High permeability and high wear resistance composite floor material

Abstract

The application discloses a kind of high permeability high wear-resistant composite floor material, including A component and B component, the A component includes lithium silicate sol, 0.1%~0.5% enzyme catalyst and 10%~50% sodium silicate are included in the B component, wherein lithium silicate sol is prepared by reacting with alkali silicon sol solution and lithium hydroxide monohydrate aqueous solution;The proportion of alkali silicon sol solution in reaction solution is 30%~60%, the proportion of lithium hydroxide monohydrate aqueous solution is 2%~10%, hydrogen ion donor is added in reaction solution, and the proportion of hydrogen ion donor is 0.1%~0.3%.The application also discloses the preparation method of the above-mentioned composite floor material.

Description

Technical Field

[0001] This invention relates to the field of wear-resistant materials, and more particularly to a high-penetration, high-wear-resistant composite flooring material and its preparation method. Background Technology

[0002] Due to the increasing demand for wear-resistant, slip-resistant, aesthetically pleasing, and clean flooring in current building facilities, researchers at home and abroad have developed a variety of permeable hardening materials for cement-based flooring. These materials further enhance the density of the cement surface, reducing the damage to the substrate surface caused by foreign substances and preventing the substrate from losing strength due to penetration into the substrate.

[0003] Currently, the main design concepts for hardening materials fall into two categories: one is based on nano-silica sol as the main component, as disclosed in patent publications CN103964737B and CN102030560B, which uses silica sol as the main component, with the addition of catalysts, surfactants, and other additives, and is directly sprayed onto the concrete surface to achieve high wear resistance, high hardness, high water repellency, and dustproofing. The other category uses silicate solutions as the main component, as disclosed in patent publication CN117447235A, which uses potassium methylsilicate and sodium methylsilicate as the main components, and adds nano-silica sol, modified graphene, and other additives to improve the surface density, surface hardness, impermeability, and durability of concrete building slabs, solving problems such as looseness, dust, sand, and peeling. The advantage of these two types of hardening materials is their strong permeability, allowing them to quickly penetrate through the pores of concrete; however, their effect on the surface is not strong, meaning the hardening reaction with cement is slow, resulting in an indistinct overall cross-linked network structure on the surface. Furthermore, because it is prone to reacting with air or itself, its storage stability decreases. Ultimately, the hardness and wear resistance of the concrete surface will gradually decrease with the extension of the service time, and its durability will deteriorate significantly.

[0004] Therefore, with the increasing demands for floor hardness and abrasion resistance in medium- and heavy-load industrial environments such as factories, garages, and logistics warehouses, there is a growing need for penetrating hardening materials to possess good stability, rapid hardening, and long-term durability. Consequently, developing a flooring material that can rapidly improve the overall performance of concrete-based substrates while also meeting their durability requirements has become a crucial need. Summary of the Invention

[0005] To address the aforementioned problems, this invention proposes a high-penetration, high-wear-resistant composite flooring material that forms a dense silicon-carbon layer, improving the density of the substrate surface, reducing the risk of cracking caused by rapid condensation, significantly enhancing wear resistance, and providing a relatively long service life for the entire coating.

[0006] The technical solution adopted in this invention is as follows:

[0007] A high-penetration, high-wear-resistant composite flooring material includes component A and component B. Component A includes lithium silicate sol, and component B includes 0.1% to 0.5% enzyme catalyst and 10% to 50% sodium silicate. The lithium silicate sol is prepared by reacting an alkaline silica sol solution with an aqueous solution of lithium hydroxide monohydrate. The alkaline silica sol solution accounts for 30% to 60% of the reaction solution, the aqueous solution of lithium hydroxide monohydrate accounts for 2% to 10%, and a hydrogen ion donor is added to the reaction solution, with the hydrogen ion donor accounting for 0.1% to 0.3%.

[0008] This solution provides a high-hardness, high-mechanical-performance penetrating hardening material with a faster reaction rate and better permeability to the substrate surface (penetration depth 3-5 mm, due to the stronger wetting effect of components A and B on the concrete surface after reaction, generating CSH nanoparticles that selectively fill capillary pores >0.1 micrometers, thus resulting in better permeability). Component A in this solution alters the overall pH of the solution system by adding a hydrogen ion donor. When component A is blended with component B, the overall pH of the solution approaches neutral, facilitating the catalytic activity.

