A material for protection and repair of wet soil sites and a preparation method thereof

Abstract

The present application relates to a kind of material and preparation method for wet soil site protection repair, belong to new wall material technical field, the present application uses light porous ceramic granule filling material, active metakaolin, overfire red clay, volcanic ash modified mineral polymer, organic-inorganic hybrid binder based on biological, tributyl citrate, diethyl phthalate, modified vermiculite powder etc. as raw material, each component is used in preparation composite material, applied in ordinary environment or wet environment in the wall protection repair of soil site cracking, collapse and other diseases, with good compatibility, strength is appropriate, stress uniform, durable and other advantages, can effectively realize good site repair protection effect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of new wall materials, and particularly relates to a material for protection and repair of a humid soil site and a preparation method, which is used for wall repair of a site building. BACKGROUND

[0002] Most of the soil sites are unearthed by archaeological excavation, most of which are exposed to the natural environment or covered with protective housing facilities, and are basically in a lower area. The environment of the soil site is relatively humid, and with the passage of display time, different degrees of disease problems have occurred, such as wall soil pulverization, cracking, peeling, etc., which seriously damages the artistic expression value of the site building cultural relics. In order to improve the durability of these site building cultural relics, it is necessary to develop some new wall materials to protect and repair the site building cultural relics, especially the wall, and improve its mechanical properties, moisture resistance, freeze-thaw ability, etc.

[0003] According to the composition of the material, the repair and reinforcement material can be divided into inorganic reinforcement material and organic reinforcement material. Among them, the organic reinforcement material (such as polyacrylic acid resin, epoxy resin, etc.) has good bonding performance and strong fluidity, and has certain advantages in the filling and reinforcement treatment of small cracks, but its durability is low and it is easy to cause secondary damage to the site building wall. Inorganic reinforcement materials have similar composition and structure to walls, have high compatibility, and have been widely studied by researchers in recent years.

[0004] Common inorganic reinforcement materials include cement, lime, water glass, etc., which have been applied to cultural relic walls. For example, Chinese patent CN114933461A, a nano-silicon ball modified metakaolin-based composite material for fissure grouting and its preparation and application, the composite material includes inorganic cementing material, and porous silica microspheres dispersed in the inorganic cementing material, and the inorganic cementing material is a composite of metakaolin and natural hydraulic lime. However, inorganic materials also have certain disadvantages, such as poor fusion with site cultural relic walls, difficulty in applying to humid soil, large difference in strength between the material and the site cultural relic, uneven material stress, and damage to the site cultural relic.

[0005] Therefore, it is necessary to develop a material more suitable for site building walls to achieve better fusion and protection and improve the service life of the overall site cultural relic. SUMMARY

[0006] The present application provides a kind of material for humid soil site protection repair and preparation method, using light porous ceramic granule powder filling material, active metakaolin, over-fired red clay, volcanic ash modified mineral polymer, bio-based organic-inorganic hybrid binder, tributyl citrate, diethyl phthalate, modified vermiculite powder and the like as raw material, each component is prepared composite material by cooperation, applied to the wall protection repair of general environment or humid environment in soil site cracking, collapse and other diseases, with good compatibility, strength is appropriate, stress uniform, durable and other advantages, can effectively realize good site repair protection effect.

[0007] A kind of material for humid soil site protection repair, including the following mass fraction of raw materials: 15 portions-20 portions light porous ceramic granule powder filling material, 20 portions-25 portions active metakaolin, 10 portions-15 portions over-fired red clay, 15 portions-20 portions natural hydraulic lime, 15 portions-20 portions volcanic ash modified mineral polymer, 10 portions-15 portions bio-based organic-inorganic hybrid binder, 3 portions-5 portions tributyl citrate, 1 portion-3 portions diethyl phthalate, 5 portions-8 portions modified vermiculite powder, 0 portion-3 portions pigment, 5 portions-8 portions liquid potassium silicate, 0.5 portions-1 portion tartaric acid, 2 portions-3 portions organic silicon waterproof agent, 0.1 portions-0.5 portions organic silicon defoaming agent, the rest is water.

[0008] In the above raw materials, active metakaolin is kaolin calcined at 700 DEG C to 750 DEG C for 2h to 2.5h.

[0009] In the above raw materials, over-fired red clay is red clay calcined at 500 DEG C to 550 DEG C for 0.5h to 1h, at 600 DEG C to 650 DEG C for 0.5h to 1h, at 700 DEG C to 750 DEG C for 0.5h to 1h, at 800 DEG C to 850 DEG C for 0.5h to 1h and at 900 DEG C to 950 DEG C for 0.5h to 1h.

[0010] In the above raw materials, the particle size of light porous ceramic granule powder filling material is between 80 mesh and 150 mesh.

[0011] In the above raw materials, the particle size of active metakaolin is under 1250 mesh screen.

[0012] In the above raw materials, the particle size of over-fired red clay is between 460 mesh and 6000 mesh.

[0013] In the above raw materials, the particle size of natural hydraulic lime is under 150 mesh screen.

[0014] In the above raw materials, the particle size of volcanic ash modified mineral polymer is under 600 mesh screen.

[0015] In the raw materials, the particle size of the bio-based organic-inorganic hybrid binder is below 100 mesh.

[0016] In the raw materials, the particle size of the modified vermiculite powder is below 200 mesh.

[0017] In the raw materials, the pigment is an ilmenite powder, that is, a Fe2O3-TiO2 composite pigment.

