CN109485299B - Multi-effect concrete structure self-waterproof additive with self-repairing capability - Google Patents
Multi-effect concrete structure self-waterproof additive with self-repairing capability Download PDFInfo
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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
- C04B2103/65—Water proofers or repellants
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Abstract
The invention discloses a multiple-effect concrete structure self-waterproof additive with self-repairing capability, which is composed of the following raw materials in percentage by mass: 40-60% of expanding agent, 2-6% of alumina, 2-5% of zinc sulfate, 7-15% of water-retaining agent, 4-12% of modified fluorine-containing silicone oil, 12-26% of anti-crack fiber and 2-8% of modified terephthalic acid polyvalent metal salt. The multiple-effect concrete structure self-waterproof additive with self-repairing capability can improve the dispersibility of various raw materials in concrete, reduce pores in the concrete, increase the compactness of the concrete, improve the water retention performance, reduce the contractility, and improve the waterproofness, crack resistance, permeability resistance and frost resistance.
Description
Technical Field
The invention relates to the field of concrete admixtures, and particularly provides a multi-effect concrete structure self-waterproof additive with self-repairing capability.
Background
With the progress of society and the improvement of living standard of people, people have higher and higher requirements on the quality and the function of modern building materials, especially on the anti-cracking and waterproof performance and the durability of concrete. Cracking of concrete is mainly caused by the following reasons: firstly, the concrete is deformed due to temperature shrinkage and drying shrinkage in the hydration hardening process to cause cracking and water seepage phenomena, which seriously affect the durability of the concrete; and secondly, fine air holes are uniformly distributed in the formed concrete, so that the water seepage phenomenon of the concrete can occur due to the hydrostatic pressure and the capillary action, and the water seepage can greatly affect the concrete, mortar and even a building structure in the day and month. Therefore, the waterproof property has important influence on the engineering quality, and the solution of the cracking and water seepage problems is one of the important directions for the research of the concrete.
The water-proofing agent can be divided into inorganic water-proofing agent, organic water-proofing agent and inorganic-organic composite concrete water-proofing agent according to its chemical composition. The inorganic waterproof agent is mainly used for reducing the pores in concrete by inorganic compounds (such as chloride salts of iron or aluminum) and improving the compactness and impermeability. The organic waterproof agent is mainly used for forming a hydrophobic surface on the surface of concrete through an organic compound (such as stearic acid) so as to improve the impermeability. The inorganic-organic composite concrete water-proofing agent is an inorganic-organic composite system, and can play the role of water proofing and plasticizing.
The concrete can be divided into a self-cracking-resistant waterproof agent and an outer coating waterproof agent according to different ways of solving the cracking and water seepage problems of the concrete: the self-cracking-resistant waterproof structure generally adopts an expanding agent, the cracking and water seepage problems are reduced by means of expansion compensation shrinkage, the expanding agent is generally powder, the dispersibility of the expanding agent is not easy, and the use risk is increased; the external waterproof agent is mainly a silane waterproof anticorrosive coating, the construction process is complicated, the coating on the surface is easy to wear or fall off, and the service life is generally not more than 20 years. Engineering fibers are often used in concrete structures as a reinforcing material to improve the impact resistance and bending resistance of concrete and further improve the crack resistance and water resistance of concrete, but generally, engineering fibers have the defects of difficult dispersion in concrete, poor adhesion with a matrix and the like, so that the application of the engineering fibers is limited and the crack resistance effect of the engineering fibers is unstable.
