CN108821680B - Preparation process of wet-grinding modified cement-based rigid self-waterproof material - Google Patents
Preparation process of wet-grinding modified cement-based rigid self-waterproof material Download PDFInfo
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- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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Abstract
The invention relates to a preparation process of a wet-grinding modified cement-based rigid self-waterproof material, which adopts the technical scheme that the wet-grinding modified cement-based rigid self-waterproof material is prepared by mixing the following raw materials: 50-60 parts of wet-grinding modified silicon-aluminum solid waste waterproof slurry, 30-50 parts of Portland cement, 300 parts of inert filler 100, 20-30 parts of active filler and 15-45 parts of water; wherein, the wet-milling modified silicon-aluminum solid waste waterproof slurry is prepared by adopting the following method: 1) carrying out wet grinding on 100 parts of silicon-aluminum solid waste powder, 1-8 parts of alkali, 0.1-0.4 part of polycarboxylic acid dispersant and 40-50 parts of water, and grinding to obtain silicon-aluminum solid waste slurry; 2) adding 1-10 parts of surface modifier into the solid waste slurry of the silicon and aluminum obtained in the step 1), and carrying out wet grinding until the median particle size is 300nm-1 mu m to obtain the wet grinding modified solid waste waterproof slurry of the silicon and aluminum. The invention has the advantages of simple process, low cost, no pollution hazard, excellent durability, excellent mechanical property and good impermeability.
Description
Technical Field
The invention relates to a cement-based waterproof material, in particular to a preparation process of a wet-grinding modified cement-based rigid self-waterproof material.
Background
The service life, durability and use safety of the concrete structure are greatly related to the waterproof performance of the building material in the natural environment. On one hand, some structures such as subways, pipe galleries, tunnels and the like need to be repaired and maintained soon after being put into use due to infiltration and corrosion of environmental water with corrosive media, and even cause durability damage; on the other hand, underground works have the problems of long-term leakage, undercurrent scouring and the like due to improper arrangement of a waterproof structure, so that the engineering disasters such as settlement, collapse, sudden water burst and the like sometimes occur.
At present, the most common building waterproof materials at home and abroad mainly comprise asphalt waterproof coiled materials, high-molecular waterproof coiled materials, polymer-based waterproof coatings, elastomer sealants and the like. The common characteristic of the waterproof materials is that the waterproof materials are all polymer waterproof materials, and the problems of high cost, high temperature sensitivity, weak aging resistance, easy water leakage at a bonding interface between the waterproof materials and a cement-based building material and the like exist mainly.
The cement-based waterproof material is usually formed by adding a polymer material into a cement-based material and forming a certain waterproof function through an organic-inorganic interpenetrating network formed between a polymer demulsification film and a cement matrix. At present, organic materials such as polymer emulsion, latex and the like are commonly added into cement-based waterproof materials to block capillary pores, so that waterproof capability is formed. For example, chinese patent CN107686297A discloses a cement-based waterproof material comprising acrylic emulsion, acrylic ester-styrene copolymer emulsion, styrene-butadiene copolymer emulsion, vinyl acetate-ethylene copolymer emulsion; chinese patent CN107572967A discloses a cement-based waterproof material containing latex and epoxy resin emulsion; chinese patent CN107540318A discloses a cement-based waterproof plugging material containing organosilane and a microporous emulsifier; chinese patent CN106145823A discloses a polymer modified cement-based waterproof slurry containing acrylic emulsion and rubber powder; chinese patent CN107628788A discloses a cement-based waterproof material containing butyl acrylate, methacrylic acid, vinyl versatate and beta-carboxyethyl acrylate. The cement-based waterproof material is mainly used for improving a cement stone structure through a polymer material. However, in order to ensure a better waterproof effect, the amount of the polymer is generally higher, which increases the cost on one hand and also has a great influence on the performance (such as strength) of the cement-based material on the other hand. Meanwhile, the polymer cement-based waterproof material also has the defects of potential toxic substances, pungent odor and the like.
Disclosure of Invention
The invention aims to solve the technical problems and provides a preparation process of a wet-grinding modified cement-based rigid self-waterproof material, which has the advantages of simple process, high waste utilization rate, low cost, no pollution hazard, excellent durability, excellent mechanical property and good impermeability.