[0018] In the raw materials, the preparation method of the volcanic ash modified mineral polymer comprises the following steps: reacting the volcanic ash with an alkaline activator, drying, and crushing to obtain the volcanic ash modified mineral polymer.

[0019] The mass ratio of the volcanic ash to the alkaline activator is 1:(4-6); the alkaline activator is a mixed aqueous solution of sodium hydroxide and sodium silicate, containing 15wt%-20wt% of sodium hydroxide and 22wt%-28wt% of sodium silicate; the reaction temperature is 50°C-60°C, the reaction time is 2h-3h, and the stirring speed is 400r / min-600r / min; and the particle size of the volcanic ash is below 600 mesh.

[0020] In the raw materials, the preparation method of the bio-based organic-inorganic hybrid binder comprises the following steps: adding pregelatinized starch and glutaraldehyde into water to perform a cross-linking reaction, thereby obtaining a cross-linked biological material solution; ultrasonically dispersing nano-titanium dioxide in ethanol to obtain a dispersion liquid; mixing the dispersion liquid with the cross-linked biological material solution, stirring and reacting, drying, and crushing, thereby obtaining the bio-based organic-inorganic hybrid binder.

[0021] The mass ratio of the pregelatinized starch, glutaraldehyde, and water is (1-1.2):(0.03-0.1):(6-8); the mass ratio of the nano-titanium dioxide and ethanol is (1-1.5):(8-10); the volume ratio of the dispersion liquid to the cross-linked biological material solution is 1:(1.5-3); the cross-linking reaction temperature is 20°C-30°C, the cross-linking reaction time is 2h-3h, and the cross-linking reaction stirring speed is 150r / min-250r / min; the stirring and reaction temperature is 40°C-50°C, the stirring and reaction time is 4h-5h, and the stirring and reaction speed is 200r / min-400r / min.

[0022] In the raw materials, the preparation method of the modified vermiculite powder comprises the following steps: ultrasonically dispersing vermiculite powder in an ethanol aqueous solution, adding hexadecyl trimethoxysilane, stirring and reacting, drying, and crushing, thereby obtaining the modified vermiculite powder.

[0023] The mass ratio of the vermiculite powder, the ethanol aqueous solution and the hexadecyl trimethoxysilane is (1-1.5):(8-10):(0.3-0.8); the volume concentration of the ethanol aqueous solution is 30%-50%; the stirring reaction temperature is 60-70 DEG C; the stirring reaction time is 5-6 hours; and the stirring reaction speed is 300-500 r / min; and the particle size of the vermiculite powder is less than 200 mesh.

[0024] The preparation method of the material for the protection and repair of the humid soil site comprises the following steps:

[0025] S1: according to the mass fraction, light porous ceramic granule filling material, active metakaolin, over-fired red clay, natural hydraulic lime, volcanic ash modified mineral polymer, bio-based organic-inorganic hybrid binder, modified vermiculite powder, tartaric acid and pigment are poured into a stirring container, and are stirred and mixed uniformly to obtain a mixture A;

[0026] S2: tributyl citrate, diethyl phthalate, liquid potassium silicate, organic silicon waterproof agent and organic silicon defoaming agent are added into the mixture A, and are stirred and mixed uniformly to obtain a mixture B;

[0027] S3: water is added into the mixture B, and is uniformly stirred and mixed, and is left to stand and age for 10-15 minutes, and then is uniformly mixed to obtain a uniform slurry.

[0028] The material for the protection and repair of the humid soil site and the preparation method have the following beneficial effects:

[0029] I. The active metakaolin is obtained by calcining kaolin, the crystal structure is destroyed, the specific surface area is increased, and the active points are increased. Compared with kaolin, the active metakaolin can react with water and alkaline substances more quickly, generate more gelatinous products, significantly improve the early strength and later durability of the material, better work with other materials, and improve the overall performance.

[0030] II. The over-fired red clay is calcined in multiple stages, the water and organic matter in the internal structure are removed, the crystal structure is changed, and the pore structure is more reasonable. Compared with red clay, the over-fired red clay has better stability, stronger water resistance and smaller shrinkage, can maintain better performance in a humid environment, and can improve the overall stability and anti-deformation ability of the material when mixed with other ingredients.

[0031] III. The volcanic ash modified mineral polymer is excited by an alkaline activator to form a more stable three-dimensional network structure. Compared with pure volcanic ash, the volcanic ash modified mineral polymer has higher reactivity, can produce more gelatinous substances in a shorter time, greatly improves the strength and durability of the material, and significantly enhances the impermeability and chemical corrosion resistance.

[0032] Four, bio-based organic-inorganic hybrid binder has both the flexibility of organic materials and the rigidity and stability of inorganic materials through cross-linking reaction and the introduction of nano-titanium dioxide. Compared with gelatinized corn starch, it has higher bonding strength, better water resistance, stronger anti-aging performance, can maintain good bonding effect in humid environment, and has better durability and anti-microbial erosion ability.

[0033] Five, tributyl citrate and diethyl phthalate, both are plasticizers, when used together, can play a role in different temperature and humidity conditions, more comprehensively reduce the glass transition temperature of the material, make the material maintain good flexibility and plasticity in a wider temperature range, and effectively reduce the porosity of the composite material, enhance the processing performance and use performance of the material, and improve the comprehensive performance of the material. The selection and addition ratio of the two components are designed according to the site soil characteristics, which can well integrate the material with the site. The use of the two components in a certain proportion has a good synergistic effect on the repair material.

