Geopolymer-based permeable crystalline waterproofing coating for marine environments and method of preparation

Abstract

The application is a geopolymer-based permeable crystallization waterproof coating for marine environment and a preparation method, the waterproof coating is prepared from the following components in parts by weight: quartz sand 80-100 parts, water 80-100 parts, wool keratin 6-8 parts, slag powder 20-40 parts, iron tailings powder 8-12 parts, fly ash 8-12 parts, silica ash 8-12 parts, SP1 type nano silicon dioxide 1-2 parts, alkaline activator 12-18 parts, isobutyl triethoxysilane 10-16 parts, glycerol 4-8 parts, penetrant 1-2 parts, crystallization precipitant 2-6 parts, and complexing agent 1-3 parts. The geopolymer-based permeable crystallization waterproof coating provided by the application can be brushed or sprayed on the surface of cement concrete, has good durability, and when cracks occur in the concrete, the active substances in the permeable crystallization waterproof coating are activated by water to form dense crystals, thereby playing a self-repairing role.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of building materials, and particularly relates to a geopolymer-based permeable crystalline waterproof coating for marine environment and a preparation method. BACKGROUND

[0002] The average salinity of seawater is as high as 3.5%, mainly including Na + , Mg 2+ , Cl - , SO4 2- and other ions. The multiple complex factors such as salt and climate in the marine environment are superimposed, and the marine environment is recognized as the most severe service environment for concrete. Common corrosion conditions are divided into chemical corrosion and physical corrosion. Under the action of chemical corrosion, the deterioration of concrete is mainly divided into two types: one is the deterioration caused by the consumption of alkaline oxides in concrete due to Mg 2+ and SO4 2- in the marine environment, which leads to the gradual reduction of the cementitious strength of concrete and even the peeling of the surface concrete. The other is that high-concentration Cl - penetrates into the interior of concrete through surface penetration, destroys the passivation film on the surface of the steel bar and forms a corrosion cell, and then causes steel bar corrosion and concrete cracking due to rust expansion.

[0003] The traditional waterproof coating such as asphalt, polyurethane and epoxy resin generally blocks the pores on the surface of concrete by surface covering, so as to prevent the intrusion of external water. However, the waterproof protective layer is easily damaged under the action of long-term freeze-thaw cycle and temperature stress in the marine environment, and then the service life of the waterproof coating is significantly shortened. In addition, these traditional waterproof coatings will age, fade and peel off when exposed to the natural environment for a long time, and have the inherent defects such as small adhesion and poor durability.

[0004] The permeable crystalline waterproof coating is a new type of self-repairing waterproof coating, which is generally a powdery material made of silicate cement, quartz sand as main components and a certain amount of active chemicals, and is mixed with water to be brushed or sprayed on the surface of cement concrete. After the action of water, the active chemicals contained in the material penetrate into the concrete with water as the carrier, and generate needle-shaped crystals that are insoluble in water with the cement hydration products, so as to improve the compactness and waterproofness of concrete.

[0005] However, the common penetration crystallization type waterproof coating on the market uses silicate cement as the main raw material, has poor durability, is easily eroded by chloride salt, sulfate salt and the like, is not suitable for surface protection of concrete in marine environment, and has problems such as high energy consumption and large carbon emission. SUMMARY

[0006] The present application aims to solve the problems of the prior art and provides a geopolymer-based penetration crystallization waterproof coating for marine environment and a preparation method.

[0007] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0008] The geopolymer-based penetration crystallization waterproof coating for marine environment comprises the following components and weight fractions:

[0009] 80-100 parts of quartz sand, 80-100 parts of water, 6-8 parts of wool keratin, 20-40 parts of slag powder, 8-12 parts of iron tailings powder, 8-12 parts of fly ash, 8-12 parts of silica fume, 1-2 parts of SP1 type nano silicon dioxide, 12-18 parts of alkaline activator, 10-16 parts of isobutyl triethoxysilane, 4-8 parts of glycerol, 1-2 parts of penetrating agent, 2-6 parts of crystallization precipitant and 1-3 parts of complexing agent.