The technical scheme is that the material is prepared by mixing the following raw materials in parts by weight: 50-60 parts of wet-grinding modified silicon-aluminum solid waste waterproof slurry, 30-50 parts of Portland cement, 300 parts of inert filler 100, 20-30 parts of active filler and 15-45 parts of water;
wherein, the wet-milling modified silicon-aluminum solid waste waterproof slurry is prepared by adopting the following method:
1) wet grinding 100 parts of silicon-aluminum solid waste powder, 1-8 parts of alkali, 0.1-0.4 part of polycarboxylic acid dispersant and 40-50 parts of water for 4-10 hours to obtain silicon-aluminum solid waste slurry;
2) adding 1-10 parts of surface modifier into the solid waste slurry of the silicon and aluminum obtained in the step 1) for wet grinding for 30min-2h until the median particle size is 300nm-1 mu m, thus obtaining the wet grinding modified solid waste waterproof slurry of the silicon and aluminum.
In the step (1), during wet grinding, the ratio of the mixture to the grinding balls is 3:7, and the rotating speed is 60 Hz; in the step (2), the ratio of the mixture to the grinding balls is 3:7, and the rotating speed is 20 Hz.
In the step (1), the silicon-aluminum solid waste powder is any one of phosphorus slag, coal gangue, steel slag, manganese slag, copper slag and zinc slag, and the median particle size is 10-30 μm.
In the step (1), the alkali is sodium hydroxide or sodium silicate.
In the step (1), the surface modifier is a mixture of silanol and hydroxyl silicone oil.
In order to improve the utilization rate of waste, the inventor expects more possible use of industrial waste, but good chemical bonding force and adhesion effect cannot be formed between common industrial waste and a waterproof surface modifier, so that the use of a large amount of waste cannot ensure the full play of a waterproof function, and simultaneously, the reduction of structural compactness is caused, and the self-waterproofing of a structure is not facilitated. The nanometer-scale (300nm-1 μm) silicon-aluminum solid waste particles prepared by wet grinding are combined with the special liquid phase ion environment of wet grinding, and the dissolution of calcium ions and silicon-aluminum phases is obviously increased, so that the number of broken bonds and unsaturated bond sites (such as silicon hydroxyl) on the surface of the silicon-aluminum solid waste particles is accelerated; furthermore, alkaline substances such as sodium hydroxide or sodium silicate and the like are added in the wet grinding process, the quantity of silicon hydroxyl exposed on the surface of the solid waste of the silicon and the aluminum is further increased, the grinding time is 4-10 hours, and sufficient polymerization sites are provided for the subsequent surface modifier.
And adding a surface modifier containing hydroxyl after grinding for 4-10 hours, and carrying out polycondensation with the silicon hydroxyl exposed on the surface of the wet-ground silicon-aluminum solid waste to form the sealed waterproof molecular film. By introducing surface modifiers such as silanol, hydroxyl silicone oil and the like, the hydroxyl carried by the surface modifiers and the silicon hydroxyl exposed on the surface of the wet-milled particles are subjected to condensation polymerization, and a sealing waterproof molecular film is formed on the surface of mineral particles, so that the wet-milled modified silicon-aluminum solid waste waterproof slurry with the self-waterproof function is formed.
The nano-scale silicon-aluminum solid waste ultrafine particles prepared by a wet grinding process not only can play a role of crystal nucleus induced hydration, but also can obviously improve the structural compactness of the cement-based waterproof material and improve the self-waterproof capability of the structure. The addition amount of the wet-grinding modified silicon-aluminum solid waste waterproof slurry is controlled to be 50-60 parts, excessive addition is not beneficial to uniform dispersion of nano ultrafine particles, the material cost is obviously increased, too little addition is not obvious in crystal nucleus induced hydration effect, and the self-waterproof capability of the structure is limited.
Furthermore, except for silicate cement, the used inert filler and active filler are industrial waste residues, the inert filler is one of phosphorus tailings, copper tailings, vanadium-titanium smelting waste residues and ceramic waste residues, the median particle size is 50 micrometers-5 mm, the waste residues are mainly inert components, obvious volume instability cannot be generated in the later stage, and the filler has high mechanical strength and can be used as the inert filler; the active filler is any one of fly ash, blast furnace slag and lithium slag, the median particle size is 10-20 mu m, the waste slag has the characteristic of potential pozzolan reactivity, can perform a late-stage reaction under the action of alkali generated by cement hydration, and can be used as the active filler.