Chinese patent CN102701635A discloses a nano-composite expansion crack-resistant agent, which comprises the following components in percentage by weight: 9.2 to 27.5 percent of calcium sulphoaluminate, 6.8 to 11.2 percent of calcium aluminate, 7.1 to 15.4 percent of calcium hydroxide, 4.8 to 13.6 percent of PSP organic silicon powder, 3.6 to 7.5 percent of sodium silicate, 0.1 to 3.2 percent of ethylenediamine sodium phosphate, 0.5 to 2.5 percent of iron powder, 1.0 to 3.3 percent of borax, 0.1 to 0.5 percent of manganese dioxide, 0.1 to 2.4 percent of polypropylene fiber, 0.1 to 0.8 percent of disodium ethylenediamine tetraacetic acid, 1.8 to 4.3 percent of sodium tripolyphosphate, 15.2 to 22.5 percent of fly ash, 5.3 to 11.6 percent of amino phenoxy naphthalene sulfonate and 5.1 to 8.5 percent of FP nano polymer. The expansion produced by the product of the invention and the concrete shrinkage develop synchronously, and the generated filler can be effectively filled in the concrete pore gaps under different periods, different magnitudes and different action mechanisms of different crystal minerals. When the concrete is restrained by the steel bars and the adjacent positions, the pre-stress of 0.3MPa-0.8MPa can be generated, different expansion mineral phases are generated in different ages of the concrete, and the generation and development of non-structural cracks such as early plastic shrinkage, dry shrinkage and the like of the concrete and cement mortar are effectively controlled. However, the direct addition of the fibers to concrete in this patent has the problems of difficulty in dispersibility, easy generation of a large number of bubbles during mixing, and poor adhesion of the fibers to the matrix, which reduces the crack resistance stability. And the anti-cracking agent of the invention can not improve the surface hydrophobic property and impermeability of the concrete, once the concrete has tiny cracks, the water is easy to permeate into the concrete from the cracks, which can greatly reduce the service life of the concrete.
Chinese patent CN104944822A discloses an expansive concrete waterproof agent and a preparation method thereof, wherein the waterproof agent is prepared from the following components in parts by weight: 15-65 parts of magnesium phosphate, 5-15 parts of magnesium slag powder, 10-30 parts of fly ash, 0.5-1 part of aluminum slag powder, 1-5 parts of calcium silicate, 1-3 parts of talcum powder and 1-3 parts of dilute hydrochloric acid. The preparation method of the waterproof agent comprises the steps of accurately weighing the components in parts by weight, firstly placing the weighed magnesium phosphate into a stirring barrel, then sequentially adding the weighed magnesium slag powder, fly ash, aluminum slag powder, calcium silicate, talcum powder and dilute hydrochloric acid into the magnesium phosphate, and stirring by using a mechanical stirrer. And fully stirring, and obtaining the expansive type concrete waterproof agent after the uniform material does not contain aggregates. The preparation method is simple, the operation is easy, the cost is low, the prepared waterproof agent has the advantages of no toxicity, small mixing amount, low alkali content and the like, but the impact resistance and the bending resistance of the concrete are not improved, so that the concrete is still easy to generate cracks due to external force or freeze thawing, the surface hydrophobicity and the impermeability of the concrete cannot be improved by the anti-cracking agent, and once the concrete has fine cracks, the service life of the concrete is greatly shortened because moisture is easy to permeate into the concrete from the cracks.
The existing waterproof agent has single action, poor waterproof and anti-cracking effects and poor effect of improving the durability of concrete. Therefore, the development of a concrete waterproof additive with excellent comprehensive performance is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the problems in the prior art and provide the multi-effect self-waterproof additive with the self-repairing capability for the concrete structure, which can improve the dispersibility of various raw materials in the concrete, reduce the pores in the concrete, increase the compactness of the concrete, improve the water retention performance, reduce the contractility, and improve the waterproofness, crack resistance, impermeability and frost resistance effects of the concrete.
The invention discloses a multi-effect concrete structure self-waterproof additive with self-repairing capability, which comprises the following raw materials in percentage by mass: 40-60% of expanding agent, 2-6% of alumina, 2-5% of zinc sulfate, 7-15% of water-retaining agent, 4-12% of modified fluorine-containing silicone oil, 12-26% of anti-crack fiber and 2-8% of modified terephthalic acid polyvalent metal salt.
Preferably, the anti-crack fiber is at least one of polypropylene fiber, polyester fiber, polyamide fiber, polyvinyl alcohol fiber, polyacrylonitrile fiber and basalt fiber.
Preferably, the water retaining agent is one or more of carboxymethyl cellulose ether, hydroxyethyl methyl cellulose ether and ethyl cellulose ether.
Preferably, the swelling agent is one or more of azodicarbonamide, tosylhydrazide, calcium oxide, calcium sulfoaluminate and magnesium oxide swelling agent.