[0010] The preparation method of the wool keratin comprises the following steps:

[0011] S1, the waste wool is crushed and washed to form a stable emulsion of lanolin, and the impurities float in the washing liquid, and after the impurities are removed, the wool is dried in a drying oven for 24 hours;

[0012] S2, 2g of the dried wool obtained in step S1 is taken, 0.6mol / L of sodium pyrosulfite, 9mol / L of urea and 0.12mol / L of sodium dodecyl sulfate are added, and the mixture is uniformly mixed at a bath ratio of 1:50, heated to 70℃ in a constant temperature water bath, and fully dissolved by low-speed stirring for 12 hours;

[0013] S3, the mixed solution is filtered and dialyzed, and the wool keratin is obtained by freeze-drying.

[0014] The particle size range of the quartz sand is 0.5-0.8mm; the particle size range of the slag powder is 400-450μm; the particle size range of the iron tailings powder is 5-10μm; the particle size range of the fly ash is 0.5-300μm; the particle size range of the silica fume is 0.1-0.3μm; and the particle size range of the SP1 type nano silicon dioxide is 20-50nm.

[0015] The iron tailings powder is made of iron tailings, and the type of the iron tailings is one or more of high-silicon type, high-aluminum type, high-calcium-magnesium type, Jiujiang-steel type and multi-metal type.

[0016] The alkaline activator is one or more of sodium water glass, potassium water glass, potassium hydroxide, sodium hydroxide or sodium silicate; the modulus of sodium water glass and potassium water glass is 1.2-2.4, and the purity of potassium hydroxide, sodium hydroxide and sodium silicate is analytical pure.

[0017] The penetrating agent is composed of fatty alcohol polyoxyethylene ether and sodium polyformate with a mass ratio of 3:2.

[0018] The crystallization precipitant is anhydrous sodium carbonate or potassium methyl silicate.

[0019] The complexing agent is sodium nitrilotriacetic acid or calcium diethylenetriamine pentacarboxylate.

[0020] The preparation method of the geopolymer-based penetrating crystallization waterproof coating for marine environment described above has the following specific steps:

[0021] P1, the alkaline activator, the penetrating agent, the crystallization precipitant and the complexing agent are weighed and mixed and stirred for 90s, then 1 / 3 of the total water is added and stirred for 120s, the water is added while stirring, and the mixed liquid A is obtained after cooling to room temperature;

[0022] P2, after the blender is wet, the quartz sand, the slag powder, the iron tailings powder, the fly ash, the silica fume and the SP1 type nano silicon dioxide are added and stirred for 90s, then 2 / 3 of the total water is added and stirred for 120s, the water is added while stirring, and the mixed liquid B is obtained;

[0023] P3, the mixed liquid A and the mixed liquid B are mixed and stirred for 90s, the wool keratin is added and stirred for 120s, and the geopolymer-based penetrating crystallization waterproof coating is obtained.

[0024] The geopolymer-based penetrating crystallization waterproof coating provided by the present application can be brushed or sprayed on the surface of cement concrete, has good durability, and when cracks occur in the concrete, the active substances in the penetrating crystallization waterproof coating are activated by water to form dense crystals, thereby achieving the self-repairing effect. DETAILED DESCRIPTION

[0025] The principles and characteristics of the present application are described below in conjunction with specific embodiments, and the embodiments are used to explain the present application and are not used to limit the scope of the present application. The advantages and characteristics of the present application will be more apparent according to the following description.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0027] The application will be further described below in connection with specific embodiments:

[0028] The geopolymer-based permeable crystallization waterproof coating for marine environment, the constituent ingredients and weight fractions are as follows:

[0029] Quartz sand 80-100 parts, water 80-100 parts, wool keratin 6-8 parts, slag powder 20-40 parts, iron tailings powder 8-12 parts, fly ash 8-12 parts, silica fume 8-12 parts, SP1 type nano silicon dioxide 1-2 parts, alkaline activator 12-18 parts, isobutyl triethoxysilane 10-16 parts, glycerol 4-8 parts, penetrant 1-2 parts, crystallization precipitant 2-6 parts and complexing agent 1-3 parts.

