CN113024148A - Concrete composite antifreezing agent and preparation method thereof - Google Patents
Concrete composite antifreezing agent and preparation method thereof Download PDFInfo
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- CN113024148A CN113024148A CN202011448501.8A CN202011448501A CN113024148A CN 113024148 A CN113024148 A CN 113024148A CN 202011448501 A CN202011448501 A CN 202011448501A CN 113024148 A CN113024148 A CN 113024148A
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- antifreeze
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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
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/601—Agents for increasing frost resistance
Abstract
The invention discloses a concrete composite antifreezing agent and a preparation method thereof, and the concrete composite antifreezing agent comprises the following raw materials in parts by mass: 15-30 parts of water reducing component, 10-50 parts of antifreezing component, 1-3 parts of early strength component, 0.1-0.3 part of air entraining component and 30-50 parts of water. The composite antifreezing agent obtained by the invention has no pungent smell; the mixing amount in the cementing material is less; the chlorine-free low-alkali concrete corrosion-resistant agent has no corrosion effect on reinforced concrete; the antifreeze solution is stored for 7 days at the temperature of-20 ℃ without overflowing of flocculent substances; the compression strength ratio of the concrete composite antifreeze agent at the temperature of minus 20 ℃ is obviously higher than the set requirement of minus 15 ℃ specified in JC 457-2004.
Description
Technical Field
The invention belongs to the technical field of concrete admixtures, and particularly relates to a concrete composite antifreezing agent and a preparation method thereof.
Background
The demand for the production market of reinforced concrete is increasing, the construction quality and safety of concrete become a hot problem which is very concerned by people, the concrete is in a low-temperature state in winter in approximately 3-4 months every year in alpine regions, and the concrete antifreezing agent becomes an essential important component for protecting concrete in winter low-temperature construction. At present, the concrete antifreezer in China is preparedThe categories can be mainly divided into: sodium nitrite type antifreeze: the antifreezing agent mainly has the advantages that the freezing point is greatly reduced, and the antifreezing agent has the characteristics of rust prevention and early strength, and the sodium nitrite additive is still one of the conventional antifreezing agents and has good effect. Other additives such as JP type antifreeze, etc., have disadvantages mainly in that the range of use of the additives is limited by the amount and degree of the additives, and the cost thereof is relatively high. Carbonate type: the carbonate as the antifreezing agent is a better one of inorganic salts of concrete at present, the carbonate antifreezing agent can be generally constructed at low temperature in winter at the low temperature of-25 ℃, the corrosion to reinforcing steel bars can not be directly caused, but the composite antifreezing agent is easy to react with SiO in cement aggregate concrete2The reaction has the functions of corrosion and reinforcing steel bar damage, and is not suitable for reinforced concrete in areas with abnormally changed water level. Ammonia water type composite antifreeze: the composite antifreezing agent mainly takes an ammonia-containing aqueous solution in the aggregate as a main raw material, and can avoid the corrosion of the reinforcing steel bar under the condition of lower temperature. The composite antifreezing agent does not play a role in accelerating and plasticizing, and the strength of concrete is slowly increased by adding the composite antifreezing agent. The ammonia water solution in the aggregate has strong chemical irritation and smell, so the composite antifreezing agent is gradually and widely eliminated by domestic markets. Chloride compound antifreezing agent: the composite antifreezing agent mainly takes sodium chloride, calcium chloride hydrochloride and other components as main antifreezing agent components, but the composite antifreezing agent has extremely strong chemical corrosivity on reinforcing steel bars and is widely replaced by other composite antifreezing agents. The concrete antifreezing agent has the greatest effect of preventing the concrete from freezing under the low-temperature condition and avoiding the strength reduction of the concrete caused by the low temperature. The concrete antifreezing agent can accelerate the hardening and the condensation of the concrete during the construction in the low-temperature environment in winter, and the early strength of the concrete can be obviously increased without influencing the later strength.
