CN111793165B - Seawater-eroded fair-faced concrete additive and preparation method thereof - Google Patents
Seawater-eroded fair-faced concrete additive and preparation method thereof Download PDFInfo
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- CN111793165B CN111793165B CN202010567031.0A CN202010567031A CN111793165B CN 111793165 B CN111793165 B CN 111793165B CN 202010567031 A CN202010567031 A CN 202010567031A CN 111793165 B CN111793165 B CN 111793165B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- 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
- C04B2111/24—Sea water resistance
-
- 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
- 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
Abstract
The invention discloses a seawater erosion resistant clear water concrete admixture, which comprises the following components in percentage by weight: 3-6 parts of unsaturated carboxylic acid, 3-6 parts of unsaturated carboxylic acid derivative, 0.3-0.7 part of unsaturated sulfonate, 1-4 parts of silane coupling agent, 0.2-0.6 part of initiator, 0.15-0.5 part of vitamin C and 85-95 parts of water. The invention directly prepares the seawater corrosion resistant concrete admixture by adopting a free radical polymerization method, improves the stability of the concrete admixture, provides the strength between hardened concrete aggregate slurry, reduces microcracks and further improves the durability of concrete. The additive does not contain nitrite, complex acid salt and the like, is chlorine-free, does not have heat source reaction at normal temperature, has mild reaction conditions, simple process, environmental protection and high efficiency, can greatly improve the durability of concrete serving in marine environment, and is suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a seawater erosion bare concrete additive and a preparation method thereof.
Background
In recent years, with the continuous development of economy in China, a large amount of heavy and large basic engineering is under construction or planning in marine areas in China, however, the areas where the basic engineering is located are difficult to transport, the coarse and fine aggregate of concrete is poor in grading, and the prepared high-fluidity fair-faced concrete is easy to have the problems of poor slurry stability and the like: when the concrete is hardened, moisture in the cement paste can migrate to the hydrophilic aggregate, a water film layer is formed on the surface of the aggregate, and fine gaps are left in the hardened concrete; on the other hand, the ocean weather is severe, the deformation caused by the change of the environmental humidity and the temperature is different, and the micro-cracks are easily generated due to the stress existing on the interface of the aggregate and the cement paste. Based on the problems, the interface of the obtained concrete is full of original microcracks before the concrete bears the load; under the action of load, shearing stress and tensile stress are further generated on the interface of the slurry and the aggregate, so that the original microcracks are expanded. Along with the increase of stress, cracks continuously grow and extend to cement stones, and finally fracture of slurry is caused, so that an engineering structure fails prematurely, the service life of the engineering structure does not reach the designed service life, and further huge economic loss is caused.
In order to improve the durability of the fair-faced concrete material in ocean engineering, the fair-faced concrete structure is prepared by firstly ensuring that the concrete has good slurry stability and the compactness of hardened concrete so as to resist the erosion and penetration of external harmful substances, and meanwhile, the structural strength of an aggregate and a slurry interface in the concrete should be paid more attention.
Disclosure of Invention
The invention mainly aims to provide the seawater erosion bare concrete admixture aiming at the defects in the prior art, which can effectively improve the stability of concrete mixture, improve the pore structure and enhance the structural strength of the concrete aggregate and slurry interface.
In order to realize the purpose, the invention adopts the technical scheme that:
an admixture for seawater erosion bare concrete comprises the following components in parts by weight: 3-6 parts of unsaturated carboxylic acid, 3-6 parts of unsaturated carboxylic acid derivative, 0.3-0.7 part of unsaturated sulfonic acid, 1-4 parts of silane coupling agent, 0.2-0.6 part of initiator, 0.15-0.5 part of vitamin C and 85-95 parts of water.
In the above scheme, the unsaturated carboxylic acid is one or two of acrylic acid and methacrylic acid.
In the above scheme, the unsaturated carboxylic acid derivative is acrylamide.
In the above scheme, the unsaturated sulfonate is sodium methallyl sulfonate.
In the scheme, the silane coupling agent is one or more of aminopropyltrimethoxysilane, diethylenetriaminomethyloxysilane, vinyltrimethyloxysilane, vinyl (2-methylethoxy) silane and gamma-aminopropyltrimethoxysilane.
In the scheme, the initiator is one or more of hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate.
