CN112194406B - HBSY-KL type temperature-inhibiting anti-cracking anticorrosion waterproof additive for concrete - Google Patents

HBSY-KL type temperature-inhibiting anti-cracking anticorrosion waterproof additive for concrete Download PDF

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CN112194406B
CN112194406B CN202010920557.2A CN202010920557A CN112194406B CN 112194406 B CN112194406 B CN 112194406B CN 202010920557 A CN202010920557 A CN 202010920557A CN 112194406 B CN112194406 B CN 112194406B
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concrete
water
hbsy
silicon dioxide
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CN112194406A (en
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姚晓敏
年夫喜
高峰
方周
邹佳佳
杨晓明
杨仕志
张晋锋
潘亚辉
陈杰君
汤升才
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Hubei Provincial Water Resources and Hydropower Planning Survey and Design Institute
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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
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
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    • C04B20/023—Chemical treatment
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    • 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
    • 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
    • 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
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/61—Corrosion inhibitors
    • 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
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/67—Biocides
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00293—Materials impermeable to liquids
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/2015—Sulfate resistance
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/26—Corrosion of reinforcement resistance
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/34—Non-shrinking or non-cracking materials
    • C04B2111/343—Crack resistant materials
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    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

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Abstract

The invention discloses an HBSY-KL type temperature-inhibiting anti-cracking anticorrosion waterproof additive for concrete, which comprises the following raw materials in percentage by mass: 0.5-5% of nano calcium silicate hydrate seed crystal with the concentration of more than or equal to 0.05mol/L, 0.5-5% of modified nano silicon dioxide, 1-5% of polyethylene glycol, 0.5-3% of citric acid or sorbitol, 0.3-0.8% of modified polystyrene, 0.5-2% of triisopropanolamine, 0.5-10% of sodium metasilicate, 1-6% of sodium hexametaphosphate or white sugar, 0.5-1% of borate coupling agent and the balance of water. The modified nano silicon dioxide and the modified polystyrene treated by adopting a special modification mode can effectively improve the compactness, impermeability, corrosion resistance and waterproofness of the concrete, inhibit hydration heat and improve the early-stage and later-stage strength of the concrete.

Description

HBSY-KL type temperature-inhibiting anti-cracking anticorrosion waterproof additive for concrete
Technical Field
The invention belongs to the field of concrete additives, and particularly relates to a temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additive for concrete.
Background
At present, in concrete engineering, along with the development of large-volume concrete and high-performance concrete technologies, higher requirements are provided for concrete preparation technologies and additive technologies, and a plurality of projects need to use a plurality of additives to meet actual requirements, but the variety of the additives is too many, so that the adaptability problem is easy to occur, and the project quality is influenced. For example, common water reducing agents, waterproofing agents and expanding agents cannot solve the problem of hydration heat of mass concrete, wherein the expanding agents are commonly adopted for anti-cracking and waterproofing structures, and the cracking and water seepage problems are reduced by means of expansion compensation and shrinkage. In practical use, too high and too low expansion rates are harmful, and the optimal mixing amount needs to be determined. In addition, because the powder is not easy to disperse, the use risk is increased. The stability of concrete volume is one of the most important factors for durability, and once cracking occurs, the mechanical property and durability are greatly reduced. The cracking of the concrete is mainly caused by temperature shrinkage and drying shrinkage, and in the early stage of concrete setting, due to the rapid hydration of mineral phases, hydration heat is too concentrated, and the cracking is generated due to too large internal and external temperature difference; meanwhile, because a large number of capillary channels and gaps exist in the concrete, the evaporation of water can also cause the concentration of shrinkage stress, and finally the later-stage concrete structure is cracked. The general shrinkage reducing agent (expanding agent) product achieves the purpose of thinning capillary channels and reducing the generation of shrinkage cracks only by enhancing the water retention performance of concrete and changing the surface tension of a liquid phase, and has the advantages of single effect, high cost and no contribution to popularization. Therefore, the method can comprehensively improve the micro-gaps of the concrete, enhance the compactness of the concrete and the water retention property of a system and reduce drying shrinkage cracks; the liquid concrete admixture product can regulate and control hydration reaction, reduce the temperature shrinkage crack of mass concrete, resist the erosion of harmful salt ions and enhance the corrosion resistance and water resistance of the concrete, and is also an urgent need of the industry.
