CN115627103B - Multilayer coating for improving carbonization resistance of concrete and preparation method thereof - Google Patents
Multilayer coating for improving carbonization resistance of concrete and preparation method thereof Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
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- C04B41/65—Coating or impregnation with inorganic materials
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Abstract
The invention discloses a concrete carbonization resistant paint, which is prepared by compounding a sacrificial carbonization component A, a concrete inner surface intercalation blocking component B, a concrete inner layer microstructure regulating component C and a composite solvent D as main raw materials; the sacrificial carbonization component A is obtained by mixing and ball milling a lime-based component and triethanolamine; the internal intercalation barrier component B of the concrete is mainly obtained by modifying hexagonal boron nitride by using concentrated sulfuric acid and potassium permanganate; the concrete surface microstructure regulating and controlling component C is modified nano titanium dioxide dispersion liquid; the compound solvent D is formed by compounding polyacrylic emulsion, alcohol ester-12, hydrophilic fumed silica, polyvinylpyrrolidone, methanol and water. The invention combines multiple carbonization mechanisms, can obviously improve the carbonization resistance of concrete, and simultaneously has good abrasion resistance and long-acting protection effect; the related construction process is simple, convenient to operate and suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a coating capable of improving carbonization resistance of concrete in multiple layers and a preparation method thereof.
Background
In recent years, with the increase of engineering technology difficulty and the change of construction environment, higher requirements are put on the long-term durability of concrete. At present, besides the specific durability requirements of regional climate environments on concrete, the problems of concrete carbonization and the like become more common and serious, and the problems of concrete carbonization and the like gradually occur in coastal and inland cities, including mountain east, henan, gansu, qinghai, xinjiang and other regional projects. And carbonization can cause problems of alkali reduction affecting reinforcement corrosion, carbonization shrinkage affecting volume deformation, toughness reduction affecting surface cracking and the like on concrete, so that the method has important significance in developing a concrete cracking technology of new construction.
At present, regarding the concrete carbonization resistance technology, besides the durability design of the concrete material, the carbonization resistance performance of the hardened concrete can be further improved by coating the surface of the concrete with a coating with carbonization resistance effect. However, the existing concrete anti-carbonization paint is mainly organic paint, namely an organic protective layer is formed on the surface of the concrete, and the contact path of carbon dioxide and the concrete is directly cut off, but the paint has larger smell during construction and has poorer aging resistance effect after drying and film forming; the common inorganic paint mostly uses heavy metals, formaldehyde and the like as main constituent materials, and has the problems of high production cost, large pollution to concrete, difficult recycling of the coated concrete and the like; meanwhile, the method is not beneficial to forming long-term stable carbonization protection for concrete.
Disclosure of Invention
Aiming at the problems and defects existing in the prior art, the invention provides a novel anti-carbonization coating, which combines multiple protection mechanisms such as active sacrifice carbonization of an outer surface layer (an outer surface adhesion layer with the thickness of about 1mm formed on the outer surface of concrete), intercalation blocking of a concrete surface layer (within the depth range of about 1mm from the surface of concrete) and refinement of a pore structure of a concrete inner layer (within the depth range of about 1-5 mm from the surface of concrete), and the like, thereby remarkably improving the anti-carbonization capability and long-acting protection effect of the concrete; and the related construction process is simpler, convenient to operate, low in cost and suitable for popularization and application.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a concrete anti-carbonization paint is prepared from sacrificial carbonization component A, intercalation barrier component B on the inner surface of concrete,
The concrete inner layer microstructure regulating and controlling component C and the composite solvent D are obtained by compounding main raw materials, wherein:
the sacrificial carbonization component A is obtained by mixing and ball milling a lime-based component and triethanolamine;
the preparation method of the intercalation barrier component B on the inner surface of the concrete comprises the following steps: firstly, carrying out ultrasonic treatment on hexagonal boron nitride by using concentrated sulfuric acid and potassium permanganate, then carrying out heating reaction under a protective atmosphere, centrifugally separating, cleaning and filtering to be neutral, drying and cooling;
the preparation steps of the concrete inner layer microstructure regulating component C comprise: dispersing nano titanium dioxide and a superplasticizer, namely the multi-ammonium polyacrylate, in water, stirring and carrying out ultrasonic treatment to obtain a nano titanium dioxide suspension, then adding ethanol, uniformly mixing, adding alkali liquor (such as ammonia water and the like) to adjust the pH value to 8-10, and carrying out stirring reaction under the water bath condition;
the composite solvent D comprises the following components in parts by weight: 80-100 parts of polyacrylic emulsion, 1-3 parts of alcohol ester-12 (TEXANOL), 3-5 parts of hydrophilic fumed silica, 1-2 parts of polyvinylpyrrolidone (PVP), 2-4 parts of methanol and 200-210 parts of water.