The preparation method of the seawater erosion resistant fair-faced concrete additive comprises the following steps:
1) weighing the raw materials according to the proportion, wherein the raw materials and the weight parts of the raw materials comprise: 3-6 parts of unsaturated carboxylic acid, 3-6 parts of unsaturated carboxylic acid derivative, 0.3-0.7 part of unsaturated sulfonic acid, 1-4 parts of silane coupling agent, 0.2-0.6 part of initiator, 0.15-0.5 part of vitamin C and 85-95 parts of water;
2) adding the weighed unsaturated carboxylic acid derivative, the silane coupling agent and water into a reaction kettle; then controlling the temperature to be 10-40 ℃ under the condition of stirring; adding an initiator, dropwise adding an aqueous solution of unsaturated carboxylic acid, unsaturated sulfonate and vitamin C under the stirring condition, and controlling the dropping within 2.5-3.5 hours; and after the water is dripped, stirring at normal temperature for reaction for 1-1.5 hours to obtain the seawater corrosion resistant fair-faced concrete admixture.
The principle of the invention is as follows:
in the high molecular polymer prepared by the invention, the amide group is combined with water to form a hydrogen bond, so that the viscosity of the solution is improved, the migration rate of water to the aggregate is reduced, a silicon-oxygen bond in a molecular structure can form a firm chemical bond with calcium ions in cement particles, so that the bridging effect between the cement particles is enhanced, the movement resistance of the aggregate and water molecules is increased, the periphery of the aggregate can be uniformly wrapped by the cement particles, meanwhile, the surface tension of the solution is reduced by hydrophobic groups such as alkoxy groups in the molecular structure, the water molecules required by wetting the cement particles and the aggregate are reduced, the water molecules between the aggregate and the cement particles are reduced, the strength between the hardened concrete aggregate and slurry is increased, and microcracks are reduced.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention directly prepares the clear water concrete admixture product for resisting seawater erosion by a free radical polymerization method, has no chlorine, does not contain nitrite, complex acid salt and the like, and can greatly improve the durability of the concrete serving in the marine environment on the basis of effectively ensuring or further improving the strength of the concrete;
2) the reaction conditions involved in the invention are mild, normal-temperature non-heat-source reaction is adopted, the process is simple, environment-friendly and efficient, and the method is suitable for popularization and application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The preparation method of the seawater corrosion resistant fair-faced concrete additive comprises the following steps:
adding 5 parts by weight of acrylamide, 2 parts by weight of aminopropyltrimethoxysilane and 70 parts by weight of deionized water into a reaction kettle; then, under the conditions of stirring and the temperature of 35 ℃, 0.3 part by weight of ammonium persulfate is added into a reaction kettle at one time, and then an aqueous solution (containing 15 parts by weight of deionized water) containing 5 parts by weight of acrylic acid, 0.6 part by weight of sodium methallyl sulfonate and 0.3 part by weight of vitamin C is dripped, and the dripping is finished within 3 hours; after the dripping is finished, stirring and reacting for 1 hour at normal temperature to obtain the seawater corrosion resistant fair-faced concrete admixture (K1).
Example 2
The preparation method of the seawater corrosion resistant fair-faced concrete additive comprises the following steps:
adding 4 parts by weight of acrylamide, 3 parts by weight of diethylenetriaminomethyloxysilane and 75 parts by weight of deionized water into a reaction kettle; then, under the conditions of stirring and temperature of 30 ℃, 0.4 part by weight of sodium persulfate is added into the reaction kettle at one time, and then an aqueous solution (containing 10 parts by weight of deionized water) containing 5.5 parts by weight of acrylic acid, 0.7 part by weight of sodium methallyl sulfonate and 0.25 part by weight of vitamin C is dropwise added, and the dropping is finished within 3.5 hours; after the dripping is finished, stirring and reacting for 1 hour at normal temperature to obtain the seawater corrosion resistant fair-faced concrete admixture (K2).
