic tile, and the consumption amount of the pretreatment solution in the embodiment is about 110mL/m²；

Then, standing the ceramic tile ground coated with the pretreatment solution for 15min, then washing the surface of the ceramic tile substrate coated with the pretreatment solution at high pressure by using a sodium bicarbonate solution with the pH value of 10.5, and then monitoring the Zeta potential of the damaged part of the ceramic tile by using a Zeta potential meter until the Zeta potential of the damaged part of the glaze surface of the ceramic tile substrate to be repaired is between-20 mV and-35 mV; in this example, Zeta potential is selected to be-30 mV, so that the tile surface has high density of negative charges to selectively adsorb and strongly interact with the positively charged polyamine-induced molecules.

S2: coating sol:

firstly, preparing biomimetic mineralization sol, wherein the biomimetic mineralization sol comprises the following raw materials in parts by mass:

20 parts of inorganic silicate, 0.3 part of tetraethyl orthosilicate (TEOS), 3 parts of nano aluminum phosphate, 3 parts of primary ammonium salt type cationic polymer, 3 parts of sodium bicarbonate and 100 parts of deionized water;

then, after mixing the raw materials of the biomimetic mineralization sol, treating the raw materials for 8min by adopting ultrasonic mixing equipment, and shaking up the biomimetic mineralization sol.

Then, the evenly shaken biomimetic ore is put into a mixing tankThe sol is evenly coated on the surface of the ceramic tile substrate, and the dosage is 80mL/m²And drying and standing for 60min under the condition of air convection, and then cleaning the ceramic tile substrate by using purified water to remove sol residues at the undamaged part of the ceramic tile.

S3: and (3) crystallization:

firstly, preparing a water-soluble amino acid solution, wherein the water-soluble amino acid solution comprises the following raw materials in parts by mass:

0.3 part of water-soluble amino acid, 8 parts of sodium bicarbonate and 125 parts of purified water are prepared into a water-soluble amino acid solution which is used as a molecular switch of silicon dioxide crystals;

then, the ceramic tile substrate treated by the biomimetic mineralization sol in the step S2 is fully infiltrated by a water-soluble amino acid solution, and the dosage is 80mL/m²Standing for 25min, and crystallizing the amorphous silica precursor in the biomimetic mineralized sol to form a highly ordered silica and polyamine composite porous layer with Mohs hardness of more than or equal to 2.0. And finally, washing the ceramic tile substrate by using purified water, drying at room temperature for 2-4 hours, and finishing the ceramic tile repairing treatment.

Example 3:

the tile repairing method based on the biomimetic mineralization technology comprises the following steps:

s1: regulating and controlling the surface charge of the ceramic tile:

firstly, preparing a pretreatment solution, wherein the raw materials comprise the following components in parts by weight:

20 parts of inorganic sylvite, 5 parts of surfactant, 20 parts of fruit acid, 20 parts of sodium bicarbonate, 0.5 part of ethylene glycol, 150 parts of deionized water, 5 parts of anionic emulsifier and 0.5 part of titanium sulfate;

then, the prepared pretreatment solution is uniformly coated on the surface of the substrate of the ceramic tile to be repaired in an atomizing and spraying manner, wherein the spraying amount of the pretreatment solution is related to the area and the damage degree of the ceramic tile, and the consumption amount of the pretreatment solution in the embodiment is about 120mL/m²；

Then, standing the ceramic tile floor coated with the pretreatment solution for 30 min; then, washing the surface of the ceramic tile substrate coated with the pretreatment solution at high pressure by using a sodium bicarbonate solution with the pH value of 11; then, a Zeta potential meter is adopted to monitor the Zeta potential at the damaged part of the ceramic tile, whether the Zeta potential at the damaged part of the glaze surface of the ceramic tile substrate to be repaired is between-20 mV and-35 mV is judged, and the pretreatment process is finished when the Zeta potential value at the damaged part of the glaze surface of the ceramic tile substrate to be repaired reaches-35 mV in the embodiment.

At this time, the tile surface with high density negative charges can selectively adsorb the polyamine induced molecules with positive charges and generate strong interaction with the polyamine induced molecules.

S2: coating sol:

firstly, preparing biomimetic mineralization sol, wherein the biomimetic mineralization sol comprises the following raw materials in parts by mass:

30 parts of inorganic silicate, 0.5 part of tetraethyl orthosilicate (TEOS), 5 parts of nano aluminum phosphate, 5 parts of primary ammonium salt type cationic polymer, 5 parts of sodium bicarbonate and 120 parts of deionized water;

then, mixing the raw materials of the biomimetic mineralized sol, and then shaking up the raw materials for 10min by adopting ultrasonic mixing equipment;

then, uniformly coating the evenly shaken biomimetic mineralization sol on the surface of the ceramic tile substrate, wherein the dosage is 100mL/m²And drying and standing for 90min under the air convection condition, and then cleaning the ceramic tile substrate by using purified water to remove sol residues at the undamaged part of the ceramic tile.