Meanwhile, the invention also fully considers the grain composition among different materials so as to fully play the integral compact waterproof function of the cement-based material. The particle size range of the wet-grinding modified silicon-aluminum solid waste waterproof slurry is 300nm-1 mu m, the particle size range of the active filler is 10-20 mu m, and the particle size range of the inert filler is 50 mu m-5mm, so that the continuous integral with compact structure can be formed. In a word, the wet-grinding modified cement-based rigid self-waterproof material integrates the self-waterproof function and the nano effect formed by the wet-grinding modified silicon-aluminum solid waste waterproof slurry and the self-waterproof function of a structure formed by a compact structure.
The wet-grinding modified cement-based rigid self-waterproof material avoids the use of a large amount of organic polymers such as latex and emulsion, has no pollution hazard, takes an inorganic material as a main body, and has better durability than the organic polymers.
Has the advantages that:
firstly, preparing the green and low-cost cement-based rigid self-waterproof material by taking the solid waste of the silicon and the aluminum as a raw material.
The invention breaks the traditional thought of preparing a cement-based waterproof material by taking a polymer as a main body, and the wet grinding technology is adopted to carry out waterproof modification on the solid waste of the silicon and aluminum to prepare the wet grinding modified solid waste waterproof slurry of the silicon and aluminum with the self-waterproof function. Meanwhile, the cement-based rigid self-waterproof material based on the silicon-aluminum industrial solid waste is prepared by taking the silicon-aluminum industrial solid waste such as 50-5 mm phosphorus tailings, copper tailings, vanadium-titanium smelting waste residues and ceramic waste as inert fillers and taking the silicon-aluminum industrial solid waste such as 10-20 μm fly ash, blast furnace slag and lithium slag as active fillers, and has the advantages of high waste utilization rate, no addition of irritant chemical polymers, environmental friendliness, low production cost and no generation of harmful gases;
secondly, the structure is compact, the mechanical property is excellent, and the impermeability is good.
After the traditional cement-based waterproof material is doped with polymer emulsion or polymer rubber powder, the mechanical property and rigidity are obviously reduced. The invention does not mix polymer emulsion or rubber powder, but uses wet-milling modified silicon-aluminum solid waste waterproof slurry as a waterproof functional component, and simultaneously, the nano-scale silicon-aluminum solid waste ultrafine particles with the particle size of 300nm-1 mu m can obviously improve the structural compactness and the mechanical property of the cement-based waterproof material, and have good impermeability;
thirdly, the process is simple, time-saving and labor-saving.
The wet-grinding modified silicon-aluminum solid waste waterproof slurry prepared by the invention has good storability, and when the cement-based waterproof material is prepared, the filler and the water are directly added and uniformly stirred, so that the time and the labor are saved.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1:
a wet-grinding modified cement-based rigid self-waterproof material comprises the following raw materials in parts by weight: 50 parts of wet-grinding modified silicon-aluminum solid waste waterproof slurry, 30 parts of Portland cement, 100 parts of inert filler, 20 parts of active filler and 15 parts of water.
Wherein, the wet-milling modified silicon-aluminum solid waste waterproof slurry comprises the following components in percentage by weight: 100 parts of silicon-aluminum solid waste powder, 1 part of alkali, 1 part of surface modifier, 0.1 part of polycarboxylic acid dispersant and 40 parts of water.
The wet-grinding modified silicon-aluminum solid waste waterproof slurry is prepared by the following steps:
1) grinding 100 parts of silicon-aluminum solid waste powder, 1 part of alkali, 0.1 part of polycarboxylic acid dispersant and 40 parts of water in a large wet grinder, wherein the ratio of the mixture to grinding balls is 3:7, the rotating speed is 60Hz, and the grinding time is 7 hours to obtain silicon-aluminum solid waste slurry;
2) adding 1 part of surface modifier into the solid waste slurry of the silicon and aluminum obtained in the step 1), wherein the rotating speed is 20Hz, and the grinding time is 2h, so as to obtain the wet-grinding modified solid waste waterproof slurry of the silicon and aluminum, wherein the median particle size is 500 nm.
Wherein the surface modifier is a mixture of silanol and hydroxyl silicone oil, and the mixing ratio is 1: 1; the silicon-aluminum solid waste powder is phosphorus slag, and the median particle size is 30 mu m; the base is sodium hydroxide.
