CN110156367B - Method for preparing nano C-S-H gel early strength agent by wet grinding of industrial solid wastes - Google Patents

Method for preparing nano C-S-H gel early strength agent by wet grinding of industrial solid wastes Download PDF

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CN110156367B
CN110156367B CN201910308445.9A CN201910308445A CN110156367B CN 110156367 B CN110156367 B CN 110156367B CN 201910308445 A CN201910308445 A CN 201910308445A CN 110156367 B CN110156367 B CN 110156367B
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gel
wet grinding
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parts
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CN110156367A (en
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郑正旗
胡华超
李佳伟
张雅颂
熊威
刘森野
杨建祥
杨进
王迎斌
贺行洋
苏英
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Hubei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/10—Accelerators; Activators
    • C04B2103/12—Set accelerators

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a method for preparing a nano C-S-H gel early strength agent by wet grinding of industrial solid wastes, which solves the problems of complexity, high cost, environmental pollution and the like of the existing preparation method. The technical scheme comprises the steps of grinding industrial solid waste containing amorphous silicon dioxide to powder with the average particle size of less than 1 mm; mixing 100 parts by weight of powder, 400 parts by weight of water and 600 parts by weight of water with 0.5-2 parts by weight of ionic dissolution promoter, uniformly stirring, and putting the mixture into a wet grinding machine to be subjected to wet grinding at the rotating speed of 40-50rps until the median particle size is 2-4 mu m; then adding 10-100 parts by weight of quicklime into a wet grinder, and carrying out wet grinding until the median particle size of the slurry is less than 100 nm; adding a dispersion stabilizer and uniformly mixing to obtain slurry-like nano C-S-H gel; concentrating the slurry-like nanometer C-S-H gel by a reduced pressure distillation method until the solid content is 20-60 wt%. The method is simple, the cost is low, and the prepared early strength agent is pollution-free and has good dispersion stability.

Description

Method for preparing nano C-S-H gel early strength agent by wet grinding of industrial solid wastes
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a method for preparing a nano C-S-H gel early strength agent.
Background
The future trend of the building industry is assembly type construction, and the core of the assembly type construction is the production of ultra-early-strength concrete prefabricated parts. The prior art for producing the ultra-early-strength concrete member is mainly a steam curing process, namely, the concrete formed by steam curing at the temperature of 60-80 ℃ is used, so that the stripping strength can be achieved after 8 hours of steam curing. However, the steam curing process is likely to cause coarse crystal growth of the hydration product in the concrete and delayed-type ettringite destruction, which is extremely disadvantageous to the durability of the concrete member. The common steam-curing-free alternative process comprises the following steps: (1) inorganic early strength agents (sulfate, nitrate, nitrite and the like) are used, (2) inorganic early strength agents (triethanolamine, formate, acetate and the like) are used, and (3) nano effect induction hydration (such as nano aluminum oxide, nano calcium carbonate, nano silicon dioxide, nano C-S-H gel and the like) is performed. Ions with smaller atomic radius such as K +, Na + and the like can be introduced while the inorganic early strength agent is used, and the ions are easy to cause a 'blooming' phenomenon, namely the ions migrate to the surface of concrete to influence the beauty and durability of the concrete prefabricated part; the use of inorganic early strength agents generally has a certain negative effect on the development of later strength; the nano effect induced hydration is considered as a nearly harmless steaming-free production process, but two factors restrict the application of the nano effect induced hydration in concrete at present, namely high price (caused by production cost) and non-uniform dispersion in concrete (caused by agglomeration effect of nano size).