[0034] Six, modified vermiculite powder has organic functional groups introduced through surface modification treatment, and its surface changes from hydrophilic to hydrophobic, improving the compatibility with organic and inorganic materials. Compared with vermiculite powder, it can better disperse in the material and has stronger bonding force with other components, which can more effectively improve the mechanical properties, thermal stability and waterproof performance of the material.

[0035] Seven, active metakaolin and over-fired red clay provide strength and stability; bio-based organic-inorganic hybrid binder enhances the bonding effect; modified vermiculite powder improves the comprehensive performance of the material; tributyl citrate and diethyl phthalate make the material have flexibility and plasticity. They cooperate with each other to make the material maintain good mechanical properties and stability in a humid environment, have appropriate flexibility and waterproof performance, good fusion, improve the overall durability, impermeability and anti-deformation ability of the material, and realize the synergistic improvement of multiple properties.

[0036] In summary, active metakaolin, natural hydraulic lime and other materials have certain gelation and affinity, which can better combine with the soil of the site; bio-based organic-inorganic hybrid binder also helps to enhance the adhesion to the soil, which is beneficial to fusion. The organic silicon waterproof agent can effectively improve the waterproof performance of the material and resist the humid environment to a certain extent; the reasonable collocation of various raw materials forms a dense material structure, which can reduce the influence of water on the performance of the material and is suitable for humid soil. Light-weight porous ceramsite powder filler and other materials cooperate with each other to ensure a certain strength while matching the material performance with the humid soil site to reduce the strength difference. The material has certain fluidity and flexibility, high mixing uniformity, can make the stress distribution uniform, reduce the damage of the wall layer, and is durable.

[0037] The preparation method is simple, easy to operate, fast and efficient, has large-scale application prospect, is environmentally friendly and safe in operation process, has less influence on operators and environment, has good biocompatibility and non-toxicity and non-irritation, and in addition, the inorganic reinforcing material has high durability, is more suitable for long-term protection of earthen ruins, and is suitable for protection and repair of humid earthen ruins. DETAILED DESCRIPTION

[0038] The application will be further described below in combination with specific implementation cases, but the application is not limited to these examples.

[0039] Example 1

[0040] A material for protection and repair of humid earthen ruins, comprising the following mass fractions of raw materials: 18 parts of lightweight porous ceramic particle powder filling material, 23 parts of active metakaolin, 12 parts of over-fired red clay, 18 parts of natural hydraulic lime, 18 parts of volcanic ash modified mineral polymer, 12 parts of bio-based organic-inorganic hybrid binder, 4 parts of tributyl citrate, 2 parts of diethyl phthalate, 6.5 parts of modified vermiculite powder, 6.5 parts of liquid potassium silicate, 0.8 parts of tartaric acid, 2.5 parts of organic silicon waterproof agent, 0.3 parts of organic silicon defoaming agent, and the balance being water.

[0041] The particle size of the lightweight porous ceramic particle powder filling material is between 80 meshes and 150 meshes. The particle size of the active metakaolin is below a 1250 mesh sieve. The particle size of the over-fired red clay is between 460 meshes and 6000 meshes. The particle size of the natural hydraulic lime is below a 150 mesh sieve. The particle size of the volcanic ash modified mineral polymer is below a 600 mesh sieve. The particle size of the bio-based organic-inorganic hybrid binder is below a 100 mesh sieve. The particle size of the modified vermiculite powder is below a 200 mesh sieve.

[0042] The active metakaolin is obtained by calcining kaolin at 750 DEG C for 2 hours.

[0043] The over-fired red clay is obtained by sequentially calcining red clay at 500 DEG C for 0.5 hours, at 600 DEG C for 0.5 hours, at 700 DEG C for 0.5 hours, at 800 DEG C for 0.5 hours and at 900 DEG C for 0.5 hours.

[0044] The preparation method of the volcanic ash modified mineral polymer comprises the following steps: preparing an alkaline activator, the alkaline activator being a mixed aqueous solution of sodium hydroxide and sodium silicate, containing 18wt% of sodium hydroxide and 25wt% of sodium silicate; mixing the volcanic ash below a 600 mesh sieve with the alkaline activator at a mass ratio of 1:5, stirring and reacting at 55 DEG C and 500 r / min for 2.5 hours, drying to constant weight, crushing, sieving through a 600 mesh sieve, and taking the undersize to obtain the volcanic ash modified mineral polymer.

[0045] The preparation method of the bio-based organic-inorganic hybrid binder comprises the following steps: adding pregelatinized starch and glutaraldehyde into water according to the mass ratio of 1.1:0.06:7, and carrying out cross-linking reaction for 2.5 hours under the conditions of 25 DEG C and 200 r / min stirring to obtain a cross-linked biological material solution; dispersing nano-titanium dioxide in ethanol according to the mass ratio of 1.2:9 to obtain a dispersion liquid; mixing the dispersion liquid and the cross-linked biological material solution according to the volume ratio of 1:2.2, and carrying out stirring reaction for 4.5 hours under the conditions of 45 DEG C and 300 r / min stirring speed, and then drying to constant weight, crushing, passing through a 100-mesh sieve, and taking the undersize to obtain the bio-based organic-inorganic hybrid binder.

[0046] The preparation method of the modified vermiculite powder comprises the following steps: uniformly dispersing vermiculite powder passing through a 200-mesh sieve in 40% volume concentration ethanol aqueous solution according to the mass ratio of 1.2:9:0.5, adding hexadecyl trimethoxysilane, and carrying out stirring reaction for 5.5 hours under the conditions of 65 DEG C and 400 r / min stirring speed, and then drying to constant weight, crushing, passing through a 200-mesh sieve, and taking the undersize to obtain the modified vermiculite powder.