The inert filler is phosphate tailings, and the median particle size is 50 mu m-5mm continuous gradation.
The active filler is blast furnace slag, and the median particle size is 20 mu m.
Example 2:
a wet-grinding modified cement-based rigid self-waterproof material comprises the following raw materials in parts by weight: 60 parts of wet-grinding modified silicon-aluminum solid waste waterproof slurry, 50 parts of Portland cement, 300 parts of inert filler, 30 parts of active filler and 45 parts of water.
Wherein, the wet-milling modified silicon-aluminum solid waste waterproof slurry comprises the following components in percentage by weight: 100 parts of silicon-aluminum solid waste powder, 8 parts of alkali, 10 parts of surface modifier, 0.4 part of polycarboxylic acid dispersant and 50 parts of water.
The wet-grinding modified silicon-aluminum solid waste waterproof slurry is prepared by the following steps:
1) grinding 100 parts of silicon-aluminum solid waste powder, 8 parts of alkali, 0.4 part of polycarboxylic acid dispersant and 50 parts of water in a large wet grinder, wherein the ratio of the mixture to grinding balls is 3:7, the rotating speed is 60Hz, and the grinding time is 10 hours to obtain silicon-aluminum solid waste slurry;
2) adding 10 parts of surface modifier into the solid waste slurry of the silicon and aluminum obtained in the step 1), wherein the rotating speed is 20Hz, and the grinding time is 30min, so as to obtain the wet-grinding modified solid waste waterproof slurry of the silicon and aluminum, wherein the median particle size is 300 nm.
Wherein the surface modifier is a mixture of silanol and hydroxyl silicone oil, and the mixing ratio is 1: 9; the silicon-aluminum solid waste powder is coal gangue, and the median particle size is 10 mu m; the alkali is sodium silicate.
The inert filler is copper tailings, and the median particle size is 50-5 mm continuous gradation.
The active filler is lithium slag, and the median particle size is 10 mu m.
Example 3:
a wet-grinding modified cement-based rigid self-waterproof material comprises the following raw materials in parts by weight: 55 parts of wet-grinding modified silicon-aluminum solid waste waterproof slurry, 40 parts of Portland cement, 200 parts of inert filler, 25 parts of active filler and 30 parts of water.
Wherein, the wet-milling modified silicon-aluminum solid waste waterproof slurry comprises the following components in percentage by weight: 100 parts of silicon-aluminum solid waste powder, 5 parts of alkali, 5 parts of surface modifier, 0.2 part of polycarboxylic acid dispersant and 45 parts of water.
The wet-grinding modified silicon-aluminum solid waste waterproof slurry is prepared by the following steps:
1) grinding 100 parts of silicon-aluminum solid waste powder, 5 parts of alkali, 0.2 part of polycarboxylic acid dispersant and 45 parts of water in a large wet grinder, wherein the ratio of the mixture to grinding balls is 3:7, the rotating speed is 60Hz, and the grinding time is 4 hours, so as to obtain silicon-aluminum solid waste slurry;
2) adding 5 parts of surface modifier into the solid waste slurry of the silicon and aluminum obtained in the step 1), wherein the rotating speed is 20Hz, and the grinding time is 1h, so as to obtain the wet-grinding modified solid waste waterproof slurry of the silicon and aluminum, wherein the median particle size is 1 micron.
Wherein the surface modifier is a mixture of silanol and hydroxyl silicone oil, and the mixing ratio is 9: 1; the silicon-aluminum solid waste powder is steel slag, and the median particle size is 10 mu m; the alkali is sodium silicate.
The inert filler is vanadium-titanium smelting waste residue, and the median particle size is 50 mu m-5mm continuous gradation.
The active filler is fly ash, and the median particle size is 20 mu m.
Example 4:
a wet-grinding modified cement-based rigid self-waterproof material comprises the following raw materials in parts by weight: 60 parts of wet-grinding modified silicon-aluminum solid waste waterproof slurry, 50 parts of Portland cement, 100 parts of inert filler, 30 parts of active filler and 30 parts of water.
Wherein, the wet-milling modified silicon-aluminum solid waste waterproof slurry comprises the following components in percentage by weight: 100 parts of silicon-aluminum solid waste powder, 8 parts of alkali, 5 parts of a surface modifier, 0.4 part of a polycarboxylic acid dispersant and 40 parts of water.