The prior patent application CN110997259A provides an early strength-enhanced concrete admixture, which utilizes nano-scale silicon dioxide to be dispersed in an aqueous or non-aqueous solution to form a suspension, and then adopts siloxane compound reaction treatment to prepare an additive of a hydration cementing mixture, and the additive is used for reducing resilience and improving strength in a matrix of a cementing material. For another example, the prior patent application CN109336457A provides a liquid polymer shrinkage-reducing compacting agent for concrete, in which triethanolamine, triisopropanolamine, sodium sulfate, sodium tripolyphosphate, polysiloxane, polyether and tert-butanol are added into water, so that the compacting effect, compressive strength and water permeability resistance of the concrete are significantly enhanced. For example, the high-efficiency mortar or concrete rigid waterproof agent with the self-healing effect provided by the patent application CN101279828 uses polystyrene after sulfuric acid sulfonation treatment, and the waterproof agent prepared by adding the emulsifier can obviously improve the waterproof performance of concrete. The additives can not simultaneously improve the waterproof and corrosion-resistant performance and the mechanical strength of concrete, refine capillary gaps, reduce hydration heat and reduce the generation of shrinkage cracks.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an HBSY-KL-001 type temperature-inhibiting anti-cracking anticorrosion waterproof additive for concrete, which is realized by the following technology.
An HBSY-KL-001 type temperature-inhibiting anti-cracking anticorrosion waterproof additive for concrete comprises the following raw materials in percentage by mass: 0.5-5% of nano calcium silicate hydrate seed crystal solution with the concentration of more than or equal to 0.05mol/L, 0.5-5% of modified nano silicon dioxide, 1-5% of polyethylene glycol, 0.5-3% of citric acid or sorbitol, 0.3-0.8% of modified polystyrene, 0.5-2% of triisopropanolamine, 0.5-10% of sodium metasilicate, 1-6% of sodium hexametaphosphate or white sugar, 0.5-1% of borate coupling agent and the balance of water;
the modified nano silicon dioxide is prepared by firstly dispersing 70-120nm silicon dioxide in water, stirring to form uniform suspension liquid, then adding triisopropyl aluminate accounting for 6.8% of the total amount of the suspension liquid for reaction, then heating in a water bath at 80 ℃ for 4h, naturally cooling to room temperature, and finally drying in vacuum;
the preparation method of the modified polystyrene comprises the following steps: adding polystyrene into acrylic acid to prepare a solution with the concentration of 0.01mol/L, adding an emulsifier (such as polyoxyethylene octyl phenol ether-10), and stirring for 1 h; then adding ammonium persulfate and sodium bisulfite, carrying out polymerization reaction at 50 ℃ for 3h, then dropwise adding a vinyl siloxane organic silicon monomer, heating to 90 ℃, keeping the temperature for 1h, cooling to 30 ℃, and adjusting the pH value to 7 to obtain the liquid modified polystyrene.