[0047] The preparation method of the material for protecting and repairing a humid soil site comprises the following steps:

[0048] S1: according to the mass fraction, light-weight porous ceramic particle filler, active metakaolin, over-fired red clay, natural hydraulic lime, volcanic ash modified mineral polymer, bio-based organic-inorganic hybrid binder, modified vermiculite powder and tartaric acid are poured into a stirring container, and stirring is carried out at a speed of 120 r / min for 8 minutes to obtain a mixture A;

[0049] S2: according to the mass fraction, tributyl citrate, diethyl phthalate, liquid potassium silicate, organic silicon waterproof agent and organic silicon defoaming agent are added into the mixture A, and stirring is carried out at a speed of 250 r / min for 12 minutes to obtain a mixture B;

[0050] S3: water with a mass of 50% of the mixture B is added into the mixture B, and stirring is carried out until uniform, and then standing and aging for 12 minutes, and then stirring is carried out until uniform to obtain a uniform slurry.

[0051] Example 2

[0052] A material for the protection and repair of wet soil sites, comprising the following mass fractions of raw materials: 15 parts of light porous ceramic particle powder filler, 20 parts of active metakaolin, 10 parts of over-fired red clay, 15 parts of natural hydraulic lime, 15 parts of volcanic ash modified mineral polymer, 10 parts of bio-based organic-inorganic hybrid binder, 3 parts of tributyl citrate, 1 part of diethyl phthalate, 5 parts of modified vermiculite powder, 1.5 parts of pigment, 5 parts of liquid potassium silicate, 0.5 parts of tartaric acid, 2 parts of silicone waterproof agent, 0.1 parts of silicone defoaming agent, and the balance being water.

[0053] The particle size of the light porous ceramic particle powder filler is between 80 meshes and 150 meshes. The particle size of the active metakaolin is below 1250 meshes. The particle size of the over-fired red clay is between 460 meshes and 6000 meshes. The particle size of the natural hydraulic lime is below 150 meshes. The particle size of the volcanic ash modified mineral polymer is below 600 meshes. The particle size of the bio-based organic-inorganic hybrid binder is below 100 meshes. The particle size of the modified vermiculite powder is below 200 meshes. The pigment is an iron-titanium ore powder, i.e., a Fe2O3-TiO2 composite pigment.

[0054] The active metakaolin is obtained by calcining kaolin at 730 DEG C for 2 hours.

[0055] The over-fired red clay is obtained by sequentially calcining red clay at 520 DEG C for 1 hour, at 630 DEG C for 1 hour, at 720 DEG C for 1 hour, at 830 DEG C for 1 hour, and at 920 DEG C for 1 hour.

[0056] The preparation method of the volcanic ash modified mineral polymer comprises the following steps: preparing an alkaline activator, the alkaline activator being a mixed aqueous solution of sodium hydroxide and sodium silicate, containing 15wt% of sodium hydroxide and 22wt% of sodium silicate; mixing volcanic ash below 600 meshes with the alkaline activator at a mass ratio of 1:4, stirring at 50 DEG C and 400 r / min for 2 hours, drying to constant weight, crushing, sieving through a 600-mesh sieve, and taking the undersize material to obtain the volcanic ash modified mineral polymer.

[0057] The preparation method of the bio-based organic-inorganic hybrid binder comprises the following steps: adding pregelatinized starch and glutaraldehyde into water at a mass ratio of 1:0.03:6, stirring at 20 DEG C and 150 r / min for 2 hours to obtain a cross-linked biological material solution; ultrasonically dispersing nano-titanium dioxide in ethanol at a mass ratio of 1:8 to obtain a dispersion liquid; mixing the dispersion liquid with the cross-linked biological material solution at a volume ratio of 1:1.5, stirring at 40 DEG C and 200 r / min for 4 hours, drying to constant weight, crushing, sieving through a 100-mesh sieve, and taking the undersize material to obtain the bio-based organic-inorganic hybrid binder.

[0058] The preparation method of the modified vermiculite powder comprises the following steps: vermiculite powder, an ethanol aqueous solution, and hexadecyl trimethoxysilane are uniformly dispersed in an ultrasonic wave in the ethanol aqueous solution with a volume concentration of 30%, hexadecyl trimethoxysilane is added, stirring and reaction are carried out at 60 DEG C and a rotating speed of 300 r / min for 5 h, drying is carried out until the weight is constant, crushing is carried out, the crushed product is sieved through a 200-mesh screen, and the undersize product is taken to obtain the modified vermiculite powder.

[0059] The preparation method of the material for the protection and repair of a humid soil site comprises the following steps:

[0060] S1: light-weight porous ceramic particle powder filling material, active metakaolin, over-fired red clay, natural hydraulic lime, volcanic ash modified mineral polymer, bio-based organic-inorganic hybrid binder, modified vermiculite powder, tartaric acid, and pigments are poured into a stirring container according to the mass fractions, stirring is carried out at a rotating speed of 100 r / min for 5 min, and uniform mixing is carried out to obtain a mixture A;

[0061] S2: tributyl citrate, diethyl phthalate, liquid potassium silicate, organic silicon waterproof agent, and organic silicon defoaming agent are added into the mixture A according to the mass fractions, stirring is carried out at a rotating speed of 200 r / min for 10 min, and uniform mixing is carried out to obtain a mixture B;

[0062] S3: water with a mass of 45% of the mixture B is added into the mixture B, uniform mixing is carried out, 10 min of standing and aging are carried out, and then uniform mixing is carried out to obtain a uniform slurry.