In the scheme, the mass ratio of the sacrificial carbonization component A to the concrete inner surface intercalation blocking component B to the concrete inner layer microstructure regulating component C to the composite solvent D is (2-3): (1-2): (0.5-1): (15-20).
In the scheme, the lime-based component can be calcium oxide or calcium hydroxide, etc., and the mass ratio of the lime-based component to triethanolamine is (8-10) 1; and carrying out ball milling and compounding on the two types of raw materials, wherein the adopted rotating speed is 150-200 r/min, and the time is 10-15 min.
In the scheme, the mass ratio of the hexagonal boron nitride (h-BN) to the concentrated sulfuric acid is 1 (100-120), and the addition amount of the potassium permanganate is 1-1.5% of the mass of the h-BN.
Further, the concentration of the concentrated sulfuric acid is 95-98wt%.
In the scheme, the heating reaction step is carried out at 50-70 ℃ for 4-6 hours, and the adopted protective atmosphere can be nitrogen or the like.
In the scheme, the dosage ratio of the nano titanium dioxide (NT) to the water is 1 (13-40), and the superplasticizer ammonium polyacrylate (PAA-NH) 4 ) The dosage is 10-20% of the mass of the nano titanium dioxide (NT); the mass ratio of the obtained nano titanium dioxide suspension to ethanol is 1 (8-12).
In the scheme, the stirring reaction step adopts room temperature or normal temperature conditions, the time is 0.5-1 h, and the stirring rotating speed is 1300-1500 r/min.
In the scheme, the solid content of the polyacrylic emulsion is 50-60%, and the viscosity is 5000-5500 Pa.s.
According to the scheme, the concrete carbonization resistant paint is prepared from the sacrificial carbonization component A, the intercalation blocking component B on the inner surface of the concrete, the micro-structure regulating component C on the inner layer of the concrete and the composite solvent D as main raw materials at the stirring speed of 800-900 r/min, and is stirred for 50-70 min.
The preparation method of the concrete anti-carbonization coating specifically comprises the following steps:
1) Preparation of sacrificial carbonization component A
Uniformly mixing the weighed triethanolamine with the lime-based component, and performing ball milling to obtain a sacrificial carbonized component A; the introduced triethanolamine is mainly used as a ball milling dispersing auxiliary agent, and is helpful for dispersing the lime-based component in a subsequent solvent, so that the lime-based component is finally and uniformly distributed on the surface of the concrete;
2) Preparation of the intercalation barrier component B on the inner surface of the concrete
Adding potassium permanganate into the weighed hexagonal boron nitride (h-BN) and concentrated sulfuric acid, uniformly mixing, performing ultrasonic treatment, putting into a high-temperature high-pressure reaction kettle, heating to 50-70 ℃ under protective atmosphere, and reacting for 4-6 hours; centrifuging to obtain a bottom solid substance, washing the bottom solid substance with water until the bottom solid substance is neutral (pH=7-7.5), drying, cooling, and sieving with a 500-mesh sieve to obtain the internal intercalation barrier component B of the concrete;
3) Preparing a microstructure regulating component C of the inner surface layer of the concrete;
adding a superplasticizer, namely, ammonium polyacrylate (PAA-NH 4), into nano titanium dioxide (NT) and water, and simultaneously carrying out mechanical stirring (the stirring speed is 400-600 r/min) and ultrasonic vibration (the frequency is 20-25 KHz) for 8-12 min to prepare an NT suspension with uniform dispersion; uniformly stirring and mixing the obtained NT suspension with ethanol, dropwise adding an alkaline solution to adjust the pH value of the obtained mixed solution to 8-10, and stirring at room temperature or normal temperature for 0.5-1 h at a rotating speed of 1300-1500r/min; obtaining the regulating component C of the inner layer microstructure of the concrete;
4) Preparation of composite solvent D
Firstly, adding alcohol ester-12 (TEXANOL) into polyacrylic emulsion, and stirring and reacting for 5-10 min at the temperature of 50-60 ℃ to form a reticular emulsion film; adding polyvinylpyrrolidone (PVP) and hydrophilic fumed silica, and continuing stirring for 5-10 min at the stirring speed of 500-600 r/min, so as to improve the stability and consistency of the obtained reticular emulsion film, thereby improving the overall film forming toughness of the coating; reducing the temperature to 20-25 ℃, adding methanol and water, and continuously stirring for 10-15 min (150-200 r/min), wherein the whole reaction process is carried out under a sealed condition; obtaining the composite solvent D;
5) Preparing a coating; and adding the composite solvent D, the sacrificial carbonization component A, the intercalation blocking component B on the inner surface of the concrete and the micro-structure regulating component C on the inner layer of the concrete according to a proportion, and stirring at a speed of 800-900 r/min for 50-70 min to obtain the concrete carbonization-resistant coating.