The temperature-inhibiting anti-cracking anticorrosive waterproof additive for concrete, and the 'HBSY-KL-001' refers to the model abbreviation of the No. 001 anti-cracking agent for water conservancy-anti-cracking in Hubei province. The modified nano silicon dioxide and the modified polystyrene prepared by a special method are adopted. By utilizing the synergistic effect of the modified nano silicon dioxide and the nano calcium silicate hydrate crystal seeds, the compactness of the concrete is obviously improved, the binding power is obviously enhanced, and the corrosion resistance is greatly improved; and the early strength performance of the concrete is better. Compared with the common ethylene, the modified polystyrene prepared by the preparation method provided by the invention can obviously improve the waterproof effect of concrete compared with the traditional sulfuric acid sulfonation method. The common acrylic ester and ethylene-vinyl acetate copolymer in the market can damage the mechanical strength of the concrete to a certain extent, and the liquid temperature-inhibiting, anti-cracking, anti-corrosion and waterproof additive for the concrete has no negative influence on the strength and has a certain reinforcing effect. The nanometer calcium silicate hydrate seed crystal, triisopropanolamine and sodium metasilicate are used together, so that the concrete has good early and later strength. The common use of citric acid or sorbitol and sodium hexametaphosphate (or white sugar) has high cooperativity, can reduce the hydration heat peak value and the whole hydration heat release, and does not influence the strength and the setting time of the concrete. The polyethylene glycol has obvious shrinkage reducing effect, can obviously improve the drying shrinkage of concrete and inhibit hydration heat release, and the preferable polyethylene glycol 400 and 600 has good water solubility and strong hygroscopicity and effectively inhibits the generation of drying shrinkage cracks. The used borate coupling agent can promote the connection of the organic component and the inorganic component, and can further enhance the synergistic effect of various component materials compared with the common siloxane coupling agent.
Preferably, the material comprises the following raw materials in percentage by mass: 2% of nano calcium silicate hydrate seed crystal, 3% of modified nano silicon dioxide, 2.5% of polyethylene glycol, 1.5% of citric acid or sorbitol, 0.5% of modified polystyrene, 1.2% of triisopropanolamine, 5% of sodium metasilicate, 2% of sodium hexametaphosphate or white sugar, 0.7% of borate coupling agent and the balance of water.
Preferably, the material comprises the following raw materials in percentage by mass: 4% of nano calcium silicate hydrate seed crystal, 1% of modified nano silicon dioxide, 1.5% of polyethylene glycol, 0.5% of citric acid or sorbitol, 0.5% of modified polystyrene, 0.8% of triisopropanolamine, 3% of sodium metasilicate, 5% of sodium hexametaphosphate or white sugar, 0.8% of borate coupling agent and the balance of water.
Preferably, the material comprises the following raw materials in percentage by mass: 5% of nano calcium silicate hydrate seed crystal, 5% of modified nano silicon dioxide, 1% of polyethylene glycol, 0.5% of citric acid or sorbitol, 0.5% of modified polystyrene, 2% of triisopropanolamine, 1% of sodium metasilicate, 2% of sodium hexametaphosphate or white sugar, 0.5% of borate coupling agent and the balance of water.
More preferably, the preparation method of the nano calcium silicate hydrate seed crystal solution comprises the following steps: adding water into quicklime for curing, and then adding non-calcined diatomite, wherein the weight ratio of the quicklime to the non-calcined diatomite (higher activity compared with calcined diatomite) is 1:1 according to the content of respective effective components; adding water, stirring to obtain uniform solution (the amount of water is required to ensure that the whole solution is in uniform liquid state after boiling for 5 h); boiling the solution at normal pressure for 4h, adding aluminum sulfate with the dosage of 0.5 percent of the mass of the quicklime, and continuously boiling for 1 h; naturally cooling in air for 24h, filtering with a 0.08mm square-hole sieve to remove unreacted and coarse seed crystals and directly precipitating to obtain filtrate containing nano seed crystals, wherein the filtrate is the compound solution of nano calcium silicate hydrate seed crystals and colloidal aluminum hydroxide particles with the concentration of more than or equal to 0.05 mol/L.
More preferably, the preparation method of the boric acid coupling agent is as follows: adding boric acid into toluene, stirring to prepare a 1mol/L solution, dropwise adding 0.1mol of 2-methylcyclohexanol, heating to 115 ℃, and refluxing to prepare a liquid mixture I; then 100ml of toluene is added, 0.22mol of ethanolamine is added dropwise, the temperature is raised to 115 ℃ for reflux to prepare a liquid mixture II, and the toluene and the ethanolamine by-products are removed by distillation to obtain the borate coupling agent. The distillation conditions were atmospheric distillation at 115 ℃ to remove toluene, and negative pressure distillation at 0.05MPa (i.e., 0.5 atm) at 120 ℃ to remove ethanolamine.