The development of the antifreeze in China mainly goes through several stages of chloride salt type, chloride salt rust-resisting type, chloride-free high-alkali type and chloride-free low-alkali type from the aspect of composition, wherein the antifreeze containing chloride salt is not allowed to be used for reinforced concrete and prestressed concrete structures, and is mostly used as a mortar antifreeze at present. The antifreeze undergoes the development process from high doping (10-15%) to low doping (3-5%). The morphology has also evolved from powder to liquid products. In the future years, the Beijing area can be popularized and applied with chlorine-free, low-alkali, low-doping amount, high-efficiency and liquid antifreeze, the research and development of liquid antifreeze with organic components and liquid antifreeze with compound organic and inorganic components are encouraged, and the development of air-entraining antifreeze is actively promoted. In order to improve the quality of concrete construction in winter and strengthen the control on the performance and quality of concrete antifreezes, the currently used industrial standard JC457-2004 "concrete antifreezes" stipulates the R7 compressive strength ratio, so that the antifreezes meet the two requirements of hardening the concrete at negative temperature and reaching the expected strength or enough antifreezing strength within the stipulated time, and thus, higher requirements are provided for the concrete antifreezes.
The types of the antifreeze reported in China at present are as follows: sodium nitrite type antifreeze: the antifreezing agent is prepared by utilizing the characteristics of small molecular weight and high solubility of sodium nitrite, capability of greatly reducing the freezing point and rust prevention and early strength when the sodium nitrite is doped into mortar or concrete, and the additive is still one of the currently widely used additives and has a good effect. Such as JP type antifreeze, etc., has disadvantages that its use range is limited to some extent and the cost is high. Carbonate type: the antifreezing agent is a better one in inorganic salt, can be constructed in winter at the temperature of-25 ℃, can not cause the corrosion of reinforcing steel bars, but is easy to react with SiO in aggregate2The reaction plays a destructive role and is not suitable for use in concrete in water level fluctuation areas. Ammonia water type antifreeze: the antifreezing agent takes an aqueous solution of ammonia as a raw material, has good antifreezing performance, plays roles of retarding and plasticizing cement, playing a role of inhibiting rust for reinforcing steel bars, and can ensure that concrete is not frozen under the condition of lower negative temperature. The antifreezing agent does not play a role in accelerating the setting, and the concrete strength of the concrete doped with the antifreezing agent is slowly increased. The ammonia water has strong pungent smell, so the antifreeze is gradually eliminated by the market. Urea type antifreeze: the antifreezing agent is a composite antifreezing agent which takes urea as a main component and is compounded with sodium sulfate and other components to have antifreezing and coagulation promoting effects. ChlorineSalt antifreezing agent: the antifreezing agent mainly takes sodium chloride and calcium chloride as main components, but the antifreezing agent has strong corrosivity on reinforcing steel bars and is replaced by other composite antifreezing agents. The ideal antifreezing agent should have the characteristics of no alkali/low alkali, no chlorine, good plasticity retention, liquid and the like, so the research and development focuses on the non-chlorine salt, low alkali or no alkali, environment-friendly and composite concrete antifreezing agent.
Disclosure of Invention
The problems to be solved by the invention are as follows: (1) the major problems of the concrete building in the aspects of service life, engineering quality, safety and the like in the freezing and thawing cycle process in the alpine region; (2) the mixing amount of the antifreezing agent is higher; (3) the frost resistance grade can not reach or is slightly higher than the standard requirement; (4) the antifreeze has higher alkali content or chlorine content and has corrosion effect on the steel bar; (5) antifreeze agents such as ammonia and urea contain pungent odors.
In order to solve any one or more technical problems, the invention provides a concrete composite antifreezing agent which comprises the following raw materials in parts by mass:
generally speaking, the water reducing component is a water reducing agent, the early strength component is an early strength agent, the air entraining component is an air entraining agent, and the antifreezing component is an antifreezing agent. The four components are mixed with water to prepare the liquid concrete admixture with outstanding antifreezing performance, so the concrete admixture is called as a concrete composite antifreezing agent.
Preferably, the water reducing component is a polycarboxylic acid water reducing agent; preferably, the water reducing component comprises a high-efficiency water reducing type polycarboxylate water reducer and a slow-release slump-retaining polycarboxylate water reducer.
Preferably, the mass ratio of the high-efficiency water-reducing polycarboxylate water reducer to the slow-release slump-retaining polycarboxylate water reducer is 2-4: 1.