Preferably, the multi-effect concrete structure self-waterproof additive with self-repairing capability consists of the following raw materials in percentage by mass: 50% of expanding agent, 4% of aluminum oxide, 3% of zinc sulfate, 10% of water-retaining agent, 8% of modified fluorine-containing silicone oil, 20% of anti-crack fiber and 5% of modified terephthalic acid polyvalent metal salt; the swelling agent is formed by mixing 10% of tosylhydrazide and 90% of calcium oxide; the anti-crack fiber is formed by mixing 20% of polyamide fiber and 80% of basalt fiber; the diameter of the fiber is 10 to 20 μm, and the length is 1 to 3 cm.
The modified fluorine-containing silicone oil is prepared by the following method:
(S1) mixing 100 parts of hydrogen-containing fluorosilicone oil and 30-40 parts of allyl glycidyl ether, adding a Kanster catalyst, stirring, heating, and reacting at 40-50 ℃ for 1-2 hours to obtain epoxy-containing fluorosilicone oil;
(S2) adding 0.1-0.3 part of dimethylbenzylamine and 2-3 parts of octadeca-9, 12-dienoic acid into the prepared fluorine-containing silicone oil containing the epoxy group, stirring and heating, and reacting for 3-4 hours at 100-110 ℃ to obtain the modified fluorine-containing silicone oil.
Preferably, the multivalent metal in the modified terephthalic acid multivalent metal salt is at least one of calcium, magnesium, zinc and iron.
The preparation method of the modified terephthalic acid polyvalent metal salt comprises the following steps:
(S1) preparing or preparing a sodium terephthalate solution;
one of three methods may be employed:
(1) reacting terephthalic acid with sodium hydroxide in water to generate a sodium terephthalate solution;
(2) directly dissolving sodium terephthalate in water to prepare a solution;
(3) using the recovered waste liquid of nylon fabric containing sodium terephthalate through alkali solution treatment;
(S2) adding the chloride of the polyvalent metal into the sodium phthalate solution, and stirring to generate solid precipitate of the terephthalic acid polyvalent metal salt with the crystallization water;
(S3) filtering the terephthalic acid polyvalent metal salt solid precipitate, and drying at 80-120 ℃ for 8-12 hours to obtain terephthalic acid metal salt powder without crystal water;
(S4) mixing and grinding the hydrophobic normal temperature solid organic acid and the terephthalic acid metal salt powder to obtain the modified terephthalic acid polyvalent metal salt.
Preferably, the hydrophobic normal-temperature solid organic acid is at least one of stearic acid and lauric acid.
More preferably, the modified terephthalic acid polyvalent metal salt is modified calcium terephthalate.
The polyvalent metal terephthalate without crystal water is exemplified by calcium terephthalate powder, which is dissolved and recrystallized into calcium terephthalate crystals containing crystal water when meeting water, and the volume is increased. Has the action of repairing micro cracks by crystallizing, permeating and blocking holes. Through surface modification, the secondary crystallization rate is delayed, so that in the early-stage concrete water-containing mixture condensation and hardening process, the calcium terephthalate powder without crystal water does not perform secondary crystallization, as long as water seepage occurs in later cracks, the surface coating layer is gradually damaged after being soaked in alkaline solution for a long time, and secondary crystallization is started only when the calcium terephthalate powder without crystal water inside contacts with water, so that the hole plugging repairing effect is formed.
Meanwhile, the hydrophobicity of the modified powder is also beneficial to the hydrophobicity in the concrete, and the impermeability of the concrete is improved.
The preparation method of the multiple-effect concrete structure self-waterproof additive with self-repairing capability comprises the following steps: the anti-crack fiber and the modified fluorine-containing silicone oil are stirred and dispersed uniformly, and then the expanding agent, the alumina, the zinc sulfate, the water-retaining agent and the modified terephthalic acid polyvalent metal salt are added and stirred uniformly to obtain the anti-crack fiber.
The addition amount of the multi-effect concrete structure self-waterproof additive with self-repairing capability in concrete is 2-5% of the cement consumption.