The concrete additive provided by the invention is prepared by directly adding solid components (modified nano-silica, citric acid, sorbitol, sodium metasilicate, sodium hexametaphosphate and white sugar) into water for dissolving, adding nano-calcium silicate hydrate seed crystal solution, modified polystyrene, polyethylene glycol, triisopropanolamine and a borate ester coupling agent, and uniformly stirring.
Compared with the prior art, the invention has the advantages that:
1. the concrete additive provided by the invention can obviously enhance the compaction strength of concrete and has very good early and later strength; compared with the standard concrete without any temperature-inhibiting anti-cracking anticorrosion waterproof additive, when the mixing amount of the temperature-inhibiting anti-cracking anticorrosion waterproof additive is 3%, the 7d compressive strength is enhanced by more than 30%, and the 28d compressive strength is enhanced by more than 20%;
2. the waterproof effect is good, the hydrophobicity is strong, the water absorption rate of the water absorption agent for 48 hours is more than P10, and the water absorption rate is not more than 65%, so that the waterproof effect is high;
3. can effectively prevent the corrosion of chloride ion permeation on the reinforcing steel bar, and the chloride ion permeation coefficient ratio is below 75 percent; can effectively prevent the erosion damage effect of sulfate on concrete, and the sulfate erosion coefficient ratio is more than 120 percent;
4. the liquid temperature-inhibiting anti-cracking anticorrosive waterproof additive for concrete is a uniform solution, the feeding mode is simple, the dispersion effect is high, and the production is easy to control; the cost is low, and the social benefit and the economic benefit are good; the steel bar-reinforcing agent does not contain components of chloride which corrode the steel bar, and is green and environment-friendly;
5. the liquid temperature-inhibiting anti-cracking anticorrosive waterproof additive for concrete is liquid, and is added into concrete without additionally adjusting the state of the concrete or additionally curing the concrete.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The grain size of the nano calcium silicate hydrate seed crystal used in the following examples and comparative examples is 50-100 nm; the particle size of the modified nano silicon dioxide is about 70-120nm,
example 1
The HBSY-KL-001 type temperature-inhibiting anti-cracking anticorrosion waterproof additive for the concrete provided by the embodiment comprises the following raw materials in percentage by mass: 2% of nano calcium silicate hydrate seed crystal, 3% of modified nano silicon dioxide, 2.5% of polyethylene glycol, 1.5% of citric acid, 0.5% of modified polystyrene, 1.2% of triisopropanolamine, 5% of sodium metasilicate, 2% of sodium hexametaphosphate, 0.7% of borate coupling agent and the balance of water;
the preparation method of the nano calcium silicate hydrate seed crystal comprises the following steps: adding water into quicklime for curing, and then adding non-calcined diatomite, wherein the weight ratio of the quicklime to the non-calcined diatomite is 1:1 according to the content of respective effective components; adding water and stirring to prepare a uniform solution; boiling the solution at normal pressure for 4h, adding aluminum sulfate accounting for 0.5 percent of the quicklime, and continuously boiling for 1 h; naturally cooling in air for 24h, filtering with a 0.08mm square-hole sieve to obtain filtrate, and taking the filtrate, wherein the filtrate is a compound of nano calcium silicate hydrate seed crystals and colloidal aluminum hydroxide particles with the concentration of more than or equal to 0.05 mol/L;
the modified nano silicon dioxide is prepared by firstly dispersing 15-120nm silicon dioxide in water, stirring to form uniform suspension liquid, then adding triisopropyl aluminate for reaction, and finally performing vacuum drying;
the preparation method of the modified polystyrene comprises the following steps: adding polystyrene into acrylic acid to prepare a solution with the concentration of mol/L, adding an emulsifier, and stirring for 1 h; then adding ammonium persulfate and sodium bisulfite, carrying out polymerization reaction at 50 ℃ for 3h, then dropwise adding a vinyl siloxane organic silicon monomer, heating to 90 ℃, keeping the temperature for 1h, cooling to 30 ℃, and adjusting the pH value to 7 to obtain the liquid modified polystyrene.