[0063] Example 3

[0064] A material for the protection and repair of a humid soil site comprises the following mass fractions of raw materials: 20 parts of light-weight porous ceramic particle powder filling material, 25 parts of active metakaolin, 15 parts of over-fired red clay, 20 parts of natural hydraulic lime, 20 parts of volcanic ash modified mineral polymer, 15 parts of bio-based organic-inorganic hybrid binder, 5 parts of tributyl citrate, 3 parts of diethyl phthalate, 8 parts of modified vermiculite powder, 3 parts of pigments, 8 parts of liquid potassium silicate, 1 part of tartaric acid, 3 parts of organic silicon waterproof agent, 0.5 parts of organic silicon defoaming agent, and the balance is water.

[0065] The particle size of the light-weight porous ceramic particle powder filling material is between 80 meshes and 150 meshes. The particle size of the active metakaolin is undersize of a 1250-mesh screen. The particle size of the over-fired red clay is between 460 meshes and 6000 meshes. The particle size of the natural hydraulic lime is undersize of a 150-mesh screen. The particle size of the volcanic ash modified mineral polymer is undersize of a 600-mesh screen. The particle size of the bio-based organic-inorganic hybrid binder is undersize of a 100-mesh screen. The particle size of the modified vermiculite powder is undersize of a 200-mesh screen. The pigments are Fe2O3-TiO2 composite pigments.

[0066] wherein the active metakaolin is obtained by calcining kaolin at 700℃ for 2.5h.

[0067] wherein the over-fired red clay is obtained by calcining red clay at 550℃ for 0.5h, at 650℃ for 0.5h, at 750℃ for 0.5h, at 850℃ for 0.5h and at 950℃ for 0.5h in sequence.

[0068] wherein the preparation method of the pozzolan modified mineral polymer comprises: preparing an alkaline activator, the alkaline activator being a mixed aqueous solution of sodium hydroxide and sodium silicate, containing 20wt% of sodium hydroxide and 28wt% of sodium silicate; mixing pozzolan and the alkaline activator in a mass ratio of 1:6, stirring at 60℃ and 600r / min for 3h, drying to constant weight, crushing, sieving through a 600-mesh screen, and taking the undersize to obtain the pozzolan modified mineral polymer.

[0069] wherein the preparation method of the bio-based organic-inorganic hybrid binder comprises: adding pregelatinized starch and glutaraldehyde into water in a mass ratio of 1.2:0.1:8, stirring at 30℃ and 250r / min for 3h to obtain a cross-linked biological material solution; ultrasonic dispersing nano-titanium dioxide in ethanol in a mass ratio of 1.5:10 to obtain a dispersion liquid; mixing the dispersion liquid and the cross-linked biological material solution in a volume ratio of 1:3, stirring at 50℃ and 400r / min for 5h, drying to constant weight, crushing, sieving through a 100-mesh screen, and taking the undersize to obtain the bio-based organic-inorganic hybrid binder.

[0070] wherein the preparation method of the modified vermiculite powder comprises: ultrasonic dispersing vermiculite powder sieved through a 200-mesh screen in a 50% volume concentration aqueous ethanol solution in a mass ratio of 1.5:10:0.8, adding hexadecyl trimethoxysilane, stirring at 70℃ and 500r / min for 6h, drying to constant weight, crushing, sieving through a 200-mesh screen, and taking the undersize to obtain the modified vermiculite powder.

[0071] The preparation method of the material for protecting and repairing a humid soil site comprises the following steps:

[0072] S1: pour lightweight porous ceramic pellet filler, active metakaolin, over-fired red clay, natural hydraulic lime, pozzolan modified mineral polymer, bio-based organic-inorganic hybrid binder, modified vermiculite powder, tartaric acid and pigment into a stirring container in a mass ratio, stir at a speed of 150r / min for 10min, mix uniformly to obtain a mixture A;

[0073] S2: According to mass fraction, add tributyl citrate, diethyl phthalate, liquid potassium silicate, silicone waterproof agent and silicone defoaming agent into mixture A, stir at 300 r / min for 15 min, mix uniformly, and obtain mixture B;

[0074] S3: Add water with a mass of 55% of mixture B into mixture B, mix uniformly, stand for 15 min, then mix uniformly, and obtain uniform slurry.

[0075] In the above examples, the material of the lightweight porous ceramsite filler is lightweight shale ceramsite, which is from Anhui Kong Ceramsite Products Co., Ltd. The active metakaolin is from Lingshou Jieling Mineral Products Trade Co., Ltd. The red clay is from sl-05 red clay of Lingshou Suolong Mineral Product Processing Factory. The raw material of natural hydraulic lime is from Shanghai Desai Building Materials Co., Ltd., model NHL2. The volcanic ash is from Lingshou Jiashuo Building Material Processing Co., Ltd. The pregelatinized starch is from Ningjin County Jiahe Energy-saving Material Co., Ltd., model JH-001, containing cassava starch and corn starch. The vermiculite powder is from Lingshou Baofeng Mica Processing Co., Ltd. The hexadecyl trimethoxysilane is from Guangzhou Shanghe Chemical Technology Co., Ltd., model 151. The tributyl citrate is from Shandong Shuntai Chemical Co., Ltd., model 0711. The diethyl phthalate is from Shandong Xibaihe Chemical Technology Co., Ltd., model EYZ06. The liquid potassium silicate is from Guangzhou Fur Chemical Technology Co., Ltd., model WLK-2.8-P, 40 Baume. The tartaric acid is from Suzhou Kangshi Chemical Co., Ltd., DL-tartaric acid powder. The silicone waterproof agent is from Shandong Pluss New Energy Co., Ltd., model FSJ001. The silicone defoaming agent is from Jinan Xinchun Chemical Co., Ltd., model YT-20A.