The wet-grinding modified silicon-aluminum solid waste waterproof slurry is prepared by the following steps:
1) grinding 100 parts of silicon-aluminum solid waste powder, 8 parts of alkali, 0.4 part of polycarboxylic acid dispersant and 40 parts of water in a large wet grinder, wherein the ratio of the mixture to grinding balls is 3:7, the rotating speed is 60Hz, and the grinding time is 8 hours to obtain silicon-aluminum solid waste slurry;
2) adding 5 parts of surface modifier into the solid waste slurry of the silicon and aluminum obtained in the step 1), wherein the rotating speed is 20Hz, and the grinding time is 1h, so as to obtain the wet-grinding modified solid waste waterproof slurry of the silicon and aluminum, wherein the median particle size is 400 nm.
Wherein the surface modifier is a mixture of silanol and hydroxyl silicone oil, and the mixing ratio is 4: 6; the silicon-aluminum solid waste powder is manganese slag, and the median particle size is 10 mu m; the base is sodium hydroxide.
The inert filler is ceramic waste, and the median particle size is 50-5 mm continuous gradation.
The active filler is fly ash, and the median particle size is 15 mu m.
Example 5:
a wet-grinding modified cement-based rigid self-waterproof material comprises the following raw materials in parts by weight: 60 parts of wet-grinding modified silicon-aluminum solid waste waterproof slurry, 30 parts of Portland cement, 200 parts of inert filler, 20 parts of active filler and 20 parts of water.
Wherein, the wet-milling modified silicon-aluminum solid waste waterproof slurry comprises the following components in percentage by weight: 100 parts of silicon-aluminum solid waste powder, 6 parts of alkali, 6 parts of surface modifier, 0.2 part of polycarboxylic acid dispersant and 40 parts of water.
The wet-grinding modified silicon-aluminum solid waste waterproof slurry is prepared by the following steps:
1) grinding 100 parts of silicon-aluminum solid waste powder, 6 parts of alkali, 0.2 part of polycarboxylic acid dispersant and 40 parts of water in a large wet grinder, wherein the ratio of the mixture to grinding balls is 3:7, the rotating speed is 60Hz, and the grinding time is 6 hours to obtain silicon-aluminum solid waste slurry;
2) adding 6 parts of surface modifier into the solid waste slurry of the silicon and aluminum obtained in the step 1), wherein the rotating speed is 20Hz, and the grinding time is 2h, so as to obtain the wet-grinding modified solid waste waterproof slurry of the silicon and aluminum, wherein the median particle size is 800 nm.
Wherein the surface modifier is a mixture of silanol and hydroxyl silicone oil, and the mixing ratio is 6: 4; the silicon-aluminum solid waste powder is copper slag, and the median particle size is 20 mu m; the alkali is sodium silicate.
The inert filler is copper tailings, and the median particle size is 50-5 mm continuous gradation.
The active filler is blast furnace slag, and the median particle size is 20 mu m.
Example 6:
a wet-grinding modified cement-based rigid self-waterproof material comprises the following raw materials in parts by weight: 55 parts of wet-grinding modified silicon-aluminum solid waste waterproof slurry, 45 parts of Portland cement, 300 parts of inert filler, 20 parts of active filler and 20 parts of water.
Wherein, the wet-milling modified silicon-aluminum solid waste waterproof slurry comprises the following components in percentage by weight: 100 parts of silicon-aluminum solid waste powder, 1 part of alkali, 10 parts of surface modifier, 0.3 part of polycarboxylic acid dispersant and 50 parts of water.
The wet-grinding modified silicon-aluminum solid waste waterproof slurry is prepared by the following steps:
1) grinding 100 parts of silicon-aluminum solid waste powder, 1 part of alkali, 0.3 part of polycarboxylic acid dispersant and 50 parts of water in a large wet grinder, wherein the ratio of the mixture to grinding balls is 3:7, the rotating speed is 60Hz, and the grinding time is 4 hours, so as to obtain silicon-aluminum solid waste slurry;
2) adding 10 parts of surface modifier into the solid waste slurry of the silicon and aluminum obtained in the step 1), wherein the rotating speed is 20Hz, and the grinding time is 2h, so as to obtain the wet-grinding modified solid waste waterproof slurry of the silicon and aluminum, wherein the median particle size is 1 micron.