The preparation method of the boric acid coupling agent comprises the following steps: adding boric acid into toluene, stirring to prepare a 1mol/L solution, dropwise adding 0.1mol of 2-methylcyclohexanol, heating to 115 ℃, and refluxing to prepare a liquid mixture I; then 100ml of toluene is added, 0.22mol of ethanolamine is added dropwise, the temperature is raised to 115 ℃ for reflux to prepare a liquid mixture II, and the toluene and the ethanolamine by-products are removed by distillation to obtain the borate coupling agent.
The additive for concrete of the embodiment is prepared by dissolving solid components (modified nano-silica, citric acid, sorbitol, sodium metasilicate, sodium hexametaphosphate and white sugar) in water, adding nano-calcium silicate hydrate seed crystal solution, modified polystyrene, polyethylene glycol, triisopropanolamine and borate coupling agent, and uniformly stirring to obtain a finished product.
Example 2
The HBSY-KL-001 type temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additive for the concrete provided by the embodiment is basically the same as that in the embodiment 1, and is different from that the HBSY-KL-001 type temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additive for the concrete provided by the embodiment in that the HBSY-KL-001 type temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additive for the concrete comprises the following raw materials: 4% of nano calcium silicate hydrate seed crystal solution, 1% of modified nano silicon dioxide, 1.5% of polyethylene glycol, 0.5% of sorbitol, 0.5% of modified polystyrene, 0.8% of triisopropanolamine, 3% of sodium metasilicate, 5% of sodium hexametaphosphate, 0.8% of borate coupling agent and the balance of water.
Example 3
The HBSY-KL-001 type temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additive for the concrete provided by the embodiment is basically the same as that in the embodiment 1, and is different from that the HBSY-KL-001 type temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additive for the concrete provided by the embodiment in that the HBSY-KL-001 type temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additive for the concrete comprises the following raw materials: 5% of nano calcium silicate hydrate seed crystal, 5% of modified nano silicon dioxide, 1% of polyethylene glycol, 0.5% of citric acid, 0.5% of modified polystyrene, 2% of triisopropanolamine, 1% of sodium metasilicate, 2% of white sugar, 0.5% of borate ester coupling agent and the balance of water.
Example 4
The HBSY-KL-001 type temperature-inhibiting anti-cracking anticorrosion waterproof additive for concrete provided by the comparative example uses the same raw materials and preparation method as those of the example 1, and the difference is that the existing preparation method of the hydrated calcium silicate seed crystal is adopted by the hydrated calcium silicate seed crystal (Chinese patent application)CN101182000) The method specifically comprises the following steps: firstly, uniformly mixing a calcareous material and a siliceous material according to the weight ratio of 1.2:1, then grinding to the fineness of 3-10% of sieve residue with the particle size of 45 mu m, adding water which is 3-4 times of the total weight of the mixture to prepare a slurry material, uniformly mixing, and carrying out thermal reaction for 4 hours under the condition of 1-3 atm to obtain the hydrated calcium silicate seed crystal.
Comparative example 1
The raw materials and the preparation method of the temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additive for concrete provided by the comparative example are basically the same as those of the example 1, and the difference is that the following raw materials in percentage by mass are adopted: 5% of nano calcium silicate hydrate seed crystal solution, 2.5% of polyethylene glycol, 1.5% of citric acid, 0.5% of modified polystyrene, 1.2% of triisopropanolamine, 5% of sodium metasilicate, 2% of sodium hexametaphosphate, 0.7% of borate coupling agent and the balance of water.