The C-S-H gel is short for calcium silicate hydrate gel and is an important one of cement hydration products. The nano C-S-H gel can induce the cement (especially the cement containing mineral admixture) to be rapidly hydrated to form higher early strength. The invention CN108911551A discloses a preparation method of a nanometer C-S-H gel material and an application of the nanometer C-S-H gel material in a cement-based material. The invention mainly adopts sodium silicate solution, calcium nitrate solution and sodium hydroxide solution; mixing the three solutions, transferring the mixed solution into a reaction kettle, and reacting at 50-80 ℃ for 5-11520 min (preferably, reacting the mixed slurry at 60 ℃ for 1440 min); after the reaction is finished, centrifugally washing to be neutral to prepare the nano C-S-H gel slurry. The raw materials for preparing the nano C-S-H gel mainly comprise sodium silicate, calcium nitrate and sodium hydroxide, the price of the three raw materials is high, and the cost of the prepared nano C-S-H gel is naturally high, so that the nano C-S-H gel is not suitable for popularization and application in the concrete industry. In addition, the process generates a large amount of waste liquid containing inorganic salts, which does not meet the requirement of green production.
The invention CN107287980A discloses application of synthetic calcium silicate as a papermaking filler and a papermaking method of high-filler paper. The synthetic calcium silicate is prepared by taking a low-modulus sodium silicate solution obtained by alkali dissolution of high-purity quartz sand and lime milk obtained by digestion of active quicklime as raw materials, performing a liquid-phase dynamic hydrothermal synthesis reaction, washing, dealkalizing, drying and pulverizing. Obviously, the method has the problems of high cost and poor dispersibility of the prepared nano calcium silicate. The preparation method is not suitable for the production of the nano C-S-H gel early strength agent in the field of concrete.
The invention CN108467215A discloses a nano C-S-H crystal seed early strength agent for building concrete and a preparation method thereof. The preparation process comprises the following steps: (1) adding an acrylic monomer, a silane coupling agent and modified polyoxyethylene ether into ammonium persulfate, vitamin C and dodecyl mercaptan to prepare a polymer solution; (2) preparing sodium metasilicate into a solution A with the mass concentration of 45-50%, and preparing calcium nitrate into a solution B with the mass concentration of 30-40%; (3) and adding the solution A and the solution B into a polymer solution, and reacting to obtain the uniform and stable nano C-S-H crystal seed early strength agent for building concrete. Obviously, the method has high cost, and the preparation of a large amount of organic reagents is involved, so the process difficulty is slightly higher. In addition, the process obviously generates a large amount of waste liquid containing inorganic salts and organic matters, thereby polluting the environment.
Disclosure of Invention
The invention aims to solve the technical problems and provides a preparation method of a nano C-S-H gel early strength agent, which is simple in method, low in cost, free of pollution and good in dispersion stability.
The technical scheme comprises the following steps:
(1) grinding industrial solid waste containing amorphous silicon dioxide to an average particle size of less than 1 mm;
(2) uniformly mixing and stirring 100 parts by weight of powder, 400 parts by weight of water and 600 parts by weight of ionic cosolvent in the step (1), and putting the mixture into a wet grinder to be subjected to wet grinding at a rotating speed of 40-50rps until the median particle size is 2-4 mu m;
(3) then adding 10-100 parts by weight of quicklime into a wet grinder, and carrying out wet grinding until the median particle size of the slurry is less than 100 nm;
(4) adding 0.1-2 parts by weight of dispersion stabilizer, and uniformly mixing to obtain slurry-like nanometer C-S-H gel;
(5) concentrating the slurry-like nanometer C-S-H gel by a reduced pressure distillation method until the solid content is 20-60 wt%.
The industrial solid waste containing the amorphous silicon dioxide in the step (1) is one of phosphorus slag, fly ash, manganese slag or nickel slag;
the ionic cosolvent in the step (2) is one of sodium benzoate, sodium salicylate and triethanolamine.
And (3) keeping the materials isolated from the external atmospheric environment during the operation of the wet grinding machine in the steps (2) and (3).
And (3) the wet grinding machine in the step (2) and the step (3) is a wet medium stirring mill.
And (4) adding quicklime in the step (3), controlling the rotation speed of the wet grinder to be 80-100rps, and wet grinding until the median particle size of the slurry is less than 100 nm.