[0009] Component A primarily prepared a high-modulus lithium silicate sol with excellent stability. Component B used an enzyme catalyst to modify an aqueous sodium silicate solution. The enzyme selectively catalyzed the transesterification reaction between the silanol groups in sodium silicate and organic molecules (such as fatty acids and phenolic compounds), while simultaneously lowering the activation energy of the reaction and promoting the grafting of organic functional groups on the surface of sodium silicate. This introduced hydrophobic alkyl chains onto the silicon-oxygen framework, which can significantly reduce the surface water absorption of the material over 24 hours. After enzyme modification, sodium silicate forms a dense silicon-carbon layer, improving the density of the substrate surface (and the structure generated by the enzyme-catalyzed reaction is even denser, reducing the risk of cracking caused by rapid condensation compared to other methods). The wear resistance is significantly improved, and the entire coating has a relatively long service life.

[0010] Furthermore, the technical solution provided in this method uses enzyme-catalyzed (modified) sodium silicate aqueous solution, carried out under medium temperature (40~60℃) and near-neutral pH (i.e., pH 6~8) conditions, reducing energy consumption by 40~60% compared to traditional strong alkali / high temperature sodium silicate modification processes, and avoiding energy waste caused by high temperature and high pressure. This method also replaces strong acids (such as concentrated sulfuric acid) and heavy metal catalysts (such as chromium salts) with biological enzymes (such as lipase and laccase), eliminating the emission of toxic waste liquid. Because the enzymatic reaction generates a dense silicon-oxygen network, the bonding strength with the substrate (concrete) is increased, and it exhibits high stability in acidic and alkaline environments.

[0011] In this scheme, when lithium ions (small radius) and sodium ions (large radius) coexist, lithium ions fill the gaps in the silicon-oxygen network, neutralize surface charge, reduce colloidal aggregation, and improve the zeta potential stability of the mixed solution by 40%, resulting in a more uniform colloidal particle size distribution. Sodium silicate hydrolysis easily generates highly polymerized silicic acid (such as cubic octasilicic acid), while lithium ions inhibit excessive polymerization and promote the formation of a dense oligomeric silicic acid-metal ion cross-linked structure, enhancing the coating's density. This is because oligomers exhibit a narrow molecular weight distribution, and their properties are easily affected by changes in the monomers within the system, while polymers are mostly dispersed systems (homogeneous mixtures). Lithium silicate releases [resources] during the reaction. and SiO3 2- It competes with sodium silicate hydrolysis products for binding sites, interfering with the conversion of silicic acid nuclei into large-sized gel particles.

[0012] In summary, this composite floor coating uses a mixture of component A and component B. Component A mainly prepares a high-modulus lithium silicate sol with excellent stability. Component B uses an enzyme catalyst to modify the sodium silicate aqueous solution. The enzyme selectively catalyzes the silanol groups in sodium silicate to undergo transesterification with organic molecules, thereby lowering the activation energy of the reaction and promoting the grafting of organic functional groups on the surface of sodium silicate. This introduces hydrophobic alkyl chains onto the silicon-oxygen framework, reducing the surface water absorption of the material. After enzyme modification, sodium silicate forms a dense silicon-carbon layer, improving the density of the substrate surface, reducing the risk of cracking caused by rapid condensation, and significantly improving wear resistance. The entire coating has a relatively long service life.

[0013] Optionally, the enzyme catalyst includes one or more of lipases, esterases, and hydrolases.

[0014] Optionally, the hydrogen ion donor is hydrochloric acid, sulfuric acid, nitric acid, or acetic acid.

[0015] Optionally, the lithium hydroxide monohydrate aqueous solution is a battery-grade lithium hydroxide monohydrate aqueous solution.

[0016] Optionally, when not in use, components A and B are not mixed. When in use, components A and B are mixed in a mass ratio of 3:2 to form a mixture. After the mixture is applied, dried, and hardened, a layer of component A is then applied to the surface of the mixture.

[0017] First, mix component A and component B and apply the mixture. After it dries and hardens, apply another layer of component A. This is because when the liquid components A and B are thoroughly mixed, the silica-coated enzymes combine with lithium silicate. The redox activity of the enzymes catalyzes the oxidation of hydroxyl groups on the surface of lithium silicate, generating reactive silicon free radicals, which accelerate their coupling with organic matter. After the reaction, the enzymes still retain some activity, allowing component A to be applied again to react with the undeactivated enzymes, thus increasing the lifespan of the permeation-hardening material.