Preferably, the high-efficiency water-reducing polycarboxylate superplasticizer is one or a mixture of JWPCE-503A, JWPCE-503 and JWPCE-903S; the slow-release slump-retaining type polycarboxylate water reducer is one or a mixture of JWPCE-904P, JWPCE-904S, JWPCE-504A.
Preferably, the antifreezing component comprises an alcohol antifreezing component and a salt antifreezing component, wherein the ratio of the alcohol antifreezing component to the salt antifreezing component is 0.5-4: 1.
Preferably, the alcohol antifreezing component is one or more of methanol, ethanol, ethylene glycol, propylene glycol and glycerol; and/or the salt antifreezing component is one or more of sodium nitrate, sodium nitrite, sodium sulfate, sodium thiosulfate and sodium acetate.
Preferably, the antifreeze component consists of glycerol and sodium nitrite; preferably, the mass ratio of the glycerol to the sodium nitrite is 1-3: 1; more preferably, the mass ratio of glycerol to sodium nitrite is 2: 1.
Preferably, the early strength component is triethanolamine; the air entraining component is sodium alkyl benzene sulfonate.
Preferably, the concrete composite antifreezing agent comprises the following raw material components in parts by mass:
the invention also provides a preparation method of the concrete composite antifreezing agent, which comprises the steps of placing the metered components into a container, and stirring and dispersing; thus obtaining the concrete composite antifreezing agent.
Specifically, the following steps may be included:
(1) placing the metered water and the water-reducing component into a container and stirring;
(2) adding a metered amount of an antifreeze component into the container and stirring;
(3) adding metered early strength components and air entraining components into the container, and stirring; thus obtaining the concrete composite antifreezing agent.
Compared with the traditional antifreezing agentThe difference lies in that a water reducing agent, an antifreezing agent, an early strength agent and an air entraining agent are combined, in particular, a high-efficiency water reducing and slow-setting slump-retaining polycarboxylic acid water reducing agent is combined, and is mixed with antifreezing components (glycerol and sodium nitrite) according to a certain proportion, the materials are fully stirred to be completely compatible, and then the materials are prepared, the prepared antifreezing agent is taken out and placed in a transparent plastic bottle, the plastic bottle is placed in a freezing box at the temperature of-20 ℃, the plastic bottle is taken out after being frozen for 72 hours, the solution is good in compatibility, and no crystallization is generated. The glycerol as the antifreezing component can be mutually dissolved with water in any proportion, and can reduce the mixing amount of the sodium salt antifreezing component in the antifreezing agent and reduce the crystallization amount in a low-temperature environment after being mixed with the sodium nitrite. The polycarboxylate water reducing agent is a high-efficiency water reducing agent, hydrophobic groups of the polycarboxylate water reducing agent are directionally adsorbed on the surfaces of cement particles, hydrophilic groups point to water solution, so that the cement particles have the same charges, the cement is separated under the action of repulsion force, free water in a flocculation structure is released, the fluidity of the cement is increased, the workability is improved, the surface tension of the cement is reduced, and the strength of the concrete is improved. The early strength agent in concrete construction is mainly one of concrete admixtures, and refers to an admixture which can effectively improve certain early cement strength of concrete and has no obvious influence on the stability of later concrete strength; triethanolamine is the most common organic matter early strength component with the characteristics of less mixing amount, small side effect, obvious early strength effect and certain strengthening effect in the later period. The N atom in triethanolamine has a pair of common electrons, which can easily form covalent bonds with metal ions to generate complex reaction, and forms stable complexes with the metal ions, and the complexes form a plurality of soluble areas in solution, thereby improving the diffusion rate generated by hydration. This inevitably destroys C formed on the surface of clinker particles at the beginning of hydration due to complex formation3A hydrate and other products, to C3A、C4The dissolution rate of AF is increased, the reaction with gypsum is accelerated, calcium sulphoaluminate is rapidly generated, the conversion speed between ettringite and calcium sulphoaluminate monosulfate is accelerated, the generation amount of calcium sulphoaluminate is increased, and Ca in a liquid phase is inevitably reduced+、Al3+To further promoteC3And (3) hydrating the A. The air entraining component is added to make concrete form non-communicated fine pores, so that the air entraining component plays a role of a buffering agent, absorbs the expansion stress of ice crystals and plays a role of decompression, and the pores can prevent or inhibit the formation of fine ice bodies in cement paste during the process that the concrete is frozen. The key factor affecting the frost resistance of concrete is the degree to which the air entraining agent introduces air bubbles into the uniform distribution in the cement slurry, i.e., the size and number of the spacing of the air bubbles, rather than the total air entraining amount.