Comparative example 2
The raw materials and the preparation method of the temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additive for concrete provided by the comparative example are basically the same as those of the example 1, and the difference is that the following raw materials in percentage by mass are adopted: 2% of nano calcium silicate hydrate seed crystal solution, 3% of nano silicon dioxide (the particle size is the same as that of modified nano silicon dioxide), 2.5% of polyethylene glycol, 1.5% of citric acid, 0.5% of modified polystyrene, 1.2% of triisopropanolamine, 5% of sodium metasilicate, 2% of sodium hexametaphosphate, 0.7% of borate coupling agent and the balance of water
Comparative example 3
The raw materials and the preparation method of the temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additive for concrete provided by the comparative example are basically the same as those of the example 1, and the difference is that the adopted preparation method of the modified polystyrene is as follows: adding 2-dichloroethane into polystyrene, heating to 50-60 ℃ to swell the polystyrene, then dropwise adding concentrated sulfuric acid, heating to 80 ℃ and continuously stirring for reaction for 5 hours, then continuously heating to evaporate the 2-dichloroethane, continuously reacting for 5 hours, cooling, then adding distilled water, heating and stirring to slightly boil, then stirring and cooling, filtering, washing and drying to obtain the sulfonated polystyrene.
Comparative example 4
The raw materials and the preparation method of the temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additive for concrete provided by the comparative example are basically the same as those of the example 1, and the difference is that the following raw materials in percentage by mass are adopted: 8.2% of nano calcium silicate hydrate seed crystal solution, 3% of modified nano silicon dioxide, 2.5% of polyethylene glycol, 1.5% of citric acid, 0.5% of modified polystyrene, 2% of sodium hexametaphosphate, 0.7% of borate ester coupling agent and the balance of water.
Comparative example 5
The raw materials and the preparation method of the temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additive for concrete provided by the comparative example are basically the same as those of the example 1, and the difference is that the following raw materials in percentage by mass are adopted: 2% of nano calcium silicate hydrate seed crystal solution, 3% of modified nano silicon dioxide, 2.5% of polyethylene glycol, 1.5% of citric acid, 0.5% of modified polystyrene, 6.2% of triisopropanolamine, 2% of sodium hexametaphosphate, 0.7% of borate coupling agent and the balance of water.
Comparative example 6
The raw materials and the preparation method of the temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additive for concrete provided by the comparative example are basically the same as those of the example 1, and the difference is that the following raw materials in percentage by mass are adopted: 2% of nano calcium silicate hydrate seed crystal, 3% of modified nano silicon dioxide, 2.5% of polyethylene glycol, 3.5% of citric acid, 0.5% of modified polystyrene, 1.2% of triisopropanolamine, 5% of sodium metasilicate, 0.7% of borate coupling agent and the balance of water.
Comparative example 7
The raw materials and the preparation method of the temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additive for concrete provided by the comparative example are basically the same as those of the example 1, and the difference is that the following raw materials in percentage by mass are adopted: 2% of nano calcium silicate hydrate seed crystal solution, 3% of modified nano silicon dioxide, 2.5% of polyethylene glycol, 0.5% of modified polystyrene, 6.2% of triisopropanolamine, 3.5% of sodium hexametaphosphate, 0.7% of borate coupling agent and the balance of water.
Comparative example 8
The raw materials and the preparation method of the temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additive for concrete provided by the comparative example are basically the same as those of the example 1, and the difference is that the adopted coupling agent is a siloxane coupling agent.
Application example 1: the performance of the reference concrete prepared using the additives of examples 1 to 3 and comparative examples 1 to 8 was examined
The temperature-inhibiting, crack-resisting, corrosion-preventing and waterproof additives prepared in the above examples and comparative examples were blended into concrete for testing and comparing workability, mechanical properties and crack resistance. The concrete compressive strength is according to GB/T50081-2002 standard of mechanical property test method of common concrete, the chloride ion permeability coefficient ratio is according to GB/T50082-2009 test method of long-term property and durability of common concrete, and the size of a test piece is the standard size specified in the standard; the shrinkage ratio is tested according to JCT474-2008 'mortar concrete waterproofing agent industry Standard', and the early crack resistance measurement test is carried out in T/CECS 10001-2017 'crack-resistant and impervious composite material for concrete'. The impermeability grade test is carried out according to GB50108-2008 'underground engineering waterproof technical Specification'. The formula of the reference concrete as a control group is shown in the following table 1, wherein a blank example without any temperature-inhibiting, crack-resisting, corrosion-preventing and water-proofing additives is arranged, and the detection results of the additive amount and each performance of the examples and the comparative examples are shown in the following table 2.