In the scheme, the particle size of the nano titanium dioxide is 20-30 nm; the particle size of the hexagonal boron nitride is 1-2 mu m.
Above-mentioned concrete anti-carbonization coatingThe application method of the material comprises the following steps: coating the concrete carbonization resistant paint prepared according to the scheme on the surface of a concrete structure of which the form is just disassembled, wherein the total coating amount is 400-600 g/m 2 Covering a plastic film after coating, standing for 1-2 d under normal temperature (more than or equal to 15 ℃), and forming an anti-carbonization coating on the concrete surface when each component effectively permeates, namely the coated substrate reaches a surface dry state.
Further, when the ambient temperature exceeds 30 ℃, coating is performed in two times; and coating once when the ambient temperature is 0-30 ℃.
In the scheme, the concrete comprises the following components in parts by weight: 350-500 kg/m of cement 3 100-150 kg/m of fly ash 3 600-720 kg/m of sand (0-5 mm) 3 The amount of stone (5-25 mm) is 950-1250 kg/m 3 180-200 kg/m of water 3 。
The principle of the invention is as follows:
the invention adopts a multiple carbonization-resistant mechanism based on active sacrifice carbonization of the surface layer, intercalation blocking of the inner surface and refinement of the pore structure of the inner surface layer of the concrete:
1) According to the invention, calcium oxide or calcium hydroxide is taken as a main sacrificial carbonization component A, triethanolamine is further introduced for ball milling, so that the dispersion of the calcium oxide or calcium hydroxide in a subsequent solvent is facilitated, and the calcium oxide or calcium hydroxide is promoted to be finally and uniformly distributed on the surface of concrete;
2) The hydroxyl modification is carried out on the hexagonal boron nitride by utilizing concentrated sulfuric acid and potassium permanganate, and meanwhile, the dispersion performance and the permeability of the obtained nano titanium dioxide suspension can be obviously improved by adopting the superplasticizer of the multi-ammonium polyacrylate and combining with an optimized mechanical stirring and ultrasonic process and a pH value regulating means;
the obtained B-OH can be dehydrated and condensed with cement-based material-OH to form stable hydrogen bond, and further form stable combined water layer, and can greatly bind water molecules in solution, and can be deep layer carbon fixation (CO leaked from sacrificial carbon fixation layer) 2 CO penetrating into the inside after the carbon fixing layer is sacrificed to fall off 2 ) Providing a moist environment; in addition, hydroxylated hexagonal boron nitride and nano TiO 2 Is used in combination of (a)The layered structure of square boron nitride is utilized to bind moisture and resist a part of CO 2 At the same time, a part of nano TiO which diffuses to deeper parts inside the concrete is reserved 2 Further ensuring the carbon fixation and anti-fouling effects of the inner surface of the obtained concrete; in addition, the calcium carbonate generated by sacrificing the carbonization component, the inner surface intercalation blocking component and the microstructure regulation and control function of part of nano titanium dioxide are beneficial to promoting the improvement of the wear resistance of the obtained concrete surface layer (the concrete surface is in the depth range of about 1mm inwards);
4) Firstly, adding 12-ester alcohol into polyacrylic emulsion, and carrying out heating and stirring reaction to form a monomolecular reticular emulsion film; then adding polyvinylpyrrolidone (PVP) and hydrophilic fumed silica, continuing stirring treatment, improving the stability and consistency of the obtained emulsion, further improving the overall film-forming toughness of the obtained coating, enabling film-forming components and corresponding carbonization active components to be firmly coated on the surface of the concrete, and increasing the adhesion force with the surface of the concrete; in addition, the strong permeability of the methanol component in the composite solvent D is beneficial to promoting the micro-nano component to permeate into the surface/layer defect of the cement-based material, improving the bonding effect of the micro-nano component and the cement-based material, promoting the formation of a layering modification mechanism based on three types of carbonization-resistant components on the surface layer of the concrete, and reducing the influence of the methanol component on the hydration process of the cement due to the strong volatility after the methanol is assisted in permeation.