[0018] A method for preparing the high-penetration, high-wear-resistant composite flooring material as described above includes the following steps:

[0019] The preparation steps for component A are as follows: alkaline silica sol solution and battery-grade lithium hydroxide monohydrate aqueous solution are added sequentially to the first reaction vessel and stirred at 40℃~60℃ for 1 h~5 h; then a hydrogen ion donor is added, the pH is adjusted to 4~6, and the mixture is refluxed at 40℃~60℃ while stirring for 4 h~12 h to carry out the reaction. After the reaction is completed, the temperature is lowered to below 25℃, and the filtrate obtained by filtering the product through filter paper is component A.

[0020] In the preparation step of component B, the enzyme and sodium silicate aqueous solution are added to the second reaction vessel and stirred at 30℃~50℃ for 10~60 min; the resulting mixture is component B.

[0021] Optionally, the stirring speed is 300 rpm to 800 rpm when preparing component A, and 200 rpm to 500 rpm when preparing component B.

[0022] Optionally, both the solutions in component A and component B can be prepared using deionized water.

[0023] Deionized water is used to ensure that the components of each solution have high purity.

[0024] The beneficial effects of this invention are: a dense silicon-carbon layer is formed, which improves the density of the substrate surface, reduces the risk of cracking caused by rapid condensation, significantly improves wear resistance, and the entire coating has a relatively long service life. Detailed Implementation

[0025] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0026] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0027] Part One: Implementation Scheme of the Invention

[0028] A high-penetration, high-wear-resistant composite flooring material is composed of component A and component B; wherein,

[0029] Component A is a stable lithium silicate sol, which is prepared by reacting an aqueous solution of lithium silicate with an alkaline silica sol solution and an aqueous solution of battery-grade lithium hydroxide monohydrate. The weight ratio of alkaline silica sol to battery-grade lithium hydroxide monohydrate is 100:1 to 10:1. During the reaction, a hydrogen ion donor is also required, which accounts for 1‰ to 3‰ of the total solution mass.

[0030] Component B is a liquid composed of sodium silicate, additives, and enzyme catalyst solution.

[0031] The enzymes include at least one of lipase, esterase, and hydrolase.

[0032] The hydrogen ion donor is one of HCl (hydrochloric acid), H2SO4 (sulfuric acid), HNO3 (nitric acid), or CH3COOH (acetic acid).

[0033] The solution is prepared with deionized water.

[0034] The application method of the above composite flooring materials is as follows:

[0035] At room temperature (25℃), mix component A liquid and component B liquid in a mass ratio of 3:2 until homogeneous; then apply the mixture to the floor surface after curing, using 10~20g / m² of the mixture.

[0036] Continue drying at room temperature (25℃) for 4 hours or more to form a hardened material layer on the surface of the floor. Then, the floor is professionally ground and cleaned using multi-pass grinding equipment.

[0037] After cleaning the surface, apply another coat of component A, let it dry, and then polish it multiple times with fine abrasive pads to finally obtain a high-performance floor with a hardened material layer.

[0038] This embodiment further provides a method for preparing the above-mentioned composite flooring material, including the following steps:

[0039] The first step is to weigh the raw materials of each component in component A and component B according to the stated mass ratio;

[0040] The second step involves first adding an alkaline silica sol solution and a battery-grade lithium hydroxide monohydrate aqueous solution sequentially into the first reaction vessel. The mixture is then stirred at 300-800 rpm for 1-5 hours in an oil bath at 40-60°C. Next, a hydrogen ion acceptor is added, and the pH is adjusted to 4-6. The mixture is then refluxed at 40-60°C while maintaining stirring at 300-800 rpm for 4-12 hours to carry out the reaction. After the reaction is complete, the mixture is cooled to room temperature. The filtrate obtained by filtering the product through filter paper is component A, which is then sealed for later use.

[0041] The third step involves adding the enzyme and sodium silicate aqueous solution to the second reaction vessel and stirring at 200-500 rpm for 10-60 minutes at 30℃-50℃. The resulting mixture is component B, which should be sealed and kept for later use.

[0042] Referring to the preparation method section above, the hardening materials of Examples 1-5 were prepared. The relevant process parameters during the preparation process are shown in Table 1.

[0043] Table 1

[0044]

[0045] Comparative Example 1

[0046] The penetrating nano-curing agent comprises the following components in the indicated mass percentages: potassium methylsilicate 18.0%~18.5%, sodium methylsilicate 48.0%~48.5%, amine-modified graphene 3%~3.5%, nano-Al2O3 sol 6%~6.5%, and surfactant 0.5%~1.0%, with the balance being deionized water; wherein the mass ratio of the amine to the graphene is 1:0.1~0.3.