The dispersion stabilizer in the step (4) is one of a polycarboxylic acid water reducer, naphthalene sulfonate, a fatty acid dispersant and a polyacrylamide dispersant;
the temperature range in the reduced pressure distillation method in the step (4) is 30-50 ℃.
Aiming at the problems in the background art, the inventor considers that the procurement cost of industrial solid wastes is low, the industrial solid wastes can be used as raw materials to prepare the early strength agent, and the industrial solid wastes have the problems of large particle size, high strength and difficulty in grinding, so that the materials can only be subjected to superfine treatment of 2-4 mu m even if wet grinding is used, but the particle size is difficult to continuously reduce, and particularly, the grinding of the materials to the nanometer level is almost impossible, so that the method becomes a technical problem for preparing the nanometer C-S-H gel early strength agent by using the industrial solid wastes.
In contrast, the inventors have conducted intensive studies on raw materials, and since industrial solid wastes containing amorphous silica are generally obtained by quenching at a high-temperature molten state, various oxides in the solid wastes are uniformly distributed, and the solid wastes can be completely used for preparing an early strength agent without separating wastes to pollute the environment. The method comprises the following steps of (1) taking industrial solid waste containing amorphous silicon dioxide as a raw material, and under the action of an ionic cosolvent, physically grinding by means of wet grinding to realize ultrafine treatment; at the moment, the further nanocrystallization of the material is realized, the chemical action is synchronously introduced on the basis of wet grinding, and the quicklime is added, so that on one hand, OH formed by the quicklime in water is utilized-Depolymerizing amorphous silica, OH, in solid waste-The depolymerized amorphous silicon dioxide is also a defect of material particles in nature, and the solid waste particles can be further refined to reach a nanometer level under the mechanical force stripping effect of wet grinding and the turbulent high-pressure effect of liquid phase; in addition, calcium ions in the liquid phase can capture short chain silicate ions to form C-S-H gel, and the C-S-H gel cannot grow under the mechanical force stripping action of the medium ball and the turbulent high pressure action of the liquid phase and can only maintain the nanometer size, so that most materials are stabilized under the nanometer size. When wet grinding is finished, a stabilizing dispersant is added to maintain the stability of the nano C-S-H gel early strength agent and prevent agglomeration.
Further, in the steps (2) and (3), the wet grinding machine should keep the material isolated from the external atmosphere environment during the operation process, and prevent CO in the atmosphere2Dissolving in the slurry to cause carbonization; in the step (3), the rotating speed of the wet grinding machine is controlled to be 80-100rps, the high-rotating-speed wet grinding can improve the stress frequency and the stress intensity in the wet grinding process, and more importantly, research shows that: when the wet grinder keeps the rotating speed of 80-100rps, a turbulent high-pressure area can be formed in a liquid phase, so that the material is easier to refine under the condition of turbulent high pressure, and the nano-crystallization of the material is ensured while the energy is saved and the consumption is reduced. The ionic cosolvent used in the step (2)The surface defect is formed by promoting the dissolution of the surface ions of the particles so as to be beneficial to the refinement of the particles, the adding amount is 0.5-2 parts by weight, the effect cannot be continuously enhanced even if the adding amount is too much, the cost is increased, and the corresponding effect cannot be achieved if the adding amount is too little. In the step (3), the addition amount of the quicklime is 10 to 100 parts by weight, more preferably 30 to 50 parts by weight, compared with 100 parts of the powder, and if the addition amount of the quicklime is too large, a large amount of water is consumed to increase the viscosity of the slurry, so that the grinding is not facilitated, and if the addition amount of the quicklime is too small, OH is caused to be unfavorable-And Ca2+Can not continuously diffuse into liquid phase and can not be amorphous SiO2The depolymerization reaction and the formation reaction of C-S-H of (A) provide sufficient reactants; in the reduced pressure distillation method in the step (4), the temperature range is 30-50 ℃, the nano C-S-H gel is easily thermally decomposed when the temperature is too high, and the concentration rate is too slow when the temperature is too low.