Compared with the prior art, the invention has the beneficial effects that:
1) According to the invention, multiple modification mechanisms such as active surface layer sacrificial carbonization, intercalation blocking, surface concrete pore structure refinement and the like are combined, the carbonization resistance of the concrete is optimized from multiple layers such as the outer surface layer of the concrete, the surface of the concrete and the interior of the concrete, and the concrete still can show excellent carbonization resistance under the conditions of breakage, falling and the like of the surface coating in the later period;
2) The lime-based component, the hexagonal boron nitride, the nano titanium dioxide and the like are respectively improved in dispersibility, permeability and the like, so that the dispersion effect of three types of carbonization-resistant components in the whole coating can be ensured, meanwhile, the effective distribution of each carbonization-resistant component on different parts of the outer surface, the surface layer, the inner surface layer and the like of the concrete is facilitated, the obtained concrete can effectively achieve good carbonization resistance, wear resistance (the carbonization-resistant depth can reach 5 mm), acid resistance (still has excellent service performance in an acidic environment) and the like, and good comprehensive durability is shown;
3) The construction process is simple, the operation is convenient, and the service life of the obtained carbonization resistant coating is long, so that the carbonization resistant coating is suitable for popularization and application.
Detailed Description
The invention is not limited to the embodiments described above, but a number of modifications and adaptations can be made by a person skilled in the art without departing from the principle of the invention, which modifications and adaptations are also considered to be within the scope of the invention. What is not described in detail in this specification is prior art known to those skilled in the art.
In the following examples, the superplasticizer, the polyammonium polyacrylate, was provided by Jining Sanshi Biotechnology Co., ltd, and had a molecular weight of 2000 to 5000.
The average grain diameter of the adopted nano titanium dioxide (HL-380) is 20-30 nm; the particle size of the hexagonal boron nitride is 1-2 μm.
Example 1
The preparation method of the concrete anti-carbonization coating comprises the following steps:
1) Preparation of sacrificial carbonization component A
Weighing 48g of calcium oxide and 6g of triethanolamine, putting into a planetary ball mill, uniformly mixing, and running for 10min at the rotating speed of 150r/min to obtain a sacrificial carbonization component A;
2) Preparation of the intercalation barrier component B on the inner surface of the concrete
Weighing 10g of hexagonal boron nitride (h-BN) and 1000g of concentrated sulfuric acid with the concentration of 95%, adding 0.1g of potassium permanganate, uniformly mixing, and performing ultrasonic treatment (the frequency is 20 KHz) for 20min; then put into a high-temperature high-pressure reaction kettle and filled with N 2 Heating to 50 ℃ for reaction for 4 hours; after the reaction was completed, the mixture was centrifuged at 10000 rpm for 20min at a high speed to obtain a bottom solidWashing and filtering the mixture to be neutral (pH=7) for many times by using deionized water, drying the mixture at 80 ℃ for 6 hours, carrying out powder treatment on the cooled solid, and screening the solid by using a 500-mesh fine screen to obtain a component B which can play a role in intercalation blocking in the concrete;
3) Preparing a microstructure regulating component C of the inner surface layer of the concrete;
weighing 4.5g of nano titanium dioxide (NT) and 180g of water, mixing, adding 0.45g of super plasticizer and the poly-ammonium polyacrylate PAA-NH4, and simultaneously mechanically stirring (stirring speed is 400 r/min) and ultrasonically vibrating (frequency is 20 KHz) for 8min to prepare a uniformly dispersed NT suspension; uniformly stirring and mixing the obtained NT suspension with 1500g of ethanol, dropwise adding ammonia water with the mass concentration of 28% to adjust the pH value of the obtained mixed solution to 8, and stirring at constant temperature for 0.5h (1300 r/min) in a water bath environment with the temperature of 20+/-5 ℃; obtaining the concrete surface microstructure regulating and controlling component C;