TABLE 1 Standard concrete ratio (unit Kg/m)3)
Figure GDA0003314078930000071
Figure GDA0003314078930000081
TABLE 2 results of performance testing of reference concrete doped with different additives
Figure GDA0003314078930000082
The detection data in the table 1 show that the performance differences of the concrete in the examples 1-4 are not large, which indicates that the raw material formulas of the 4 examples can achieve better anti-cracking, waterproof and anti-corrosion effects and have high compressive strength in the early and later periods; compared with the concrete performance of the example 1, the concrete performance of the comparative example 1 has the advantages that the compressive strength ratio of the concrete in the early and later periods is obviously reduced, the chloride ion permeability coefficient is obviously improved, and the crack reduction coefficient is obviously reduced, which shows that when the nano silicon dioxide is lacked, the compactness and the corrosion resistance of the concrete are obviously reduced, and the compressive strength of the concrete in the early and later periods is also influenced; compared with the concrete of example 1, the concrete performance of comparative example 2 has influence on the compressive strength, chloride ion permeability coefficient and crack reduction coefficient (namely generated hydration heat) in the early and later stages, which shows that the effect of using common nano-silica is not as good as that of using nano-silica modified by the method of the invention;
compared with the example 1, the impermeability grade of the comparative example 3 is obviously reduced, and the permeability coefficient of chloride ions is obviously increased, which shows that the modification method of polystyrene can influence the waterproofness and impermeability of concrete;
compared with the example 1, the comparative examples 4 and 5 have the advantages that the early-stage compressive strength and the shrinkage ratio are not changed greatly, the later-stage compressive strength is reduced obviously, and the impermeability grade is also reduced, which shows that triisopropanolamine and sodium metasilicate have obvious influence on the later-stage compressive strength of concrete and can also influence the impermeability grade to a certain depth. According to analysis, probably because the sodium metasilicate and the triisopropanolamine can promote the generation of compact calcium silicate gel in the concrete, the flocculent stable corrosion-resistant gel is filled in gaps of the concrete, and the compressive strength and the impermeability grade of the concrete can be improved.
Comparative examples 6 and 7 compared with example 1, the crack reduction rate of the concrete is increased, and the impermeability grade is reduced, which shows that the crack generation cannot be effectively prevented in the absence of citric acid or sodium hexametaphosphate, so that the impermeability performance is affected.
Comparative example 8 the performance of all tests on concrete was reduced compared to example 1, indicating that the performance of the inventive feed when treated with a siloxane coupling agent was not as significantly improved as when the inventive feed was treated with a borate coupling agent.

Claims (6)

1. The HBSY-KL type temperature-inhibiting anti-cracking anticorrosion waterproof additive for concrete is characterized by comprising the following raw materials in percentage by mass: 0.5-5% of nano calcium silicate hydrate seed crystal solution with the concentration of more than or equal to 0.05mol/L, 0.5-5% of modified nano silicon dioxide, 1-5% of polyethylene glycol, 0.5-3% of citric acid or sorbitol, 0.3-0.8% of modified polystyrene, 0.5-2% of triisopropanolamine, 0.5-10% of sodium metasilicate, 1-6% of sodium hexametaphosphate or white sugar, 0.5-1% of borate coupling agent and the balance of water;
the modified nano silicon dioxide is prepared by firstly dispersing 70-120nm silicon dioxide in water, stirring to form 2% of uniform suspension, then adding triisopropyl aluminate accounting for 6.8% of the total amount of the suspension for reaction, then heating in a water bath at 80 ℃ for 4h, naturally cooling to room temperature, and finally drying in vacuum;
the preparation method of the modified polystyrene comprises the following steps: adding polystyrene into acrylic acid to prepare a solution with the concentration of 0.01mol/L, adding an emulsifier, and stirring for 1 h; then adding ammonium persulfate and sodium bisulfite, carrying out polymerization reaction at 50 ℃ for 3h, then dropwise adding a vinyl siloxane organic silicon monomer, heating to 90 ℃, keeping the temperature for 1h, cooling to 30 ℃, and adjusting the pH value to 7 to obtain the liquid modified polystyrene.