The modified fluorine-containing silicone oil has better compatibility with concrete than unmodified fluorine-containing silicone oil, can improve the water permeability resistance of concrete when used in the concrete, obviously reduces bubbles in the concrete, can be adsorbed on the surfaces of anti-crack fibers and the concrete, improves the dispersibility of the anti-crack fibers and the concrete, enables the anti-crack fibers to be uniformly dispersed in the concrete, improves the adhesion between the anti-crack fibers and the concrete by active groups on the modified fluorine-containing silicone oil, and greatly improves the toughness, the breaking strength and the frost resistance of the concrete by the modified fluorine-containing silicone oil in cooperation with the anti-crack fibers; the expanding agent, the alumina, the zinc sulfate and the like are matched with each other to slowly react in the hardening process of the concrete to continuously generate expansion compensation temperature shrinkage and drying shrinkage; the water retention property of the concrete can be improved by adding the water retention agent, and the water retention agent and the modified fluorine-containing silicone oil synergistically reduce the surface tension of a liquid phase of the concrete, reduce capillary channels and reduce the generation of drying cracks. The synergistic effect of the modified terephthalic acid polyvalent metal salt and the fluorine-containing silicone oil greatly improves the internal hydrophobicity of concrete and improves the impermeability.
Compared with the prior art, the multi-effect concrete structure self-waterproof additive with self-repairing capability has the beneficial effects that:
(1) the air bubbles in the concrete can be obviously reduced only by lower mixing amount, the compactness of the concrete is improved, and the concrete is improved
The hydrophobic and impervious properties of soil.
(2) The modified fluorine-containing silicone oil is cooperated with the anti-crack fiber, so that the dispersibility and the adhesiveness of the anti-crack fiber and concrete are improved, and the improvement is greatly
High toughness, high breaking strength and high freezing resistance.
(3) The modified terephthalic acid polyvalent metal salt has the function of repairing the blocked holes and synergistically modifies the fluorine-containing silicone oil and the anti-crack fibers
The dimension can greatly improve the hydrophobicity in the concrete and the impermeability of the concrete.
(4) Expanding agent, alumina, zinc sulfate, water-retaining agent, modified fluorine-containing silicone oil and modified poly-valent gold terephthalate
The salt is mutually cooperated to greatly reduce the generation of cracks and improve the impermeability and frost resistance.
Detailed Description
For better comparative experimental effect, the modified polyvalent metal terephthalate salt in this embodiment is prepared by the same method as follows:
(S1) directly dissolving sodium terephthalate in water to prepare a solution;
(S2) adding the sodium phthalate solution to the polyvalent metal chloride and stirring to generate a solid precipitate of a polyvalent metal salt of terephthalic acid with crystal water;
(S3) filtering the terephthalic acid polyvalent metal salt solid precipitate, and drying at 80-120 ℃ for 8-12 hours to obtain terephthalic acid metal salt powder without crystal water;
(S4) the modified terephthalic acid polyvalent metal salt is prepared by mixing lauric acid and terephthalic acid metal salt powder in a mass ratio of 1:3, and grinding the mixture in a ball mill for 20 min.
The technical solutions of the present invention are described in detail and fully below with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention. Equivalent changes or substitutions of method, process route, function and the like by those skilled in the art according to the following embodiments are within the scope of the present invention.
Example 1
The multiple-effect concrete structure self-waterproof additive with the self-repairing capability is prepared from the following raw materials in percentage by mass: 60% of calcium oxide expanding agent, 2% of aluminum oxide, 2% of zinc sulfate, 12% of carboxymethyl cellulose ether, 4% of modified fluorine-containing silicone oil, 12% of polypropylene fiber (the diameter is 3-5 mu m, and the length is 5-8 mm), and 8% of modified ferric terephthalate.
The modified fluorine-containing silicone oil is prepared by the following method:
(S1) mixing 100 parts of hydrogen-containing fluorosilicone oil (with the hydrogen content of 0.4 percent and the viscosity of 50cs) and 40 parts of allyl glycidyl ether, adding a Kanst catalyst to enable the Pt content in the mixture to be 20ppm, stirring and heating, and reacting at 50 ℃ for 1h to obtain epoxy-containing fluorosilicone oil;
(S2) adding 0.3 part of dimethylbenzylamine and 3 parts of octadeca-9, 12-dienoic acid into the prepared fluorine-containing silicone oil containing epoxy groups, stirring and heating, and reacting for 4 hours at 110 ℃ to obtain the modified fluorine-containing silicone oil.
Example 2
The multiple-effect concrete structure self-waterproof additive with the self-repairing capability is prepared from the following raw materials in percentage by mass: 40% of azodicarbonamide expanding agent, 6% of aluminum oxide, 5% of zinc sulfate, 10% of hydroxyethyl methyl cellulose ether, 11% of modified fluorine-containing silicone oil, 26% of basalt fiber (the diameter is 30-50 mu m, and the length is 1-3 cm), and 2% of modified magnesium terephthalate.