The composite antifreezing agent has no crystallization and precipitation, good liquid fluidity, is completely suitable for winter, can be used for construction at the temperature of-20 ℃, has low mixing amount, good durability, good fluidity, no toxicity, low alkali, no chlorine and good adaptability with cement, can play a role in preventing concrete from being damaged by freezing, and can obviously improve the performance of the concrete after being newly mixed and hardened.
Compared with the prior art, the invention has the advantages that:
(1) the antifreeze sample has no pungent odor; (2) the mixing amount of the antifreezing agent in the cementing material is less by 0.5 to 1.0 percent; (3) the chlorine-free low-alkali concrete corrosion-resistant agent has no corrosion effect on reinforced concrete; (4) the antifreeze solution is stored for 7 days at the temperature of-20 ℃ without overflowing of flocculent substances; (5) the compression strength ratio of the concrete composite antifreeze agent at the temperature of minus 20 ℃ is obviously higher than the set requirement of minus 15 ℃ specified in JC 457-2004.
Detailed Description
The present invention will be further described with reference to the following examples.
Note: if not specifically stated, the high-efficiency water-reducing polycarboxylic acid water reducing agent in the examples and the comparative examples of the invention is JWPCE-503A (characterized by high water reducing rate and low blending amount), the slow-release slump-retaining polycarboxylic acid water reducing agent is JWPCE-504A (characterized by high water reducing rate and low blending amount), the air entraining agent is sodium alkyl benzene sulfonate, the early strength agent is triethanolamine, and each raw material component is mixed according to the proportion of 10 g.
Example 1
The embodiment provides a concrete composite antifreezing agent, which comprises the following raw materials in parts by mass:
the preparation method comprises the following steps:
(1) putting 45g of deionized water, 15g of high-efficiency water-reducing polycarboxylic acid water reducing agent and 5g of slow-release slump-retaining polycarboxylic acid water reducing agent into a reaction kettle, adjusting the rotating speed to 200rpm, and stirring for 10min at the temperature of 27 ℃;
(2) placing 20g of glycerol (anti-freezing component) in the reaction kettle, and stirring for 10min while keeping the temperature and the rotating speed unchanged;
(3) 10g of sodium nitrite (an antifreezing component) is placed in the reaction kettle, and the temperature and the rotating speed are kept unchanged and the stirring is carried out for 10 min;
(4) 2 portions of the early strength agent and 0.15 portion of the air entraining agent are measured and placed in the reaction kettle, and the temperature and the rotating speed are kept unchanged and stirred for 20 min; thus obtaining the concrete composite antifreezing agent.
Example 2
This example provides a concrete composite antifreeze, which has substantially the same composition and preparation method as those of example 1, except that: no glycerol is added; the antifreeze component is selected from a single antifreeze component of sodium nitrite.
Example 3
This example provides a concrete composite antifreeze, which has substantially the same composition and preparation method as those of example 1, except that: equal parts by mass of methanol are used instead of glycerol.
Example 4
This example provides a concrete composite antifreeze, which has substantially the same composition and preparation method as those of example 1, except that: equal parts by mass of ethanol are used to replace glycerol.
Example 5
This example provides a concrete composite antifreeze, which has substantially the same composition and preparation method as those of example 1, except that: equal parts by mass of ethylene glycol are used instead of glycerol.
Example 6
This example provides a concrete composite antifreeze, which has substantially the same composition and preparation method as those of example 1, except that: equal parts by mass of sodium nitrate were used instead of sodium nitrite.
Example 7
This example provides a concrete composite antifreeze, which has substantially the same composition and preparation method as those of example 1, except that: sodium nitrite was replaced by equal parts by mass of sodium acetate.
Example 8
This example provides a concrete composite antifreeze, which has substantially the same composition and preparation method as those of example 1, except that: the amount of glycerin is adjusted to 10 parts.