[0076] Comparative Example 1

[0077] In the material, the active metakaolin is replaced by kaolin, i.e. without calcination; other parameters and methods are the same as in Example 1.

[0078] Comparative Example 2

[0079] In the material, the fired red clay is replaced by red clay, i.e. without calcination; other parameters and methods are the same as in Example 1.

[0080] Comparative Example 3

[0081] In the material, the volcanic ash modified mineral polymer is replaced by volcanic ash, i.e. without modification; other parameters and methods are the same as in Example 1.

[0082] Comparative Example 4

[0083] In the material, the bio-based organic-inorganic hybrid binder is replaced by gelatinized corn starch; other parameters and methods are the same as in Example 1. The gelatinized corn starch is from Henan Fengwei Biotechnology Co., Ltd.

[0084] Comparative Example 5

[0085] In the material, no tributyl citrate is added, and the amount of tributyl citrate is replaced by diethyl phthalate; other parameters and methods are the same as in Example 1.

[0086] Comparative Example 6

[0087] In the material, no diethyl phthalate is added, and the amount of diethyl phthalate is replaced by tributyl citrate; other parameters and methods are the same as in Example 1.

[0088] Comparative Example 7

[0089] In the material, no tributyl citrate and diethyl phthalate are added, and the amount of tributyl citrate and diethyl phthalate is replaced by active metakaolin; other parameters and methods are the same as in Example 1.

[0090] Comparative Example 8

[0091] In the material, the modified vermiculite powder is replaced by vermiculite powder; other parameters and methods are the same as in Example 1.

[0092] Comparative Example 9

[0093] The active metakaolin is replaced by kaolin, the over-fired red clay is replaced by red clay, the bio-based organic-inorganic hybrid binder is replaced by gelatinized corn starch, and the modified vermiculite powder is replaced by vermiculite powder; other parameters and methods are the same as in Example 1.

[0094] Comparative Example 10

[0095] The active metakaolin is replaced by kaolin, the over-fired red clay is replaced by red clay, the bio-based organic-inorganic hybrid binder is replaced by gelatinized corn starch, and the modified vermiculite powder is replaced by vermiculite powder; no tributyl citrate and diethyl phthalate are added, and the amount of tributyl citrate and diethyl phthalate is replaced by active metakaolin; other parameters and methods are the same as in Example 1.

[0096] The slurries prepared in each of the above examples and comparative examples are subjected to use detection.

[0097] I. Fusion detection: Take a small sample of a mixed wall of a certain site Qing building (which combines the characteristics of brick wall and rammed earth wall, with a compressive strength of about 15 MPa) as the test matrix, evenly apply the slurry material on the surface of the sample, and control the thickness to be 5 mm. The curing process is carried out in a standard curing room, the temperature is maintained at 20±2℃, the relative humidity is maintained above 95%, and the curing time is 28 days. After the curing period, randomly select 5 different positions to measure the width of the interface transition zone, and take the average value to quantify the fusion. The smaller the width, the better the fusion. The test results are shown in Table 1 below.

[0098] II. Compressive strength and moisture soil applicability detection: Prepare 6 cylindrical test pieces with a diameter of 50 mm and a height of 50 mm. After standard curing for 28 days, test the compressive strength of 3 test pieces and take the average value as the pre-soaking compressive strength. The remaining 3 test pieces are subjected to a simulated moist soil environment. The test pieces are placed in a constant temperature and humidity chamber, the humidity is set to 95%, the temperature is set to 25℃, and the test pieces are completely immersed in water below the simulated groundwater level. The soaking time is strictly controlled for 3 months. After soaking, the test pieces are taken out and tested for compressive strength using a universal material testing machine. The average value is the post-soaking compressive strength. Calculate the compressive strength retention rate, the formula is: compressive strength retention rate = post-soaking compressive strength / pre-soaking compressive strength x 100%. The test results are shown in Table 1 below.

[0099] III. Stress uniformity detection: Prepare a material test piece with dimensions of 100mm x 100mm x 100mm, evenly paste 10 high-precision strain gauges on the surface of the material test piece, and use a material testing machine to perform uniaxial compression loading on the test piece at a loading rate of 0.05mm / min until the material test piece fails. Real-time acquisition of strain data from different position strain gauges is achieved through a data acquisition system, and the standard deviation of strain is calculated. The smaller the standard deviation, the better the stress uniformity. The test results are shown in Table 1 below.

[0100] Table 1 Test Data Results

[0101]

[0102]

[0103] From the above results, the materials of Example 1 to Example 3 have better fusion after use, which means that the mechanical properties between the two materials change more gently. When the external material is combined with the wall of the historical site, if the transition zone is too large, a clear mechanical property gradient will be formed between the two, and stress concentration will easily occur in this transition area when an external force is applied, causing cracks, peeling and other problems at the junction. A moderate transition zone means that the mechanical properties between the materials are closer, the stress can be transmitted more evenly, the overall structure is more stable, and the fusion is better. If the transition zone is too large, it means that there is excessive chemical reaction or physical penetration between the materials, which will change the original structure and properties of the wall of the historical site, such as causing the composition of the wall material to be excessively diluted, the crystal structure to be destroyed, etc. A moderate transition zone means that the materials can have a certain binding force, but will not interfere too much with the original properties of the historical site wall, thereby ensuring good fusion. The compressive strength of the materials of each example is moderate, which matches the strength of the historical site wall, has good adaptability to moist soil, high compressive strength retention rate, uniform stress, and can play a good protective role.