The modified fluorine-containing silicone oil is prepared by the following method:
(S1) mixing 100 parts of hydrogen-containing fluorosilicone oil (with the hydrogen content of 0.6 percent and the viscosity of 25cs) and 30 parts of allyl glycidyl ether, adding a Kanst catalyst to enable the Pt content in the mixture to be 10ppm, stirring and heating, and reacting at 40 ℃ for 2 hours to obtain epoxy-containing fluorosilicone oil;
(S2) adding 0.3 part of dimethylbenzylamine and 3 parts of octadeca-9, 12-dienoic acid into the prepared fluorine-containing silicone oil containing epoxy groups, stirring and heating, and reacting for 3 hours at 100 ℃ to obtain the modified fluorine-containing silicone oil.
Example 3
The multiple-effect concrete structure self-waterproof additive with the self-repairing capability is prepared from the following raw materials in percentage by mass: 50% of expanding agent, 4% of aluminum oxide, 3% of zinc sulfate, 10% of ethyl cellulose ether, 8% of modified fluorine-containing silicone oil, 20% of anti-crack fiber and 5% of modified calcium terephthalate; the swelling agent is formed by mixing 10% of tosylhydrazide and 90% of calcium oxide; the anti-crack fiber is formed by mixing 20% of polyamide fiber and 80% of basalt fiber; the diameter of the fiber is 10 to 20 μm, and the length is 1 to 3 cm.
The modified fluorine-containing silicone oil is prepared by the following method:
(S1) mixing 100 parts of hydrogen-containing fluorosilicone oil (with the hydrogen content of 0.5 percent and the viscosity of 30cs) and 35 parts of allyl glycidyl ether, adding a Kanst catalyst to enable the Pt content in the mixture to be 15ppm, stirring and heating, and reacting at 40 ℃ for 2 hours to obtain epoxy-containing fluorosilicone oil;
(S2) adding 0.2 part of dimethylbenzylamine and 3 parts of octadeca-9, 12-dienoic acid into the prepared fluorine-containing silicone oil containing epoxy groups, stirring and heating, and reacting for 3 hours at 110 ℃ to obtain the modified fluorine-containing silicone oil.
Comparative example 1
Compared with the example 3, the comparative example replaces the modified fluorine-containing silicone oil in the example 3 with the hydrogen-containing fluorosilicone oil which is not modified, and the rest is the same as the example 3.
The waterproof additive of the comparative example is uniformly mixed with concrete, and then is kept still for 10min, so that more floating oil appears on the surface of the concrete.
Comparative example 2
In comparison with example 3, the shrinkage reducing component of this comparative example does not contain anti-crack fibers, and the rest is the same as example 3.
Comparative example 3
Compared with example 3, the modified fluorine-containing silicone oil of the comparative example is prepared by the following method:
(S1) mixing 100 parts of hydrogen-containing fluorosilicone oil (with the hydrogen content of 0.5 percent and the viscosity of 30cs) and 35 parts of allyl glycidyl ether, adding a Kanst catalyst to enable the Pt content in the mixture to be 15ppm, stirring and heating, and reacting for 2 hours at 40 ℃ to obtain the modified fluorine-containing silicone oil.
The waterproof additive of the comparative example is uniformly mixed with concrete, and then is kept still for 10min, so that a small amount of floating oil appears on the surface of the concrete.
Comparative example 4
In comparison with example 3, this comparative example was conducted in the same manner as in example 3 except that the modified fluorosilicone oil was replaced with glycerin.
Comparative example 5
This comparative example, which was compared to example 3, had modified calcium terephthalate removed, and was otherwise identical to example 3.
The performance of each of the examples and comparative examples was tested by using a reference concrete as a control group, adding no waterproof additive to the reference concrete, and adding the waterproof additives of the examples and comparative examples to the concrete at 3% by mass of cement. The raw material ratios used for the reference concrete are shown in table 1.
The test items include: static contact angle between the concrete surface and water, mechanical property, impermeability, frost resistance and the like. The concrete compression strength, the bending strength and the shrinkage ratio are tested according to JCT474-2008 'mortar concrete waterproofing agent industry standard', and the early crack resistance performance test is carried out in reference T/CECS10001-2017 'crack-resistant and impervious composite material used in concrete'. The impermeability grade test is carried out according to GB50108-2008 'underground engineering waterproof technical Specification'; the frost resistance rating test is carried out according to GBJ50164-2011 concrete quality control Standard. The test results are shown in Table 2.