S3: and (3) crystallization:

firstly, preparing a water-soluble amino acid solution, wherein the water-soluble amino acid solution comprises the following raw materials in parts by weight:

0.5 part of water-soluble amino acid, 10 parts of sodium bicarbonate and 150 parts of purified water are prepared into a water-soluble amino acid solution which is used as a molecular switch of silicon dioxide crystals;

and then, fully infiltrating the ceramic tile substrate treated by the biomimetic mineralization sol in the step S2 by using a water-soluble amino acid solution, wherein the using amount is 100mL/m2, standing for 40min, and crystallizing an amorphous silica precursor in the biomimetic mineralization sol to form a highly ordered crystallized silica and polyamine composite porous layer with the Mohs hardness of more than or equal to 2.0.

And finally, washing the ceramic tile substrate by using purified water, drying at room temperature for 2-4 hours, and finishing the ceramic tile repairing treatment.

Experimental test of friction coefficient:

the silica and polyamine composite porous layer can form strong interaction even under the wetting condition of water and ethanol. Under the condition, the local friction coefficient of the repaired ceramic tile is remarkably improved, and the ceramic tile has a certain anti-skidding function. The ceramic tiles and the parameters thereof which can achieve good anti-slip effect in the prior art are listed in the following table 1, but are not limited to the types of the ceramic tiles in the table 1.

TABLE 1 comparison of friction coefficients before and after anti-skid treatment for eight typical types of floor building materials

Species of	Brand	Before repair	After repair
				Vitrified brick	Dongpeng (Dongpeng)	COF＝0.363	COF＝0.648
Glazed tile	Mark Polo	COF＝0.261	COF＝0.752
				Homogeneous brick	Dongpeng (Dongpeng)	COF＝0.253	COF＝0.854
Archaizing brick	Root of Asian Meadowrue	COF＝0.602	COF＝0.883
				Square brick	Wan Shu	COF＝0.459	COF＝0.838
Granite	Made in China	COF＝0.402	COF＝0.711
				Marble	Made in China	COF＝0.407	COF＝0.643
Holland brick	Is free of	COF＝0.501	COF＝0.663

The friction coefficient test result shows that the silicon dioxide/polyamine composite porous layer can effectively strengthen the local friction coefficient of the ceramic tile, has good anti-skid performance, and the friction coefficients of more than 20 types of processed ceramic tiles are all larger than 0.50 and all meet the requirements of the national anti-skid safety standard.

Comparative example 1:

the preparation process is the same as that of example 1, except that: the dosage of the biomimetic mineralization sol is increased to 200mL/m²To obtain a silica/polyamine mineralized layer with a light yellow surface and improved anti-skid performanceAnd a certain color difference is generated between the repaired part and the undamaged part of the ceramic tile, so that less biomimetic mineralization sol can be adopted when repairing the light-color ceramic tile, and the dosage of the biomimetic mineralization sol can be properly increased when repairing the dark-color ceramic tile so as to ensure the repairing effect and avoid the color difference.

Comparative example 2:

the preparation process is the same as that of example 1, except that: the soaking time of the water-soluble amino acid solution is shortened to 5min, the crystallinity of the silicon dioxide is reduced, the Mohs hardness of the silicon dioxide and polyamine composite porous layer is as low as 1.0, and the durability of the repairing effect is greatly reduced, so the soaking time by the water-soluble amino acid solution cannot be too short and is at least more than 10 min.

Comparative example 3:

the preparation process is the same as that of example 1, except that: the pretreatment cleaning process is omitted, the silicon dioxide and polyamine composite porous layer cannot be selectively attached to the damaged part of the glazed surface of the ceramic tile, and the matte phenomenon appears on the surface of the treated ceramic tile.

Comparative example 4:

the preparation process is the same as that of example 1, except that: the bionic mineralized sol residue on the undamaged part of the ceramic tile is not removed, the silicon dioxide/polyamine mineralized layer is also arranged on the undamaged area of the ceramic tile, the gloss and brightness of the mineralized layer are influenced to a certain extent, and the mineralized layer formed on the undamaged area of the ceramic tile is easy to clean and scrape.

Comparative example 5:

the preparation process is the same as that of example 1, except that: polyamine with larger molecular weight is selected as an inducing molecule, the uniformity of a silicon dioxide/polyamine mineralized layer is greatly influenced, obvious marks appear on the repaired ceramic tile, and a large amount of rough particles are generated on the repaired surface.

Comparative example 6:

the preparation process is the same as that of example 1, except that: the ceramic tile repairing effect cannot be maintained without soaking the mineralized layer with water-soluble amino acid solution.

Comparative example 7:

the preparation process is the same as that of example 1, except that: if the surface of the repaired tile is soaked in an organic solvent for a long time, the silica/polyamine mineralized layer is easily softened and peeled off.

It should be noted that when the following claims refer to numerical ranges, it should be understood that both ends of each numerical range and any value between the two ends can be selected, and since the steps and methods used are the same as those of the embodiments, the preferred embodiments of the present invention have been described for the purpose of preventing redundancy, but once the basic inventive concept is known, those skilled in the art may make other variations and modifications to the embodiments. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. #

In light of the foregoing description of preferred embodiments in accordance with the invention, it is to be understood that numerous changes and modifications may be made by those skilled in the art without departing from the scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.