[0030] The preparation method of the wool keratin comprises the following steps:

[0031] S1, the waste wool is crushed and washed, the lanolin forms a stable emulsion, the impurities float in the washing liquid, and the impurities are removed and then dried in a drying box for 24 hours;

[0032] S2, 2g of the dried wool obtained in step S1 is taken, 0.6mol / L of sodium pyrosulfite, 9mol / L of urea and 0.12mol / L of sodium dodecyl sulfate are added, and the mixture is uniformly mixed at a bath ratio of 1:50, heated to 70℃ in a constant temperature water bath, and fully dissolved by low-speed stirring for 12 hours;

[0033] S3, the mixed solution is filtered and dialyzed, and the wool keratin is obtained by freeze-drying.

[0034] The particle size range of the quartz sand is 0.5-0.8mm; the particle size range of the slag powder is 400-450μm; the particle size range of the iron tailings powder is 5-10μm; the particle size range of the fly ash is 0.5-300μm; the particle size range of the silica fume is 0.1-0.3μm; and the particle size range of the SP1 type nano silicon dioxide is 20-50nm.

[0035] The iron tailings powder is made of iron tailings, and the type of the iron tailings is one or more of high-silicon type, high-aluminum type, high-calcium-magnesium type, Jiujiang-steel type and multi-metal type.

[0036] The basic activator is one or more of sodium water glass, potassium water glass, potassium hydroxide, sodium hydroxide or sodium silicate; the modulus of sodium water glass and potassium water glass is 1.2-2.4, and the purity of potassium hydroxide, sodium hydroxide and sodium silicate is analytical pure.

[0037] The penetrating agent is composed of fatty alcohol polyoxyethylene ether and sodium polycarbonate with a mass ratio of 3:2.

[0038] The crystallization precipitant is anhydrous sodium carbonate or potassium methyl silicate.

[0039] The complexing agent is sodium nitrilotriacetic acid or calcium diethylene triamine penta carboxylic acid.

[0040] The ground polymer-based penetrating crystallization waterproof coating for marine environment is mixed at the construction site and is used for brushing or spraying on the surface of cement concrete.

[0041] The preparation method of the ground polymer-based penetrating crystallization waterproof coating for marine environment described above, the specific steps are:

[0042] P1, the basic activator, the penetrating agent, the crystallization precipitant and the complexing agent are weighed and mixed and stirred for 90s, then 1 / 3 of the total water is added and stirred for 120s, the water is added while stirring, and the mixed liquid A is obtained after cooling to room temperature;

[0043] P2, after the blender is wet, quartz sand, slag powder, iron tailings powder, fly ash, silica fume and SP1 type nano silicon dioxide are added and stirred for 90s, then 2 / 3 of the total water is added and stirred for 120s, the water is added while stirring, and the mixed liquid B is obtained;

[0044] P3, the mixed liquid A and the mixed liquid B are mixed and stirred for 90s, the wool keratin is added and stirred for 120s to obtain the ground polymer-based penetrating crystallization waterproof coating. Specific embodiment 1:

[0046] The ground polymer-based penetrating crystallization waterproof coating for marine environment is made of the following weight parts of raw materials:

[0047] Quartz sand 80 parts, water 100 parts, wool keratin 8 parts, slag powder 40 parts, iron tailings powder 12 parts, fly ash 10 parts, silica fume 8 parts, SP1 type nano silicon dioxide 1 part, basic activator 18 parts, isobutyl triethoxysilane 10 parts, glycerol 4 parts, penetrating agent 1 part, crystallization precipitant 2 parts, complexing agent 1 part.

[0048] The iron tailings powder is made of iron tailings, and the type of iron tailings is high-silicon iron tailings.