4) Preparation of composite solvent D
Adding 1g of TEXANOL (12-ester alcohol) into 80g of polyacrylic emulsion, mechanically stirring for 5min (500 r/min) at 50 ℃, adding 1g of polyvinylpyrrolidone (PVP) and 3g of hydrophilic fumed silica HL-380, and continuing stirring for 5min (500 r/min); reducing the temperature to 20 ℃, adding 2g of methanol and 200g of water, continuously stirring for 10min (150 r/min), and performing the whole reaction process in a sealed three-neck flask to obtain the composite solvent D;
5) Preparing a coating; 200g of sacrificial carbonization component A, 100g of concrete inner surface intercalation blocking component B, 50g of concrete inner surface microstructure regulating component C and 1500g of composite solvent D are mixed, and the mixture is stirred for 50min at the speed of 800r/min by using a mechanical stirrer, so that the concrete carbonization-resistant paint is obtained.
Example 2
The preparation method of the concrete anti-carbonization coating comprises the following steps:
1) Preparation of sacrificial carbonization component A
Weighing 54g of calcium oxide and 6g of triethanolamine, putting into a planetary ball mill, uniformly mixing, and operating for 12min at the rotating speed of 180r/min to obtain a sacrificial carbonization component A;
2) Preparation of the intercalation barrier component B on the inner surface of the concrete
Weighing 10g of hexagonal boron nitride (h-BN) and 1100g of concentrated sulfuric acid with the concentration of 98%, adding 0.15g of potassium permanganate, uniformly mixing, and performing ultrasonic treatment (the frequency is 20 KHz) for 20min; then put into a high-temperature high-pressure reaction kettle and filled with N 2 Heating at 60 ℃ for reaction for 5 hours, centrifuging the mixture at 10000 revolutions per minute for 25 minutes after the reaction is finished, taking solid substances at the bottom, washing and filtering the solid substances to be neutral (pH=7) for many times by using deionized water, drying the solid substances at 80 ℃ for 6 hours, carrying out powder treatment on the cooled solid substances, and screening the solid substances by using a 500-mesh fine screen to obtain a component B which can play a role in blocking intercalation in the concrete;
3) Preparing a microstructure regulating component C of the inner surface layer of the concrete;
9g of nano titanium dioxide (NT) and 180g of water are weighed, 1.8g of super plasticizer, namely poly ammonium polyacrylate PAA-NH4, are added after mixing, and simultaneously mechanical stirring (the stirring speed is 500 r/min) and ultrasonic vibration (the frequency is 25 KHz) are carried out for 10min, so that an NT suspension with uniform dispersion is prepared; uniformly stirring and mixing the obtained NT suspension with 1800g of ethanol, dropwise adding ammonia water with the mass concentration of 28% to adjust the pH value of the obtained mixed solution to 9, and stirring at constant temperature for 1h under the water bath environment with the temperature of 20+/-5 ℃ at the rotating speed of 14500r/min; obtaining the concrete surface microstructure regulating and controlling component C;
4) Preparation of composite solvent D
Adding 2g of TEXANOL (12-ester alcohol) into 100g of polyacrylic emulsion, mechanically stirring for 8min (550 r/min) at 55 ℃, adding 2g of polyvinylpyrrolidone (PVP) and 4g of hydrophilic fumed silica HL-380, and continuing stirring for 8min (550 r/min); reducing the temperature to 25 ℃, adding 3g of methanol and 210g of water, continuously stirring for 15min (200 r/min), and performing the whole reaction process in a sealed three-neck flask to obtain the composite solvent D;
5) Preparing a coating; mixing 250g of sacrificial carbonization component A, 150g of concrete inner surface intercalation blocking component B, 70g of concrete inner surface layer microstructure regulating component C and 1800g of composite solvent D, and stirring at a speed of 850r/min for 60min by using a mechanical stirrer to obtain the concrete carbonization-resistant paint.