TABLE 1 Standard concrete ratio (unit Kg/m)3)
Table 2: test results of different waterproof additives doped in reference concrete
From the test results, it can be seen that after the multi-effect concrete structure self-waterproofing additive with self-repairing capability of the embodiment of the invention is applied to concrete, the static water contact angle of the concrete can be greatly improved, air bubbles in fresh concrete can be reduced, the mechanical properties of the concrete, especially the 28-day flexural strength of the concrete can be improved, the shrinkage rate of the concrete can be effectively reduced, and the anti-permeability grade and the anti-freezing grade of the concrete can be improved.
After the self-waterproof additive disclosed by the embodiment of the invention is added into the reference concrete, the gas content of the reference concrete is reduced to below 1.6% from 2.4%, and compared with the concrete doped with the self-waterproof additive disclosed by the embodiment of the invention, the static contact angle of the reference concrete and water is obviously improved, the breaking strength is improved by more than 10%, particularly, the raw materials in each proportion of the embodiment 3 are matched, so that the comprehensive performance is better, the shrinkage rate and the crack coefficient are obviously reduced, and the frost resistance grade and the anti-permeability grade are obviously improved.
Compared with the independent comparative examples 1, 3 and 4 and the independent example 3, the modified fluorine-containing silicone oil is removed, replaced or changed in the preparation method, so that the gas content in the concrete is increased, the static contact angle with water is obviously reduced, the mechanical property and the anti-permeability and anti-freezing grade are also obviously reduced, and the concrete of the comparative examples 1 and 3 is easy to generate floating oil after being mixed with the additive. The modified fluorine-containing silicone oil prepared by the invention can obviously improve the surface waterproofness of concrete and reduce the gas content in the concrete, probably because the active groups in the modified fluorine-containing silicone oil can be combined with concrete or anti-cracking fibers to form grafts on the surface, thereby not only improving the dispersibility, but also improving the toughness, the water and water impermeability and the freezing resistance. The fluorine-containing silicone oil has poor compatibility in concrete without modification or change of a preparation method, and active groups in the fluorine-containing silicone oil are reduced and cannot be grafted on the surface of concrete or anti-cracking fibers, so that the dispersibility, the impermeability and the frost resistance of the fluorine-containing silicone oil cannot be obviously improved.
In comparative example 2, when no anti-crack fiber is added, the flexural strength and the anti-crack performance of the concrete are improved compared with those of the standard concrete, but the improvement effect is not as good as that of example 3, and the anti-permeability grade and the anti-freeze grade are also obviously reduced compared with example 3.
Comparative example 5 and example 3 alone can find that the static contact angle with water in the concrete without the modified terephthalic acid polyvalent metal salt is obviously reduced, and the anti-permeability and anti-freezing grade is also obviously reduced. The modified terephthalic acid polyvalent metal salt not only has the function of repairing the blocked holes, but also is beneficial to improving the hydrophobicity in the concrete and improving the impermeability of the concrete.
In summary, it can be seen that the raw materials of the anti-crack fiber, the modified fluorine-containing silicone oil, the modified terephthalic acid polyvalent metal salt, the expanding agent, the water-retaining agent and the like have mutual synergistic effect, and the strength of the concrete can be obviously improved and the performances of water resistance, permeability resistance, frost resistance and the like of the concrete can be improved only by matching various raw materials within the scope of the invention. The effect of removing or changing any raw material or changing the preparation method of the modified fluorine-containing silicone oil can be obviously influenced.