[0104] Comparative Example 1, the active meta-kaolin is replaced by kaolin, which is not calcined. The kaolin crystal structure is complete, and the active site is less, so the chemical reaction with the components in the historical site wall material cannot be fully carried out. In terms of fusion, it cannot form a tight chemical bond connection. In a humid environment, kaolin is easy to absorb water and swell, which destroys the internal structure of the material and reduces the compressive strength retention rate. The unevenness of the internal structure leads to a large difference in strain distribution when stressed, and the compressive strength is also reduced.

[0105] Comparative Example 2, the over-fired red clay is replaced by red clay, which is not calcined. The mineral structure of the uncalcined red clay has not changed, and the interparticle bonding force is weak, so it is not tightly combined with other components and the historical site wall. In terms of fusion, it is poor. In a humid environment, the soluble components in the red clay are easily dissolved and lost, causing structural damage and low compressive strength retention rate. Its strength is inferior to that of the over-fired red clay modified by calcination. The uncalcined red clay has large pores and good connectivity, which enhances the permeability of the material, and the overall uniformity of the material is poor, and the stress distribution is uneven when stressed.

[0106] Comparative Example 3, the volcanic ash modified mineral polymer is replaced by volcanic ash, which is not modified. The unmodified volcanic ash has low activity, and the degree of participation in chemical reactions of the material is low, which cannot effectively fill the internal pores of the material and improve the structure. In terms of fusion, the degree of combination with the historical site wall is general. In a humid environment, insufficient reaction leads to insufficient ability of the material to resist environmental erosion, and low compressive strength retention rate. Unmodified leads to insufficient density of the internal structure of the material, more gas permeation paths, uneven internal structure, uneven stress distribution, and low overall strength.

[0107] Example 4, bio-based organic-inorganic hybrid binder is replaced by gelatinized corn starch. The main component of gelatinized corn starch is polysaccharide, and the binding effect mainly relies on physical entanglement, which is far lower than that of bio-based organic-inorganic hybrid binder. In terms of fusion, it is unable to make the material tightly combined with the wall of the historical relics site. In a humid environment, gelatinized corn starch is easily decomposed by microorganisms, leading to material structure damage and reduction of compressive strength retention rate. It cannot effectively enhance the overall strength of the material, and the internal combination of the material is not tight, with more pore channels, unstable structure leading to extremely uneven stress distribution under stress.

[0108] Example 5, no tributyl citrate is added. Tributyl citrate as a plasticizer can reduce the intermolecular force in the material and increase flexibility. Without adding it, the material rigidity is enhanced, and it is difficult to form good micro-combination during the process of adhering to the wall of the historical relics site. In a humid environment, the material is prone to increase in brittleness, and the ability to resist volume change caused by humidity change is reduced, resulting in a reduction in compressive strength retention rate. The absence of tributyl citrate has a certain impact on the internal structure of the material, especially the increase in internal porosity, which reduces the strength and makes the stress distribution in the material uneven due to the change in flexibility.

[0109] Example 6, no diethyl phthalate is added. Diethyl phthalate also has a plasticizing effect, and its absence reduces the flexibility of the material. In terms of fusion, the fusion effect with the wall of the historical relics site is affected. In a humid environment, the ability to resist deformation caused by humidity is reduced, and the compressive strength retention rate is reduced. The stress distribution is uneven due to the change in flexibility of the material, affecting the overall performance of the material.

[0110] Example 7, no tributyl citrate and diethyl phthalate are added at the same time. The absence of both plasticizers greatly increases the brittleness of the material and almost eliminates its flexibility. In terms of fusion, the fusion with the wall of the historical relics site is even worse. In a humid environment, it is prone to cracks and other damage due to humidity changes, with extremely low compressive strength retention rate. The structure is loose, the stress distribution is extremely uneven, and the strength characteristics have changed significantly.

[0111] Example 8, modified vermiculite powder is replaced by vermiculite powder. Unmodified vermiculite powder has low surface activity and poor compatibility with other ingredients, and cannot be effectively dispersed in the material system. In terms of fusion, the combination with other ingredients and the wall of the historical relics site is affected. In a humid environment, it cannot effectively enhance and stabilize the structure, and the compressive strength retention rate is reduced. The effect on the strength enhancement of the material is limited, the overall uniformity of the material is affected, and the stress uniformity is not good.

[0112] Comparative Example 9, multiple key ingredients were not treated or replaced. The performance of multiple key ingredients was poor, leading to the overall structure of the material to be disordered. In terms of fusion, it was almost impossible to form an effective combination with the wall body of the site relics. In a humid environment, it was severely damaged, and the compressive strength retention rate was extremely low. The internal structure was disordered, and the stress distribution was extremely uneven.

[0113] Comparative Example 10, multiple key ingredients were not treated or replaced and no plasticizer was added. Multiple adverse factors superimposed, the internal structure of the material was disordered, the compatibility of each component was poor, the reaction was limited, and the water resistance was poor, and the material properties were severely deteriorated.