Example 9
This example provides a concrete composite antifreeze, which has substantially the same composition and preparation method as those of example 1, except that: the amount of glycerol was adjusted to 30 parts.
The samples obtained in the above examples were tested, and the test results were: (compressive strengths R-7 and R-7+28 were measured in accordance with GB/T50081, and the water-reducing rate, gas content and material mixing ratio were measured and calculated in accordance with GB 8076; and homogeneity was measured in accordance with GB/T8077).
In conclusion, the compound antifreezing component is prepared by compounding glycerol and sodium nitrite, so that the obtained concrete compound antifreezing agent has the most stable performance and the best antifreezing effect.
Claims (10)
1. The concrete composite antifreezing agent is characterized by comprising the following raw materials in parts by mass:
2. the composite antifreeze of claim 1, wherein said water reducing component is a polycarboxylic acid water reducer; preferably, the water reducing component comprises a high-efficiency water reducing type polycarboxylate superplasticizer and a slow-release slump-retaining polycarboxylate superplasticizer.
3. The composite antifreeze agent as set forth in claim 1 to 2, wherein the mass ratio of the high-efficiency water-reducing polycarboxylic acid water reducer to the slow-release slump-retaining polycarboxylic acid water reducer is 2-4: 1.
4. The composite antifreeze agent as set forth in claims 1 to 3, wherein the high-efficiency water-reducing polycarboxylic acid water reducing agent is one or a combination of JWPCE-503A, JWPCE-503 and JWPCE-903S; the slow-release slump-retaining type polycarboxylate water reducer is one or a combination of JWPCE-904P, JWPCE-904S, JWPCE-504A.
5. The composite antifreeze agent as set forth in claims 1 to 4, wherein said antifreeze component comprises an alcohol antifreeze component and a salt antifreeze component, wherein the mass ratio of the alcohol antifreeze component to the salt antifreeze component is 0.5 to 4: 1.
6. The composite antifreeze agent according to any of claims 1 to 5, wherein the alcoholic antifreeze component is one or more of methanol, ethanol, ethylene glycol, propylene glycol and glycerol; and/or the salt antifreezing component is one or more of sodium nitrate, sodium nitrite, sodium sulfate, sodium thiosulfate and sodium acetate.
7. The composite antifreeze agent according to any of claims 1 to 6, wherein said antifreeze component consists of glycerin and sodium nitrite; preferably, the mass ratio of glycerol to sodium nitrite is 1-3: 1.
8. The composite antifreeze of any of claims 1 to 7, wherein said early strength component is triethanolamine; the air entraining component is sodium alkyl benzene sulfonate.
9. The composite antifreeze agent according to any one of claims 1 to 8, wherein the concrete composite antifreeze agent comprises the following raw materials in parts by mass:
10. a method for preparing the composite antifreeze of any one of claims 1 to 9, wherein the components are placed in a container in metered amounts and dispersed with stirring; thus obtaining the concrete composite antifreezing agent.
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| CN202011448501.8A CN113024148A (en) | 2020-12-09 | 2020-12-09 | Concrete composite antifreezing agent and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113666660A (en) * | 2021-08-31 | 2021-11-19 | 江西省圣源商品混凝土有限公司 | Concrete antifreezing agent and application thereof |
| CN113788639A (en) * | 2021-08-24 | 2021-12-14 | 陕西科之杰新材料有限公司 | Concrete antifreezing agent and preparation method thereof |
| CN114380525A (en) * | 2021-11-17 | 2022-04-22 | 贵州天威建材科技有限责任公司 | Slump-retaining type concrete antifreezing water reducing agent and preparation method thereof |
| CN114477832A (en) * | 2022-01-25 | 2022-05-13 | 湖南先锋建材有限公司 | High-strength energy-saving polycarboxylate superplasticizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113788639A (en) * | 2021-08-24 | 2021-12-14 | 陕西科之杰新材料有限公司 | Concrete antifreezing agent and preparation method thereof |
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| CN114477832A (en) * | 2022-01-25 | 2022-05-13 | 湖南先锋建材有限公司 | High-strength energy-saving polycarboxylate superplasticizer |
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Application publication date: 20210625 |