[0049] The basic activator is a mixture of sodium water glass and potassium hydroxide with a mass ratio of 1:1.

[0050] The crystallization precipitant is anhydrous sodium carbonate.

[0051] The complexing agent is sodium nitrilotriacetate.

[0052] The preparation method is as follows:

[0053] P1, the basic activator, the penetrant, the crystallization precipitant and the complexing agent are weighed by weight parts, mixed and stirred for 90s, then 1 / 3 of the total water is added and stirred for 120s, and the water is added while stirring, and the mixed solution A is obtained after cooling to room temperature;

[0054] P2, after the blender is wet, the quartz sand, the slag powder, the iron tailings powder, the fly ash, the silica ash and the SP1 type nano silicon dioxide are added and stirred for 90s, then 2 / 3 of the total water is added and stirred for 120s, and the water is added while stirring, and the mixed solution B is obtained;

[0055] P3, the mixed solution A and the mixed solution B are mixed and stirred for 90s, the wool keratin is added and stirred for 120s, and the geopolymer-based permeable crystallization waterproof coating is obtained. Specific embodiment 2:

[0057] The geopolymer-based permeable crystallization waterproof coating for marine environment is made of the following raw materials by weight parts:

[0058] Quartz sand 80 parts, water 100 parts, wool keratin 8 parts, slag powder 40 parts, iron tailings powder 12 parts, fly ash 8 parts, silica ash 10 parts, SP1 type nano silicon dioxide 1 part, basic activator 18 parts, isobutyl triethoxysilane 10 parts, glycerol 4 parts, penetrant 1 part, crystallization precipitant 2 parts, and complexing agent 1 part.

[0059] The iron tailings powder is made of iron tailings, and the type of the iron tailings is high-aluminum type iron tailings.

[0060] The basic activator is a mixture of potassium water glass, potassium hydroxide and sodium hydroxide in a mass ratio of 2:1:1.

[0061] The crystallization precipitant is sodium methylsilicate.

[0062] The complexing agent is calcium diethylenetriamine pentacarboxylate.

[0063] The preparation method is the same as that of specific embodiment 1. Specific embodiment 3:

[0065] The geopolymer-based permeable crystallization waterproof coating for marine environment is made of the following raw materials by weight parts:

[0066] Quartz sand 90 parts, water 90 parts, wool keratin 7 parts, slag powder 30 parts, iron tailings powder 10 parts, fly ash 12 parts, silica fume 8 parts, SP1 type nano silicon dioxide 1.5 parts, alkaline activator 15 parts, isobutyl triethoxysilane 13 parts, glycerol 6 parts, penetrating agent 1.5 parts, crystallization precipitant 4 parts, complexing agent 1.5 parts.

[0067] The iron tailings powder is prepared by grinding iron tailings, and the iron tailings are high calcium and magnesium type iron tailings.

[0068] The alkaline activator is a mixture of sodium water glass, potassium hydroxide and sodium hydroxide in a mass ratio of 1:1.

[0069] The crystallization precipitant is anhydrous sodium carbonate.

[0070] The complexing agent is sodium nitrilotriacetate.

[0071] The preparation method is the same as that of specific embodiment 1. Specific embodiment 4:

[0073] The geopolymer-based penetrating crystallization waterproof coating for marine environment is prepared from the following raw materials by weight:

[0074] Quartz sand 90 parts, water 90 parts, wool keratin 7 parts, slag powder 30 parts, iron tailings powder 10 parts, fly ash 8 parts, silica fume 12 parts, SP1 type nano silicon dioxide 1.5 parts, alkaline activator 15 parts, isobutyl triethoxysilane 13 parts, glycerol 6 parts, penetrating agent 1.5 parts, crystallization precipitant 4 parts, complexing agent 1.5 parts.

[0075] The iron tailings powder is prepared by grinding iron tailings, and the iron tailings are Jiu Steel type iron tailings.

[0076] The alkaline activator is a mixture of potassium water glass, sodium hydroxide and sodium silicate in a mass ratio of 2:1:1.