Has the advantages that:
(1) the industrial solid waste containing amorphous silicon dioxide and quick lime which is widely available are used as main raw materials, so that the production cost is greatly reduced; (2) the main component of the prepared slurry-like nano material is nano C-S-H gel and simultaneously contains other nano substances, but the slurry-like nano material can be doped into cement concrete without separation, no new waste is generated in the preparation process, and the preparation method is truly green production; (3) the mechanical force stripping of the medium ball, the physical effects of the turbulent flow and high pressure of the liquid phase and OH are carried out by utilizing the wet grinding technology-Depolymerizing amorphous silica, Ca2+The short chain silicate is captured to form C-S-H gel and other chemical effects are combined, namely physical effect and chemical effect are cooperated to refine particles; (4) the liquid phase and the dispersion stabilizer are utilized to prevent the nano-slurry from agglomerating, and the stability and high dispersibility in the application process are ensured. (5) The preparation method is simple, easy to operate and low in production cost, and the prepared nano C-S-H gel early strength agent has high compressive strength, no pollution and good dispersion stability.
Drawings
FIG. 1 is a distribution diagram of the median diameter particle of the nano C-S-H gel early strength agent of examples 1-5.
FIG. 2 is a graph showing the distribution of the median diameter particles of the C-S-H gel early strength agent of comparative examples 1 to 3.
FIG. 3 is a graph of median particle size of the nano C-S-H gel early strength agents of examples 1-5 for different days of standing.
Detailed Description
The present invention will be described in detail with reference to specific examples, wherein industrial solid wastes are obtained from various metallurgical plants or thermal power plants, and quicklime and additives are commercially available. The mixing proportion of the common C60 concrete (blank group) which is not doped with the nano C-S-H gel early strength agent prepared by the invention is as follows: 380kg/m cement380kg/m of fly ash390kg/m of mineral powder3Machine-made sand 430kg/m3300kg/m of river sand3Crushed stone 1000kg/m3175kg/m of water318.7kg/m of water reducing agent (solid content is 15 percent)3(ii) a The 8-hour compressive strength is 4.3MPa, the 1-day compressive strength is 13.8MPa, the 3-day compressive strength is 45.8MPa, and the 28-day compressive strength is 62.3 MPa.
Example 1
(1) Grinding phosphorus slag containing amorphous silicon dioxide to powder (average particle size is less than 1 mm);
(2) uniformly mixing and stirring 100 parts of powdery industrial solid waste, 400 parts of water and 0.5 part of sodium benzoate in the step (1), and putting the mixture into a wet grinding machine to be subjected to wet grinding at the rotating speed of 40rps until the median particle size is 2 mu m;
(3) slowly adding 10 parts of quicklime into a wet grinder, and wet grinding at a high rotating speed of 80rps until the median particle size of the slurry is less than 100 nm;
the wet grinding machine in the step (2) and the step (3) is a wet medium stirring mill, and materials are isolated from the external atmospheric environment in the operation process of the mill, so that CO in the atmosphere is prevented2Dissolving in the slurry to cause carbonization;
(4) adding 0.1 part of polycarboxylic acid water reducing agent to obtain slurry-like nanometer C-S-H gel;
(5) concentrating the slurry-like nanometer C-S-H gel by adopting a reduced pressure distillation method until the solid content is 20 percent to obtain the nanometer C-S-H gel early strength agent 1.
The nanometer C-S-H gel early strength agent 1 is mixed into C60 concrete by 1 percent of the mass fraction of the cementing material, the 8H compressive strength is 16.3MPa (which is 3.8 times of the blank group), the 1 day compressive strength is 35.7MPa, the 3 day compressive strength is 47.9MPa, and the 28 day compressive strength is 63.8MPa, and the nanometer C-S-H gel early strength agent accords with the technical index (the 8H strength requirement reaches 15MPa) in GB-T51231-2016 (assembled concrete construction technical Standard).