Example 3
The preparation method of the seawater erosion resistant fair-faced concrete additive comprises the following steps:
adding 6 parts by weight of acrylamide, 3 parts by weight of vinyltrimethylsiloxy and 72 parts by weight of deionized water into a reaction kettle; then, under the conditions of stirring and temperature of 40 ℃, 0.4 part by weight of potassium persulfate is added into the reaction kettle at one time, and then aqueous solution (containing 14 parts by weight of deionized water) containing 4 parts by weight of acrylic acid, 0.6 part by weight of sodium methallyl sulfonate and 0.3 part by weight of vitamin C is dripped, and the dripping is finished within 3 hours; after the dripping is finished, stirring and reacting for 1.5 hours at normal temperature to obtain the seawater corrosion resistant fair-faced concrete admixture (K3).
Example 4
The preparation method of the seawater corrosion resistant fair-faced concrete additive comprises the following steps:
adding 3.5 parts by weight of acrylamide, 2 parts by weight of gamma-aminopropyltrimethoxysilane and 77 parts by weight of deionized water into a reaction kettle; then, under the conditions of stirring and the temperature of 35 ℃, 0.35 part by weight of ammonium persulfate is added into the reaction kettle at one time, and then aqueous solution (containing 13 parts by weight of deionized water) containing 6 parts by weight of acrylic acid, 0.65 part by weight of sodium methallyl sulfonate and 0.35 part by weight of vitamin C is dripped, and the dripping is finished within 3.5 hours; after the dripping is finished, stirring and reacting for 1.5 hours at normal temperature to obtain the seawater corrosion resistant fair-faced concrete admixture (K4).
Example 5
The preparation method of the seawater corrosion resistant fair-faced concrete additive comprises the following steps:
adding 5 parts by weight of acrylamide, 3 parts by weight of methylaminopropyltrimethoxysilane and 79 parts by weight of deionized water into a reaction kettle; then, under the conditions of stirring and temperature of 25 ℃, 0.4 part by weight of sodium persulfate is added into the reaction kettle at one time, and then aqueous solution (containing 8 parts by weight of deionized water) containing 4.5 parts by weight of acrylic acid, 0.6 part by weight of sodium methallyl sulfonate and 0.3 part by weight of vitamin C is dropwise added, and the dropping is finished within 3 hours; after the dripping is finished, stirring and reacting for 1.5 hours at normal temperature to obtain the seawater corrosion resistant fair-faced concrete admixture (K5).
The seawater erosion resistant fair-faced concrete admixture obtained in the embodiments 1 to 5 is applied to concrete, and compared with two commercially available seawater erosion resistant concrete admixtures (FLW-99 organosilicon waterproofing agent a, a new waterproof technology development company limited, and UC-420 polyether polymer concrete viscosity modifier B, a scientific and technological company, wuhan youcheng), the mixing ratio of the concrete is shown in table 1, and then the strength, the chloride ion diffusion coefficient, the corrosion resistance grade and other performances of the obtained concrete are tested according to the standards of GB/T50080-2016, standard of performance test methods for general concrete mixtures, JGJ/T283-2012, standard of self-compacting concrete application technical rules, standard of GB/T50082-2009, standard of test methods for long-term performance and durability of general concrete, and the like; performing a vibration segregation rate experiment on the coarse aggregate; the strength test of the interface transition area adopts a 100mm x 100mm sheet sample cut from a 28d cured 100mm x 100mm concrete sample, a grinding machine sheet is used for grinding the sample, a digital only micro-hardness instrument is used for the micro-hardness test of the interface transition area, and finally the average value of 10 groups of data is taken as the micro-hardness value of the sample; the specific test results are shown in table 2.
TABLE 1 concrete mix proportion
TABLE 2 concrete Performance test results
The above results show that: the seawater erosion resistant fair-faced concrete additive is applied to concrete, so that the slurry stability of concrete mixture can be effectively improved, the hardness of an interface transition region is improved, the chloride ion diffusion performance is reduced, and the erosion resistance of the concrete is improved; the method has the advantages of mild reaction conditions, simple process, environmental protection, high efficiency and suitability for large-scale industrial production.
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessary or exhaustive for all embodiments, and are therefore within the scope of the invention.