[0077] The crystallization precipitant is methyl sodium silicate.

[0078] The complexing agent is calcium diethylenetriamine pentacarboxylate.

[0079] The preparation method is the same as that of specific embodiment 1. Specific embodiment 5:

[0081] The geopolymer-based penetrating crystallization waterproof coating for marine environment is prepared from the following raw materials by weight:

[0082] Quartz sand 100 parts, water 80 parts, wool keratin 6 parts, slag powder 20 parts, iron tailings powder 8 parts, fly ash 12 parts, silica fume 10 parts, SP1 nano silicon dioxide 2 parts, alkaline activator 12 parts, isobutyl triethoxysilane 16 parts, glycerol 8 parts, penetrating agent 2 parts, crystallization precipitant 6 parts, complexing agent 2 parts.

[0083] The iron tailings powder is made of iron tailings, and the types of the iron tailings are high-silicon type iron tailings and high-aluminum type iron tailings mixed at a mass ratio of 1:1.

[0084] The alkaline activator is made of sodium water glass and sodium silicate mixed at a mass ratio of 1:1.

[0085] The crystallization precipitant is anhydrous sodium carbonate.

[0086] The complexing agent is sodium nitrilotriacetate.

[0087] The preparation method is the same as that in specific embodiment 1. Specific embodiment 6:

[0089] The geopolymer-based penetrating crystalline waterproof coating for marine environment is made of the following raw materials by weight:

[0090] Quartz sand 100 parts, water 80 parts, wool keratin 6 parts, slag powder 20 parts, iron tailings powder 8 parts, fly ash 10 parts, silica fume 12 parts, SP1 nano silicon dioxide 2 parts, alkaline activator 12 parts, isobutyl triethoxysilane 16 parts, glycerol 8 parts, penetrating agent 2 parts, crystallization precipitant 6 parts, complexing agent 2 parts.

[0091] The iron tailings powder is made of iron tailings, and the types of the iron tailings are high-calcium-magnesium type iron tailings and Jiu Steel type iron tailings mixed at a mass ratio of 1:1.

[0092] The alkaline activator is made of potassium water glass, potassium hydroxide and calcium silicate mixed at a mass ratio of 2:1:1.

[0093] The crystallization precipitant is methyl sodium silicate.

[0094] The complexing agent is calcium diethylenetriamine pentaacetate.

[0095] The preparation method is the same as that in specific embodiment 1.

[0096] According to GB18445-2012 "Cement-based penetrating crystalline waterproof material", the 28d performance indicators of the penetrating crystalline waterproof slurries in specific embodiments 1-6 are tested, and the test results are as follows:

[0097] Table 1 Performance test results of the geopolymer-based penetrating crystalline waterproof coating prepared in specific embodiments 1-6

[0098]

[0099]

[0100] As shown in Table 1, the foundation polymer-based permeable crystalline waterproof coating prepared by the application has good compressive strength, and the wet base bonding strength is between 2.4-2.8 MPa; and the permeability and anti-harmful medium invasion performance of the concrete are obviously improved, the permeation pressure is greater than 2.7 MPa, the chloride ion diffusion coefficient is between 5.75*10 -12 m 3 / s-8.09*10 -12 m 3 / s, and has good self-repair performance index.

[0101] The alkali excitation process of the foundation polymer-based permeable crystalline waterproof coating mainly includes the following three stages: (a) destruction-solidification; (b) condensation condensation; (c) condensation crystallization.

[0102] In the first stage, the OH - ion in the alkali excitation agent weakens the Si-O-Si bond, so that the electron density of the silicon atom is redistributed, and the-Si-OH and-Si O- substances are generated at the same time, and the alkali cation neutralizes the generated negative charge to produce Si-O-Na + bond and hinders the repair of the Si-O-Si bond.