Wherein the surface modifier is a mixture of silanol and hydroxyl silicone oil, and the mixing ratio is 5: 5; the silicon-aluminum solid waste powder is zinc slag, and the median particle size is 30 mu m; the alkali is sodium silicate.
The inert filler is vanadium-titanium smelting waste residue, and the median particle size is 50 mu m-5mm continuous gradation.
The active filler is lithium slag, and the median particle size is 15 mu m.
Comparative example 1:
the comparative example is the same as example 1 except that the solid waste of silicon and aluminum is not subjected to wet grinding process and is not subjected to waterproof modification by adding a surface modifier.
Comparative example 2:
the comparative example is the traditional polymer emulsion waterproof mortar, except that the qualities of wet-grinding modified silicon-aluminum solid waste waterproof slurry and the like are replaced by common butylbenzene emulsion in the market, the other contents are the same as the example 1.
Comparative example 3:
the comparative example is the same as example 1 except that the wet-milling modified silicon-aluminum solid waste waterproof slurry and other qualities are replaced by waterproof silane powder commonly used in the market by adopting the traditional polymer glue powder waterproof mortar.
The test method refers to JC/T984-2005 Polymer Cement waterproof mortar.
Table 1 main properties of the cement-based rigid self-waterproofing materials of examples 1 to 6 and the cement-based materials of comparative examples 1 to 3.
As can be seen from Table 1, the cement-based rigid self-waterproof materials prepared in examples 1-6 have significant advantages in mechanical properties and waterproof properties compared with comparative example 1 and the market common polymer waterproof materials (comparative example 2 and comparative example 3) which are not subjected to wet grinding waterproof modification. Meanwhile, a large amount of wet-milled waterproof modified silicon-aluminum solid waste slurry is adopted to replace polymer emulsion and latex substances commonly adopted at present, so that the method is green and environment-friendly, and no harmful gas is generated.
Claims (6)
1. A preparation process of a wet-grinding modified cement-based rigid self-waterproof material is characterized by comprising the following steps of mixing the following raw materials in parts by weight: 50-60 parts of wet-grinding modified silicon-aluminum solid waste waterproof slurry, 30-50 parts of Portland cement, 300 parts of inert filler with the median particle size of 50-5 mm, 20-30 parts of active filler with the median particle size of 10-20 μm and 15-45 parts of water;
wherein, the wet-milling modified silicon-aluminum solid waste waterproof slurry is prepared by adopting the following method:
1) wet grinding 100 parts of silicon-aluminum solid waste powder, 1-8 parts of alkali, 0.1-0.4 part of polycarboxylic acid dispersant and 40-50 parts of water for 4-10 hours to obtain silicon-aluminum solid waste slurry;
2) adding 1-10 parts of surface modifier into the solid waste silicon-aluminum slurry obtained in the step 1) for wet grinding for 30min-2h until the median particle size is 300nm-1 mu m, thus obtaining the wet grinding modified solid waste silicon-aluminum waterproof slurry; the surface modifier is a mixture of silanol and hydroxyl silicone oil.
2. The process for preparing a wet-milling modified cement-based rigid self-waterproofing material according to claim 1, wherein in the step (1), the ratio of the mixture to the grinding balls during wet milling is 3:7, and the rotation speed is 60 Hz; in the step (2), the ratio of the mixture to the grinding balls is 3:7, and the rotating speed is 20 Hz.
3. The process for preparing the wet-grinding modified cement-based rigid self-waterproofing material according to claim 1 or 2, wherein in the step (1), the solid waste powder of silicon and aluminum is any one of phosphorous slag, coal gangue, steel slag, manganese slag, copper slag and zinc slag, and the median particle size is 10 to 30 μm.
4. The process for preparing a wet milling modified cement-based rigid self-waterproofing material according to claim 1 or 2, wherein in the step (1), the alkali is sodium hydroxide or sodium silicate.
5. The process for preparing the wet-milling modified cement-based rigid self-waterproofing material according to claim 1 or 2, wherein the inert filler is one of phosphate tailings, copper tailings, vanadium-titanium smelting waste residues and ceramic waste materials, and the median particle size is 50 μm to 5 mm.
6. The process for preparing a wet-milling modified cement-based rigid self-waterproofing material according to claim 1 or 2, wherein the active filler is any one of fly ash, blast furnace slag and lithium slag, and the median particle size is 10 to 20 μm.
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