Claims (5)
1. The seawater erosion fair-faced concrete additive comprises the following components in parts by weight: 3-6 parts of unsaturated carboxylic acid, 3-6 parts of unsaturated carboxylic acid derivative, 0.3-0.7 part of unsaturated sulfonic acid, 1-4 parts of silane coupling agent, 0.2-0.6 part of initiator, 0.15-0.5 part of vitamin C and 85-95 parts of water;
The unsaturated carboxylic acid is one or two of acrylic acid and methacrylic acid;
the unsaturated carboxylic acid derivative is acrylamide;
the preparation method comprises the following steps:
1) weighing the raw materials according to the proportion, wherein the raw materials and the weight portion thereof comprise: 3-6 parts of unsaturated carboxylic acid, 3-6 parts of unsaturated carboxylic acid derivative, 0.3-0.7 part of unsaturated sulfonic acid, 1-4 parts of silane coupling agent, 0.2-0.6 part of initiator, 0.15-0.5 part of vitamin C and 85-95 parts of water;
2) adding the weighed unsaturated carboxylic acid derivative, the silane coupling agent and water into a reaction kettle; then controlling the temperature to be 10-40 ℃ under the condition of stirring; adding an initiator, dropwise adding an aqueous solution containing unsaturated carboxylic acid, unsaturated sulfonate and vitamin C under the stirring condition, and controlling the dropping within 2.5-3.5 hours; and after the water is dripped, stirring at normal temperature for reaction for 1-1.5 hours to obtain the seawater erosion resistant fair-faced concrete admixture.
2. The seawater erosion bare concrete admixture according to claim 1 wherein the unsaturated sulfonate is sodium methallyl sulfonate.
3. The seawater erosion fair-faced concrete admixture of claim 1, wherein the silane coupling agent is one or more of aminopropyltrimethoxysilane, diethylenetriaminomethyloxysilane, vinyltrimethyloxysilane, vinyl (2-methylethoxy) silane and gamma-aminopropyltrimethoxysilane.
4. The seawater erosion bare water concrete admixture according to claim 1, wherein the initiator is one or more of hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate.
5. The preparation method of the seawater erosion resistant fair-faced concrete admixture of any one of claims 1 to 4, which is characterized by comprising the following steps of:
1) weighing the raw materials according to the proportion, wherein the raw materials and the weight portion thereof comprise: 3-6 parts of unsaturated carboxylic acid, 3-6 parts of unsaturated carboxylic acid derivative, 0.3-0.7 part of unsaturated sulfonic acid, 1-4 parts of silane coupling agent, 0.2-0.6 part of initiator, 0.15-0.5 part of vitamin C and 85-95 parts of water;
2) adding the weighed unsaturated carboxylic acid derivative, the silane coupling agent and water into a reaction kettle; then controlling the temperature to be 10-40 ℃ under the condition of stirring; adding an initiator, dropwise adding an aqueous solution containing unsaturated carboxylic acid, unsaturated sulfonate and vitamin C under the stirring condition, and controlling the dropping within 2.5-3.5 hours; and after the water is dripped, stirring at normal temperature for reaction for 1-1.5 hours to obtain the seawater corrosion resistant fair-faced concrete admixture.
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| CN105754045A (en) * | 2016-03-02 | 2016-07-13 | 海南太和科技有限公司 | Silane coupling agent modified polycarboxylate superplasticizer and preparation method thereof |
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| TWI268914B (en) * | 2003-05-09 | 2006-12-21 | Nippon Catalytic Chem Ind | Polycarboxylic acid concrete admixture |
| US8623791B2 (en) * | 2010-09-29 | 2014-01-07 | China Petroleum & Chemical Corporation | Copolymer and preparation method and application thereof |
| CN105669911B (en) * | 2016-01-14 | 2018-05-04 | 厦门路桥翔通建材科技有限公司 | A kind of concrete water conservation segregation reducing agent and preparation method thereof |
| CN105924590B (en) * | 2016-04-26 | 2018-07-24 | 陕西德盛新能源有限公司 | A kind of preparation method of polycarboxylic acid series water reducing agent |
| CN108609891B (en) * | 2018-05-04 | 2021-01-15 | 厦门路桥翔通建材科技有限公司 | Polycarboxylic acid type wet-mixed mortar plasticizer and preparation method thereof |
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| US5362829A (en) * | 1992-09-30 | 1994-11-08 | Takemoto Yushi Kabushiki Kaisha | Cement dispersion agents |
| CN105754045A (en) * | 2016-03-02 | 2016-07-13 | 海南太和科技有限公司 | Silane coupling agent modified polycarboxylate superplasticizer and preparation method thereof |
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