[0103] In the second stage, the accumulation of ionic substances promotes the contact between the decomposition products and begins to condense. Under the catalysis of OH - , the silicon dioxide monomers react with each other to form dimers, and the dimers react with other monomers to form polymers. The clusters formed by the polymerization of silicates begin to produce colloids in all directions at the same time, and aluminates participate in polymerization to replace the silicon tetrahedral structure as a structural component.

[0104] In the third stage, the presence of particles in the initial solid phase promotes the precipitation of the reaction products to form the structural framework of the permeable crystalline waterproof coating.

[0105] The one-time permeable crystallization mechanism of the foundation polymer-based permeable crystalline waterproof coating mainly includes the following three stages: (a) dissolution; (b) penetration; (c) crystallization.

[0106] In the first stage, after the waterproof coating is mixed with water, it begins to hydrate and releases Ca 2+ and other metal cations, and the liquid phase is strongly alkaline. After the surfactant is dissolved in water, the surface tension of the coating is reduced, the catalyst is complexed with Ca 2+ to form calcium complexes, and the active ingredients in the coating system are in the form of non-sticky colloids.

[0107] The second stage, under the action of osmotic pressure, the surfactant penetrates into the surface capillary of concrete, reduces the surface tension of water in the capillary. 2+ Avoids the premature reaction of residual trace SiO3 2- In the capillary, and blocks the capillary.

[0108] The third stage, the active ingredient in the capillary occurs hydration reaction in the alkaline environment, the complexing agent uses the coordination center electron effect to reduce the activation energy of the hydration reaction, and promotes the generation of insoluble crystals. At the same time, the hydration active ingredient occurs polycondensation reaction and produces hydrophobic crystalline material. The complexing agent stimulates the unhydrated active material on the capillary wall and continues to hydrate, produces hydration CaSiO3 and other insoluble crystals to block the water permeation channel, thereby showing excellent impermeability.

[0109] The secondary penetration and crystallization mechanism of the foundation polymer-based penetration and crystallization waterproof coating mainly includes the following three stages: (a) diffusion; (b) enrichment; (c) crystallization.

[0110] The first stage, due to the generation of cracks, the active material in the concrete is broken, and under the action of concentration pressure difference, the active material diffuses to the small cracks.

[0111] The second stage, due to the enrichment effect, the active material in the base layer (including active ingredients, complexing agents, surfactants, etc.) provides a chemical driving force, which provides conditions for the re-generation of insoluble crystals.

[0112] The third stage, under the action of active agents such as complexing agents, insoluble crystals are generated in the places where the capillary is broken or small cracks appear. At the same time, the unhydrated cement clinker is also excited to hydrate, producing hydration CaSiO3 and other insoluble crystals to repair the seepage channel again, and generating the self-repairing function.

[0113] The advantages of the present application are:

[0114] 1, the solid waste is processed into waterproof coating, which improves the utilization rate of solid waste, and has certain environmental protection advantages and economic advantages.

[0115] 2, the waterproof coating can penetrate into the pores of the concrete after contacting with water, react with the cement hydration products to generate insoluble crystal products, and play a role in compacting the capillary pores on the surface of the concrete structure base layer, further increasing the hydrophobic waterproof ability of the surface of the concrete structure base layer.

[0116] 3. The addition of wool keratin in the waterproof coating improves the surface elasticity of the waterproof film, reduces the temperature stress of the rigid waterproof layer, enhances the durability of the waterproof layer, and when the waterproof layer is damaged by freezing and thawing, it can also absorb water vapor in the marine environment, provide a seepage channel, improve the secondary permeation crystallization efficiency, and play a role in repairing the waterproof layer and the damaged substrate of the concrete.

[0117] 4. Using a foundation polymer-based waterproof coating instead of a cement-based material not only avoids the problems of high energy consumption and high carbon emissions in the cement production process, but also produces a waterproof coating with strong durability and corrosion resistance, suitable for a variety of engineering scenarios.

[0118] The above describes the present application in conjunction with specific embodiments, and it is obvious that the specific implementation of the present application is not limited to the above-mentioned manner. Any improvement using the method concept and technical solution of the present application, or direct application to other occasions without improvement, is within the protection scope of the present application.