[0047] Comparative Example 2

[0048] The commercially available hardener, model PC-40, consists of two components, A and B. Component A comprises silane prepolymer, wear-resistant modifier, stabilizer, and solvent; component B comprises catalyst and solvent. The solvent in both components is ethanol.

[0049] The above Examples 1 to 5, Comparative Example 1 and Comparative Example 2 were tested. The mortar samples were prepared in accordance with the provisions of JC / T2158-2021. The effective time and gloss (60°) were tested in accordance with the provisions of GB / T 22374-2018 "Floor Coating Materials". The surface hardness, abrasion resistance and 24h surface water absorption were tested in accordance with the provisions of JC / T2158-202.

[0050] Test Results and Analysis

[0051] Based on the same testing method, the performance test parameters of the products in Examples 1-5 and Comparative Examples 1-2 are shown in Table 2.

[0052] Table 2

[0053]

[0054] In Table 1, the onset time, i.e., the time it takes for the hardened material layer to form, indicates a faster hardening speed. A lower 24-hour surface water absorption value indicates better waterproofing and seepage prevention. The wear resistance of the hardened material in this invention is superior to that of the comparative example, verifying that the synergistic effect of components A and B increases the wear resistance of the cement substrate surface. The table shows that while possessing excellent wear resistance, it also exhibits high surface hardness and superior 24-hour surface water absorption, demonstrating that the hardened material of this invention increases the density of the substrate surface. Furthermore, all embodiments show better performance compared to the control group.

[0055] The above-described embodiments only illustrate some aspects of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A high-penetration, high-wear-resistant composite flooring material, characterized in that, The mixture includes component A and component B. Component A includes lithium silicate sol, and component B includes 0.1% to 0.5% enzyme catalyst and 10% to 50% sodium silicate. The lithium silicate sol is prepared by reacting an alkaline silica sol solution with an aqueous solution of lithium hydroxide monohydrate. The alkaline silica sol solution accounts for 30% to 60% of the reaction solution, the aqueous solution of lithium hydroxide monohydrate accounts for 2% to 10%, and a hydrogen ion donor is added to the reaction solution, with the hydrogen ion donor accounting for 0.1% to 0.3%.

2. The high-permeability, high-wear-resistant composite flooring material according to claim 1, characterized in that, The enzyme catalyst includes one or more of lipases, esterases, and hydrolases.

3. The high-permeability, high-wear-resistant composite flooring material according to claim 1, characterized in that, The hydrogen ion donor is hydrochloric acid, sulfuric acid, nitric acid, or acetic acid.

4. The high-permeability, high-wear-resistant composite flooring material according to claim 1, characterized in that, The lithium hydroxide monohydrate aqueous solution is a battery-grade lithium hydroxide monohydrate aqueous solution.

5. The high-permeability, high-wear-resistant composite flooring material according to claim 1, characterized in that, When not in use, components A and B are not mixed. When in use, components A and B are mixed in a mass ratio of 3:2 to form a mixture. After the mixture is applied, dried, and hardened, a layer of component A is then applied to the surface of the mixture.

6. A method for preparing a high-penetration, high-wear-resistant composite flooring material as described in any one of claims 1 to 5, characterized in that, Includes the following steps, The preparation steps for component A are as follows: alkaline silica sol solution and battery-grade lithium hydroxide monohydrate aqueous solution are added sequentially to the first reaction vessel and stirred at 40℃~60℃ for 1 h~5 h; then a hydrogen ion donor is added, the pH is adjusted to 4~6, and the mixture is refluxed at 40℃~60℃ while stirring for 4 h~12 h to carry out the reaction. After the reaction is completed, the temperature is lowered to below 25℃, and the filtrate obtained by filtering the product through filter paper is component A. In the preparation step of component B, the enzyme and sodium silicate aqueous solution are added to the second reaction vessel and stirred at 30℃~50℃ for 10~60 min; the resulting mixture is component B.

7. The preparation method according to claim 6, characterized in that, When preparing component A, the stirring speed is 300 rpm to 800 rpm, and when preparing component B, the stirring speed is 200 rpm to 500 rpm.

8. The preparation method according to claim 6, characterized in that, Both the solutions in component A and component B are prepared using deionized water.

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