Example 2
(1) Grinding slag containing amorphous silica to a powder form (average particle diameter of 1mm or less);
(2) uniformly mixing and stirring 100 parts of powdered industrial solid waste, 600 parts of water and 2 parts of sodium salicylate in the step (1), and putting the mixture into a wet grinding machine to be wet-ground at the rotating speed of 50rps until the median particle size is 4 mu m;
(3) slowly adding 100 parts of quicklime into a wet grinder, and wet grinding at a high rotating speed of 100rps until the median particle size of the slurry is less than 100 nm;
the wet grinding machine in the step (2) and the step (3) is a wet medium stirring mill, and materials are isolated from the external atmospheric environment in the operation process of the mill, so that CO in the atmosphere is prevented2Dissolving in the slurry to cause carbonization;
(4) adding 2 parts of naphthalene sulfonate to obtain slurry-like nano C-S-H gel;
(5) concentrating the slurry-like nanometer C-S-H gel by adopting a reduced pressure distillation method until the solid content is 60 percent to obtain the nanometer C-S-H gel early strength agent 2.
The nanometer C-S-H gel early strength agent 2 is mixed into C60 concrete according to the mass fraction of 2% of the cementing material, the 8H compressive strength is 17.3MPa (4.0 times of the blank group), the 1 day compressive strength is 33.7MPa, and the 28 day compressive strength is 62.3MPa, and the nanometer C-S-H gel early strength agent accords with the technical indexes (the 8H compressive strength requirement reaches 15MPa) in GB-T51231-2016 (assembled concrete building technical Standard).
Example 3
(1) Grinding fly ash containing amorphous silica into powder (average particle size is less than 1 mm);
(2) uniformly mixing and stirring 100 parts of powdered industrial solid waste, 500 parts of water and 1 part of triethanolamine in the step (1), and putting the mixture into a wet grinding machine to be wet-ground at the rotating speed of 45rps until the median particle size is 3 mu m;
(3) slowly adding 50 parts of quicklime into a wet grinder, and wet grinding at a high rotating speed of 80rps until the median particle size of the slurry is less than 100 nm;
the wet grinding machine in the step (2) and the step (3) is a wet medium stirring mill, and materials are isolated from the external atmospheric environment in the operation process of the mill, so that CO in the atmosphere is prevented2Dissolving in the slurry to cause carbonization;
(4) adding 1 part of fatty acid dispersant to obtain slurry-like nano C-S-H gel;
(5) concentrating the slurry-like nanometer C-S-H gel by adopting a reduced pressure distillation method until the solid content is 40 percent to obtain the nanometer C-S-H gel early strength agent 3.
The nanometer C-S-H gel early strength agent 3 is mixed into C60 concrete by 3 percent of the mass fraction of the cementing material, the 8H compressive strength is 18.6MPa (4.3 times of the blank group), the 1 day compressive strength is 32.7MPa, the 3 day compressive strength is 49.2MPa, and the 28 day compressive strength is 64.3MPa, and the nanometer C-S-H gel early strength agent accords with the technical index (the 8H compressive strength requirement reaches 15MPa) in GB-T51231-2016 (assembled concrete construction technical Standard).
Example 4
(1) Grinding manganese slag containing amorphous silicon dioxide to powder (average particle size is less than 1 mm);
(2) uniformly mixing and stirring 100 parts of powdered industrial solid waste, 450 parts of water and 0.8 part of triethanolamine in the step (1), and putting the mixture into a wet grinding machine to be wet-ground at the rotating speed of 48rps until the median particle size is 2 mu m;
(3) slowly adding 70 parts of quicklime into a wet grinder, and wet grinding at a high rotation speed of 90rps until the median particle size of the slurry is less than 100 nm;
the wet grinding machine in the step (2) and the step (3) is a wet medium stirring mill, and materials are isolated from the external atmospheric environment in the operation process of the mill, so that CO in the atmosphere is prevented2Dissolving in the slurry to cause carbonization;
(4) adding 1.5 parts of polyacrylamide dispersant to obtain slurry-like nano C-S-H gel;
(5) concentrating the slurry-like nanometer C-S-H gel by adopting a reduced pressure distillation method until the solid content is 45 percent to obtain the nanometer C-S-H gel early strength agent 4.