2. The HBSY-KL type temperature-suppressing, crack-resisting, corrosion-preventing and waterproof additive for concrete according to claim 1 is characterized by comprising the following raw materials in percentage by mass: 2% of nano calcium silicate hydrate seed crystal, 3% of modified nano silicon dioxide, 2.5% of polyethylene glycol, 1.5% of citric acid or sorbitol, 0.5% of modified polystyrene, 1.2% of triisopropanolamine, 5% of sodium metasilicate, 2% of sodium hexametaphosphate or white sugar, 0.7% of borate coupling agent and the balance of water.
3. The HBSY-KL type temperature-suppressing, crack-resisting, corrosion-preventing and waterproof additive for concrete according to claim 1 is characterized by comprising the following raw materials in percentage by mass: 4% of nano calcium silicate hydrate seed crystal, 1% of modified nano silicon dioxide, 1.5% of polyethylene glycol, 0.5% of citric acid or sorbitol, 0.5% of modified polystyrene, 0.8% of triisopropanolamine, 3% of sodium metasilicate, 5% of sodium hexametaphosphate or white sugar, 0.8% of borate coupling agent and the balance of water.
4. The HBSY-KL type temperature-suppressing, crack-resisting, corrosion-preventing and waterproof additive for concrete according to claim 1 is characterized by comprising the following raw materials in percentage by mass: 5% of nano calcium silicate hydrate seed crystal, 5% of modified nano silicon dioxide, 1% of polyethylene glycol, 0.5% of citric acid or sorbitol, 0.5% of modified polystyrene, 2% of triisopropanolamine, 1% of sodium metasilicate, 2% of sodium hexametaphosphate or white sugar, 0.5% of borate coupling agent and the balance of water.
5. The HBSY-KL type temperature-suppressing, crack-resisting, corrosion-preventing and waterproof additive for concrete according to any one of claims 1 to 4, wherein the preparation method of the nano calcium silicate hydrate seed crystal solution comprises the following steps: adding water into quicklime for curing, and then adding non-calcined diatomite, wherein the weight ratio of the quicklime to the non-calcined diatomite is 1:1 according to the content of respective effective components; adding water and stirring to prepare a uniform solution; boiling the solution at normal pressure for 4h, adding aluminum sulfate with the dosage of 0.5 percent of the mass of the quicklime, and continuously boiling for 1 h; naturally cooling in air for 24h, and filtering with 0.08mm square mesh sieve to obtain filtrate, i.e. solution of nano calcium silicate hydrate seed crystal with concentration of more than or equal to 0.05 mol/L.
6. The HBSY-KL type temperature-suppressing, crack-resisting, corrosion-preventing and waterproof additive for concrete according to any one of claims 1 to 4, wherein the preparation method of the boric acid coupling agent comprises the following steps: adding boric acid into toluene, stirring to prepare a 1mol/L solution, dropwise adding 0.1mol of 2-methylcyclohexanol, heating to 115 ℃, and refluxing to prepare a liquid mixture I; then 100ml of toluene is added, 0.22mol of ethanolamine is added dropwise, the temperature is raised to 115 ℃ for reflux to prepare a liquid mixture II, and the toluene and the ethanolamine by-products are removed by distillation to obtain the borate coupling agent.
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