Example 3
The preparation method of the concrete anti-carbonization coating comprises the following steps:
1) Preparation of sacrificial carbonization component A
Weighing 60g of calcium oxide and 6g of triethanolamine, putting into a planetary ball mill, uniformly mixing, and operating for 15min at the rotating speed of 200r/min to obtain a sacrificial carbonization component A;
2) Preparation of the intercalation barrier component B on the inner surface of the concrete
Weighing 10g of hexagonal boron nitride (h-BN) and 1200g of concentrated sulfuric acid with the concentration of 98%, adding 0.15g of potassium permanganate, uniformly mixing, and performing ultrasonic treatment (the frequency is 20 KHz) for 20min; then put into a high-temperature high-pressure reaction kettle and filled with N 2 Heating to 70 ℃ for reaction for 6 hours, centrifuging the mixture at 10000 revolutions per minute for 30 minutes after the reaction is finished, taking solid substances at the bottom, washing and filtering the solid substances to be neutral (pH=7.5) for many times by using deionized water, drying the solid substances at 80 ℃ for 6 hours, carrying out powder treatment on the cooled solid substances, and screening the solid substances by using a 500-mesh fine screen to obtain a component B which can play a role in intercalation blocking in the concrete;
3) Preparing a microstructure regulating component C of the inner surface layer of the concrete;
13.5g of nano titanium dioxide (NT) and 180g of water are weighed, 2.7g of super plasticizer and poly ammonium polyacrylate PAA-NH4 are added after mixing, and mechanical stirring (stirring speed is 600 r/min) and ultrasonic vibration (frequency is 25 KHz) are carried out for 12min at the same time, so that NT suspension with uniform dispersion is prepared; uniformly stirring and mixing the obtained NT suspension with 2200g of ethanol, dropwise adding ammonia water with the mass concentration of 28% to adjust the pH value of the obtained mixed solution to 10, and stirring at constant temperature for 1h under the water bath environment with the temperature of 20+/-5 ℃ and the rotating speed of 1500r/min; obtaining the concrete surface microstructure regulating and controlling component C;
4) Preparation of composite solvent D
Adding 3g of TEXANOL (12-ester alcohol) into 100g of polyacrylic emulsion, mechanically stirring for 10min (600 r/min) at 60 ℃, adding 2g of polyvinylpyrrolidone (PVP) and 5g of hydrophilic fumed silica HL-380, and continuing stirring for 10min (600 r/min); reducing the temperature to 25 ℃, adding 4g of methanol and 210g of water, continuously stirring for 15min (200 r/min), and performing the whole reaction process in a sealed three-neck flask to obtain the composite solvent D;
5) Preparing a coating; 300g of sacrificial carbonization component A, 200g of intercalation blocking component B on the inner surface of concrete, 100g of micro-structure regulating component C on the inner surface of concrete and 2000g of composite solvent D are mixed, and the mixture is stirred for 70 minutes at the speed of 900r/min by using a mechanical stirrer, so that the concrete carbonization-resistant paint is obtained.
Comparative example 1
The preparation method of the concrete anti-carbonization coating comprises the following steps:
1) Preparation of sacrificial carbonization component A
Weighing 54g of calcium oxide and 6g of triethanolamine, putting into a planetary ball mill, uniformly mixing, and operating for 12min at the rotating speed of 180r/min to obtain a sacrificial carbonization component A;
2) Preparing a concrete inner surface microstructure regulating component B;
9g of nano titanium dioxide (NT) and 180g of water are weighed, 1.8g of super plasticizer, namely poly ammonium polyacrylate PAA-NH4, are added after mixing, and simultaneously mechanical stirring (the stirring speed is 500 r/min) and ultrasonic vibration (the frequency is 25 KHz) are carried out for 10min, so that an NT suspension with uniform dispersion is prepared; uniformly stirring and mixing the obtained NT suspension with 1800g of ethanol, dropwise adding ammonia water to adjust the pH value of the obtained mixed solution to 9, and stirring at constant temperature for 1h under the water bath environment of 20+/-5 ℃ at the rotating speed of 14500r/min; obtaining the concrete surface microstructure regulating and controlling component B;
3) Preparation of composite solvent C
Adding 2g of TEXANOL (12-ester alcohol) into 100g of polyacrylic emulsion, mechanically stirring for 8min (550 r/min) at 55 ℃, adding 2g of polyvinylpyrrolidone (PVP) and 4g of hydrophilic fumed silica HL-380, and continuing stirring for 8min (550 r/min); reducing the temperature to 25 ℃, adding 3g of methanol and 210g of water, continuously stirring for 15min, wherein the stirring speed is 200r/min, and performing the whole reaction process in a sealed three-neck flask to obtain the composite solvent C;
(4) Preparing a coating; mixing 250g of sacrificial carbonization component A, 70g of concrete inner surface microstructure regulation component B and 1800g of composite solvent C, and stirring at a speed of 850r/min for 60min by using a mechanical stirrer to obtain the concrete carbonization resistant paint.