Having shown and described the basic principles, essential features and advantages of the invention, while embodiments of the invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. The multiple-effect concrete structure self-waterproof additive with self-repairing capability is characterized by comprising the following raw materials in percentage by mass: 40-60% of expanding agent, 2-6% of alumina, 2-5% of zinc sulfate, 7-15% of water-retaining agent, 4-12% of modified fluorine-containing silicone oil, 12-26% of anti-crack fiber and 2-8% of modified terephthalic acid polyvalent metal salt;
the modified fluorine-containing silicone oil is prepared by the following method:
A. mixing 100 parts of hydrogen-containing fluorosilicone oil and 30-40 parts of allyl glycidyl ether, adding a Kanster catalyst, stirring, heating, and reacting at 40-50 ℃ for 1-2 hours to obtain epoxy group-containing fluorosilicone oil;
B. adding 0.1-0.3 part of dimethylbenzylamine and 2-3 parts of octadeca-9, 12-dienoic acid into the prepared fluorine-containing silicone oil containing epoxy groups, stirring and heating, and reacting at 100-110 ℃ for 3-4 hours to obtain modified fluorine-containing silicone oil;
the preparation method of the modified terephthalic acid polyvalent metal salt comprises the following steps:
(S1) preparing or preparing a sodium terephthalate solution;
(S2) adding the chloride of the polyvalent metal into the sodium phthalate solution, and stirring to generate solid precipitate of the terephthalic acid polyvalent metal salt with the crystallization water;
(S3) filtering the terephthalic acid polyvalent metal salt solid precipitate, and drying at 80-120 ℃ for 8-12 hours to obtain terephthalic acid metal salt powder without crystal water;
(S4) mixing and grinding the hydrophobic normal temperature solid organic acid and the terephthalic acid metal salt powder to obtain the modified terephthalic acid polyvalent metal salt.
2. The multi-effect concrete structure self-waterproofing additive having self-repairing capability according to claim 1, wherein the anti-crack fiber is at least one of polypropylene fiber, polyester fiber, polyamide fiber, polyvinyl alcohol fiber, polyacrylonitrile fiber, and basalt fiber.
3. The multi-effect concrete structure self-waterproofing additive with self-repairing capability according to claim 1, wherein the water retention agent is one or more of carboxymethyl cellulose ether, hydroxyethyl methyl cellulose ether and ethyl cellulose ether.
4. The multi-effect concrete structure self-waterproofing additive with self-repairing capability according to claim 1, wherein the swelling agent is one or more of azodicarbonamide, tosylhydrazide, calcium oxide, calcium sulfoaluminate, magnesium oxide swelling agent.
5. The multi-effect concrete structure self-waterproof additive with self-repairing capability of claim 1 is characterized by comprising the following raw materials in percentage by mass: 50% of expanding agent, 4% of aluminum oxide, 3% of zinc sulfate, 10% of water-retaining agent, 8% of modified fluorine-containing silicone oil, 20% of anti-crack fiber and 5% of modified terephthalic acid polyvalent metal salt;
the swelling agent is formed by mixing 10% of tosylhydrazide and 90% of calcium oxide; the anti-crack fiber is formed by mixing 20% of polyamide fiber and 80% of basalt fiber; the diameter of the fiber is 10 to 20 μm, and the length is 1 to 3 cm.
6. The pleiotropic concrete structure self-waterproofing additive with self-repairing capability according to any one of claims 1 to 5, wherein the multivalent metal in the modified terephthalic acid multivalent metal salt is at least one of calcium, magnesium, zinc and iron.
7. The multi-effect concrete structure self-waterproofing additive having self-repairing capability according to claim 1, wherein the hydrophobic normal temperature solid organic acid is at least one of stearic acid and lauric acid.
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| CN201811525000.8A CN109485299B (en) | 2018-12-13 | 2018-12-13 | Multi-effect concrete structure self-waterproof additive with self-repairing capability |
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| CN116332560A (en) * | 2023-03-16 | 2023-06-27 | 江苏同禹新材料科技有限公司 | Anti-cracking waterproof composite additive for concrete and preparation method and application thereof |
| CN117383843B (en) * | 2023-08-30 | 2024-04-12 | 福建源鑫建材有限公司 | High-strength all-solid waste cementing material and preparation method and application thereof |
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| CN101462843A (en) * | 2008-12-17 | 2009-06-24 | 同济大学 | Marine concrete corrosion resistant additive and preparation thereof |
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| CN101462843A (en) * | 2008-12-17 | 2009-06-24 | 同济大学 | Marine concrete corrosion resistant additive and preparation thereof |
| CN102815883A (en) * | 2012-08-29 | 2012-12-12 | 河南铝城聚能实业有限公司 | Fiber composite capillary-crystalline expanding agent and preparation method thereof |
| WO2014053341A1 (en) * | 2012-10-04 | 2014-04-10 | Construction Research & Technology Gmbh | Hydraulic composition |
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