Claims

1. A geopolymer-based permeable crystalline waterproofing coating for marine environments, characterized in that, The composition and weight parts are as follows: 80-100 parts of quartz sand, 80-100 parts of water, 6-8 parts of wool keratin, 20-40 parts of slag powder, 8-12 parts of iron tailings powder, 8-12 parts of fly ash, 8-12 parts of silica ash, 1-2 parts of SP1 type nano silicon dioxide, 12-18 parts of alkaline activator, 10-16 parts of isobutyl triethoxysilane, 4-8 parts of glycerol, 1-2 parts of penetrating agent, 2-6 parts of crystallization precipitant, and 1-3 parts of complexing agent; The penetrating agent is composed of fatty alcohol polyoxyethylene ether and sodium polycarbonate with a mass ratio of 3:2; The crystallization precipitant is anhydrous sodium carbonate or methyl potassium silicate; The complexing agent is sodium nitrilotriacetate or calcium diethylenetriamine pentacarboxylate.

2. The geopolymer-based permeable crystalline waterproofing coating for marine environments according to claim 1, characterized in that, The preparation method of the wool keratin comprises the following steps: S1, crushing and washing the waste wool to form a stable emulsion of lanolin, with impurities floating on the washing liquid, and then removing the impurities and drying in a drying oven for 24 hours; S2, taking 2g of the dried wool obtained in step S1, adding 0.6 mol / L sodium pyrosulfite, 9 mol / L urea, and 0.12 mol / L sodium dodecyl sulfate with a bath ratio of 1:50, uniformly mixing, heating to 70℃ in a constant temperature water bath, and fully dissolving and reacting for 12 hours under low speed stirring; S3, filtering and dialyzing the mixed solution, and freeze-drying to obtain the wool keratin.

3. The geopolymer-based permeable crystalline waterproofing coating for marine environments according to claim 1, characterized in that, The particle size of the quartz sand is 0.5-0.8mm, the particle size of the slag powder is 400-450μm, the particle size of the iron tailings powder is 5-10μm, the particle size of the fly ash is 0.5-300μm, the particle size of the silica ash is 0.1-0.3μm, and the particle size of the SP1 type nano silicon dioxide is 20-50nm.

4. The geopolymer-based permeable crystalline waterproofing coating for marine environments according to claim 1, characterized in that, The iron tailings powder is made of iron tailings, and the types of the iron tailings are one or more of high-silicon type, high-aluminum type, high-calcium-magnesium type, Jiujiang-steel type, and multi-metal type.

5. The geopolymer-based permeable crystalline waterproofing coating for marine environments according to claim 1, characterized in that, The alkaline activator is one or more of sodium water glass, potassium water glass, potassium hydroxide, sodium hydroxide, and sodium silicate; the modulus of the sodium water glass and the potassium water glass is 1.2-2.4, and the purity of the potassium hydroxide, the sodium hydroxide, and the sodium silicate is analytical pure.

6. A method for the preparation of a geopolymer-based permeable crystalline waterproofing coating for marine environments according to any one of claims 1-5, characterized by, The specific steps are as follows: P1, mixing and stirring the alkaline activator, the penetrating agent, the crystallization precipitant, and the complexing agent according to the weight parts for 90s, then adding glycerol, isobutyl triethoxysilane, and 1 / 3 of the total water amount for 120s while stirring, adding water while stirring, cooling to room temperature to obtain mixed solution A; P2, wetting the blender, adding quartz sand, slag powder, iron tailings powder, fly ash, silica ash, and SP1 type nano silicon dioxide and stirring for 90s, then adding 2 / 3 of the total water amount and stirring for 120s while adding water, to obtain mixed solution B; P3, mixing and stirring mixed solution A and mixed solution B for 90s, adding wool keratin and stirring for 120s to obtain the geopolymer-based penetrating and crystallizing waterproof coating.

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