Comparative example 2
The preparation method of the concrete anti-carbonization coating comprises the following steps:
1) Preparation of sacrificial carbonization component A
Weighing 54g of calcium oxide and 6g of triethanolamine, putting into a planetary ball mill, uniformly mixing, and operating for 12min at the rotating speed of 180r/min to obtain a sacrificial carbonization component A;
2) Preparation of the intercalation barrier component B on the inner surface of the concrete
Weighing 10g of hexagonal boron nitride (h-BN) and 1100g of concentrated sulfuric acid with the concentration of 98%, adding 0.15g of potassium permanganate, uniformly mixing, and performing ultrasonic treatment (the frequency is 20 KHz) for 20min; then put into a high-temperature high-pressure reaction kettle and filled with N 2 Heating at 60 ℃ for reaction for 5 hours, centrifuging the mixture at 10000 revolutions per minute for 25 minutes after the reaction is finished, taking solid substances at the bottom, washing and filtering the solid substances to be neutral (pH=7) for many times by using deionized water, drying the solid substances at 80 ℃ for 6 hours, carrying out powder treatment on the cooled solid substances, and screening the solid substances by using a 500-mesh fine screen to obtain a component B which can play a role in blocking intercalation in the concrete;
3) Preparing a microstructure regulating component C of the inner surface layer of the concrete;
9g of nano titanium dioxide (NT) and 180g of water are weighed, 1.8g of super plasticizer, namely poly ammonium polyacrylate PAA-NH4, are added after mixing, and simultaneously mechanical stirring (the stirring speed is 500 r/min) and ultrasonic vibration (the frequency is 25 KHz) are carried out for 10min, so that an NT suspension with uniform dispersion is prepared; uniformly stirring and mixing the obtained NT suspension with 1800g of ethanol, dropwise adding ammonia water to adjust the pH value of the obtained mixed solution to 9, and stirring at constant temperature for 1h under the water bath environment of 20+/-5 ℃ at the rotating speed of 14500r/min; obtaining the concrete surface microstructure regulating and controlling component C;
4) Preparation of composite solvent D
Adding 2g of TEXANOL (12-ester alcohol) into 100g of polyacrylic emulsion, mechanically stirring for 8min (550 r/min) at 55 ℃, adding 2g of polyvinylpyrrolidone (PVP) and 4g of hydrophilic fumed silica HL-380, and continuing stirring for 8min (550 r/min); reducing the temperature to 25 ℃, adding 210g of water, continuously stirring for 15min (200 r/min), and performing the whole reaction process in a sealed three-neck flask to obtain the composite solvent D;
5) Preparing a coating; mixing 250g of sacrificial carbonization component A, 150g of concrete inner surface intercalation blocking component B, 70g of concrete inner surface layer microstructure regulating component C and 1800g of composite solvent D, and stirring at a speed of 850r/min for 60min by using a mechanical stirrer to obtain the concrete carbonization-resistant paint.