The nanometer C-S-H gel early strength agent 4 is mixed into C60 concrete by the mass fraction of 5% of the cementing material, the 8H compressive strength is 17.6MPa (4.1 times of the blank group), the 1 day compressive strength is 32.4MPa, the 3 day compressive strength is 51.2MPa, and the 28 day compressive strength is 66.5MPa, and meets the technical index (the 8H compressive strength requirement reaches 15MPa) in GB-T51231- & 2016 & ltAssembly concrete construction technical Standard & gt).
Example 5
(1) Grinding nickel slag containing amorphous silicon dioxide to powder (average particle size is less than 1 mm);
(2) uniformly mixing and stirring 100 parts of powdery industrial solid waste, 430 parts of water and 1.4 parts of sodium benzoate in the step (1), and putting the mixture into a wet grinding machine to be subjected to wet grinding at the rotating speed of 43rps until the median particle size is 2.5 mu m;
(3) slowly adding 80 parts of quicklime into a wet grinder, and wet grinding at a high rotating speed of 95rps until the median particle size of the slurry is less than 100 nm;
the wet grinding machine in the step (2) and the step (3) is a wet medium stirring mill, and materials are isolated from the external atmospheric environment in the operation process of the mill, so that CO in the atmosphere is prevented2Dissolving in the slurry to cause carbonization;
(4) adding 1.6 parts of polyacrylamide dispersant to obtain slurry-like nano C-S-H gel;
(5) concentrating the pasty nanometer C-S-H gel by adopting a reduced pressure distillation method until the solid content is 30 percent to obtain the nanometer C-S-H gel early strength agent 5.
The nano C-S-H gel early strength agent 3 is mixed into C60 concrete by 2 percent of the mass fraction of the cementing material, the 8H compressive strength is 16.6MPa (which is 3.9 times of the blank group), the 1-day compressive strength is 33.2MPa, the 3-day compressive strength is 52.3MPa, and the 28-day compressive strength is 61.5 MPa. Meets the technical indexes (the 8h compressive strength requirement reaches 15MPa) in GB-T51231-2016 (assembled concrete building technical Standard).
Comparative example 1:
the same procedure as in example 5 was repeated except that calcium lime was changed to carbide slag (an industrial solid waste containing calcium hydroxide), to obtain comparative nano C-S-H gel early strength agent 1.
The comparative C-S-H gel early strength agent 1 is mixed into C60 concrete by 2 percent of the mass fraction of the cementing material, the 8H compressive strength is 10.6MPa (2.5 times of the blank group), the 1 day compressive strength is 25.2MPa, the 3 day compressive strength is 35.3MPa, and the 28 day compressive strength is 62.5 MPa. Can not reach the technical index in GB-T51231-2016 technical Standard for fabricated concrete buildings (the 8h compressive strength is required to reach 15 MPa).
Comparative example 2:
the same procedure as in example 5 was repeated except that the wet milling in step (3) was changed to stirring, to obtain comparative nano C-S-H gel early strength agent 1.
The comparative C-S-H gel early strength agent 2 is mixed into C60 concrete by 2 percent of the mass fraction of the cementing material, the 8H compressive strength is 5.2MPa (which is 1.2 times of the blank group), the 1 day compressive strength is 20.2MPa, the 3 day compressive strength is 31.3MPa, and the 28 day compressive strength is 62.8 MPa. Can not reach the technical index in GB-T51231-2016 technical Standard for fabricated concrete buildings (the 8h compressive strength is required to reach 15 MPa).
Comparative example 3
The same procedure as in example 5 was repeated except that the wet milling rotation speed in step (3) was changed to 43rps, to obtain comparative nano C-S-H gel early strength agent 1.