Claims

1. A material for the conservation and restoration of wet archaeological sites, characterized by, The invention comprises the following raw materials in parts by weight: 15 to 20 parts of lightweight porous ceramsite powder filler, 20 to 25 parts of activated metakaolin, 10 to 15 parts of over-fired red clay, 15 to 20 parts of natural hydraulic lime, 15 to 20 parts of volcanic ash modified mineral polymer, 10 to 15 parts of bio-based organic-inorganic hybrid binder, 3 to 5 parts of tributyl citrate, 1 to 3 parts of diethyl phthalate, 5 to 8 parts of modified vermiculite powder, 0 to 3 parts of pigment, 5 to 8 parts of liquid potassium silicate, 0.5 to 1 part of tartaric acid, 2 to 3 parts of silicone waterproofing agent, 0.1 to 0.5 parts of silicone defoaming agent, and the balance is water; The over-fired red clay is obtained by calcining red clay at 500-550°C for 0.5-1h, calcining at 600-650°C for 0.5-1h, calcining at 700-750°C for 0.5-1h, calcining at 800-850°C for 0.5-1h, and calcining at 900-950°C for 0.5-1h. The volcanic ash modified geopolymer comprises volcanic ash and an alkaline activator; The preparation method of the bio-based organic-inorganic hybrid binder includes: adding pregelatinized starch and glutaraldehyde to water for cross-linking reaction to obtain a cross-linked biomaterial solution; ultrasonically dispersing nano-titanium dioxide in ethanol to obtain a dispersion; mixing the dispersion with the cross-linked biomaterial solution, stirring for reaction, drying, and crushing to obtain the bio-based organic-inorganic hybrid binder.

2. The material for the protection and restoration of a wet earthen site according to claim 1, wherein Active metakaolin is obtained by calcining kaolin at 700°C to 750°C for 2h to 2.5h.

3. The material for the protection and restoration of a wet earthen site according to claim 1 or 2, characterized in that, The particle size of the lightweight porous ceramsite powder filler is between 80 mesh and 150 mesh; the particle size of the activated metakaolin is above 1250 mesh; the particle size of the fired red clay is between 460 mesh and 6000 mesh; the particle size of the natural hydraulic lime is above 150 mesh; the particle size of the volcanic ash modified mineral polymer is above 600 mesh; the particle size of the bio-based organic-inorganic hybrid binder is above 100 mesh; the particle size of the modified vermiculite powder is above 200 mesh; the pigment is ferro-titanium ore powder, i.e., Fe2O3-TiO2 composite pigment.

4. The material for the protection and restoration of a wet earthen site according to claim 1, wherein The preparation method of the volcanic ash modified mineral polymer comprises the steps of reacting the volcanic ash with an alkaline activator, drying, and crushing the volcanic ash to obtain the volcanic ash modified mineral polymer.

5. The material for the protection and restoration of a wet earthen site according to claim 4, wherein The mass ratio of volcanic ash to alkaline activator is 1:(4-6); the alkaline activator is a mixed aqueous solution of sodium hydroxide and sodium silicate, containing 15wt%-20wt% of sodium hydroxide and 22wt%-28wt% of sodium silicate; the reaction temperature is 50℃-60℃, the reaction time is 2h-3h, and the stirring speed of the reaction is 400r / min-600r / min; the particle size of the volcanic ash is below 600 mesh sieve.

6. The material for the protection and restoration of a wet earthen site according to claim 5, wherein In the preparation method of the bio-based organic-inorganic hybrid binder, the mass ratio of pregelatinized starch, glutaraldehyde and water is (1-1.2):(0.03-0.1):(6-8); the mass ratio of nano-titanium dioxide and ethanol is (1-1.5):(8-10); the volume ratio of the dispersion liquid and the cross-linked biological material solution is 1:(1.5-3); the cross-linking reaction temperature is 20-30 DEG C, the cross-linking reaction time is 2-3 hours, and the cross-linking reaction stirring speed is 150-250 r / min; the stirring reaction temperature is 40-50 DEG C, the stirring reaction time is 4-5 hours, and the stirring reaction speed is 200-400 r / min.

7. The material for the protection and restoration of a wet earthen site according to claim 1, wherein The preparation method of the modified vermiculite powder comprises the following steps: uniformly dispersing the vermiculite powder in an ethanol aqueous solution, adding hexadecyl trimethoxysilane, stirring and reacting, drying, and crushing to obtain the modified vermiculite powder.

8. The material for the protection and restoration of a wet earthen site according to claim 7, wherein The mass ratio of the vermiculite powder, the ethanol aqueous solution and the hexadecyl trimethoxysilane is (1-1.5):(8-10):(0.3-0.8); the volume concentration of the ethanol aqueous solution is 30-50%; the stirring reaction temperature is 60-70 DEG C, the stirring reaction time is 5-6 hours, and the stirring reaction speed is 300-500 r / min; and the particle size of the vermiculite powder is less than 200 mesh.

9. A method for preparing a material for the conservation and restoration of wet earthen sites, for preparing a material for the conservation and restoration of wet earthen sites according to claim 1, characterized in that, The preparation method comprises the following steps: S1: according to mass parts, the light porous ceramic powder filler, active metakaolin, over-fired red clay, natural hydraulic lime, volcanic ash modified mineral polymer, bio-based organic-inorganic hybrid binder, modified vermiculite powder, tartaric acid and pigment are poured into a stirring container, and are stirred and mixed uniformly to obtain a mixture A; S2: tributyl citrate, diethyl phthalate, liquid potassium silicate, organic silicon waterproof agent and organic silicon defoaming agent are added into the mixture A, and are stirred and mixed uniformly to obtain a mixture B; S3: water is added into the mixture B, and is stirred and mixed uniformly, and is left to stand and age for 10-15 minutes, and then is mixed uniformly to obtain a uniform slurry.

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