The comparative C-S-H gel early strength agent 3 is added into C60 concrete by 2 mass percent of cementing material, the 8H compressive strength is 7.6MPa (which is 1.8 times of the blank group), the 1-day compressive strength is 27.2MPa, the 3-day compressive strength is 38.3MPa, and the 28-day compressive strength is 63.5 MPa. Can not reach the technical index in GB-T51231-2016 technical Standard for fabricated concrete buildings (the 8h compressive strength is required to reach 15 MPa).
FIGS. 1 and 2 are particle size distribution diagrams of examples and comparative examples, and it can be seen from the above 5 examples and 3 comparative examples that the nano C-S-H gel with the particle size of 100nm or less cannot be prepared in the comparative examples, and although the nano C-S-H gel has early strength effect, the nano C-S-H gel is not obvious and cannot meet the requirements of GB-T51231-2016 technical Standard for fabricated concrete buildings. After the nano C-S-H gel early strength agent prepared by the invention is doped into concrete, the early strength can be greatly improved, particularly the 8H compressive strength is improved to about 4 times of that of a blank group, and the nano C-S-H gel early strength agent can be completely applied to the production of non-autoclaved concrete members.
FIG. 3 shows the median particle size of the nano C-S-H gel early strength agent prepared by the above 5 examples on different days of standing. As can be seen from the figure, the particle size of the nano C-S-H gel early strength agent prepared by each example is increased in a small range along with the increase of the number of days of standing, but the increase is less than 10nm, the nano C-S-H gel early strength agent is still in a stable dispersion state, and the stable dispersion time can last for 180 days.

Claims (7)

1. A method for preparing a nano C-S-H gel early strength agent by wet grinding of industrial solid wastes is characterized by comprising the following steps:
(1) grinding industrial solid waste containing amorphous silicon dioxide to an average particle size of less than 1 mm;
(2) uniformly mixing and stirring 100 parts by weight of powder, 400 parts by weight of water and 600 parts by weight of ionic cosolvent in the step (1), and putting the mixture into a wet grinder to be subjected to wet grinding at a rotating speed of 40-50rps until the median particle size is 2-4 mu m;
(3) adding 10-100 parts by weight of quicklime into a wet grinder, controlling the rotating speed of the wet grinder to be 80-100rps, and carrying out wet grinding until the median particle size of the slurry is less than 100 nm;
(4) adding 0.1-2 parts by weight of dispersion stabilizer, and uniformly mixing to obtain slurry-like nanometer C-S-H gel;
(5) concentrating the slurry-like nanometer C-S-H gel by a reduced pressure distillation method until the solid content is 20-60 wt%.
2. The method for preparing the nano C-S-H gel early strength agent by wet grinding of industrial solid wastes according to claim 1, wherein the industrial solid wastes containing amorphous silica in the step (1) are one of phosphorous slag, fly ash, manganese slag or nickel slag.
3. The method for preparing the nano C-S-H gel early strength agent by wet grinding of industrial solid wastes according to claim 1, wherein the ionic cosolvent in the step (2) is one of sodium benzoate, sodium salicylate and triethanolamine.
4. The method for preparing the nano C-S-H gel early strength agent by wet grinding of industrial solid wastes according to claim 1, wherein the wet grinding machine keeps the materials isolated from the external atmospheric environment during the operation in the steps (2) and (3).
5. The method for preparing the nano C-S-H gel early strength agent by wet grinding of industrial solid wastes according to claim 1 or 4, wherein the wet grinding machine in the step (2) and the step (3) is a wet medium stirring grinding machine.
6. The method for preparing the nano C-S-H gel early strength agent by wet grinding of industrial solid wastes according to claim 1, wherein the dispersion stabilizer in the step (4) is one of a polycarboxylic acid water reducing agent, a naphthalene sulfonate, a fatty acid dispersant and a polyacrylamide dispersant.
7. The method for preparing the nano C-S-H gel early strength agent by wet grinding of industrial solid wastes according to claim 1 or 6, which is characterized in that: the temperature range in the reduced pressure distillation method in the step (5) is 30-50 ℃.
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