Application example 1
The concrete anti-carbonization coating obtained in examples 1-3 and comparative example is applied to the surface treatment of concrete, and comprises the following specific steps of
1) Preparing concrete; weighing the raw materials of the concrete according to the proportion, wherein the raw materials and the dosage thereof are as follows: cement 400 kg/m 3 Fly ash 100 kg/m 3 650kg/m of sand 3 Stone 1050 kg/m 3 Water 1050 kg/m 3 ；
Wherein the cement is P.O42.5 cement, the fly ash is class II fly ash, the sand is 0-5 mm continuous graded river sand, the fineness mode is 2.8, and the stone is 5-20 mm pebble;
uniformly mixing the weighed raw materials, pouring and molding to prepare 100mm multiplied by 400mm cubic concrete test pieces (3 test pieces in each group);
2) Coating treatment is carried out on the concrete test piece
After molding for 1d, removing the mold, and coating the concrete anti-carbonization coating on the surface of the obtained concrete structure, wherein the concrete treatment method and the coating amount are shown in table 1;
3) After coating, covering a plastic film on the surface of the test piece, and standing for 1d at 25 ℃ in a normal temperature environment.
Table 1 coating process parameters of the anti-carbonization coating corresponding to examples 1 to 3 and blank groups and comparative examples 1 to 2
The surface coating modified concrete obtained by adopting different concrete anti-carbonization coatings is respectively subjected to carbonization depth test, abrasion resistance after abrasion, static pressure water penetration and other tests, and the results are as follows:
(1) Testing the carbonization depth of concrete;
performing a concrete rapid carbonization test by referring to GB/T50082, wherein the concentration of carbon dioxide is set to be 20%, the temperature is set to be 20 ℃ and the humidity is set to be 70%; the concrete test blocks obtained by adopting different anti-carbonization coatings are put into a carbonization reaction box for quick carbonization test, the test blocks are taken out in 3d, 28d and 90d, the test blocks are cut, and the measurement of carbonization depth is carried out on a section of 100mm multiplied by 100mm by using a phenolphthalein color developing agent, and the measurement results are shown in table 2:
table 2 depth of carbonization (mm) for each age of concrete of each group
(2) Testing the wear resistance of the concrete;
taking out each test piece subjected to carbonization 28d, cutting a test block with the length of 100mm multiplied by 100mm, putting the test block into a los Angeles abrasion tester for carrying out abrasion resistance test, and testing the mass loss rate of each group of test pieces after 1 h; the test results are shown in Table 3.
Table 3 results of abrasion resistance test for concrete of each group
(3) Testing the carbonization resistance effect of concrete after abrasion of 1mm and 5 mm;
for each group of test pieces after coating, standing still for 3d in a standard curing room (temperature 20 ℃ and humidity 90%) to ensure more sufficient penetration and absorption of the group of coating materials. Manually polishing the coating surfaces of the obtained concrete test piece by 1 and 5mm, and then putting the coating surfaces into a carbonization boxIn the concrete rapid carbonization test according to the carbonization test, referring to GB/T50082, setting the carbon dioxide concentration to be 20%, the temperature to be 20 ℃ and the humidity to be 70%; putting each group of test blocks into a carbonization reaction box for rapid carbonization test, wherein the test blocks are respectively 3 +3 d、28 +3 d、90 +3 d, taking out, cutting each group of test blocks, and measuring carbonization depth by using phenolphthalein developer on a section of 100mm×100mm, wherein the measurement results are shown in tables 4 and 5:
table 4 carbonization depth (mm) at each age after abrasion of 1mm for each group of concrete
Table 5 carbonization depth (mm) at each age after 5mm abrasion of each group of concrete
The results show that the coating obtained in the embodiments 1-3 of the invention can obviously improve the carbonization resistance of the obtained concrete when being coated on the concrete, and has excellent carbonization resistance even after the concrete base material is worn to a certain extent, particularly when the surface is worn to a position of 5 mm. In addition, the obtained concrete has excellent wear resistance and can promote to exert a longer-term and stable protective effect.
The invention is not limited to the embodiments described above, but a number of modifications and adaptations can be made by a person skilled in the art without departing from the principle of the invention, which modifications and adaptations are also considered to be within the scope of the invention. What is not described in detail in this specification is prior art known to those skilled in the art.
Claims (5)
1. The concrete carbonization resistant paint is characterized in that the paint is obtained by compounding a sacrificial carbonization component A, a concrete inner surface intercalation blocking component B, a concrete inner layer microstructure regulating component C and a composite solvent D as main raw materials, wherein:
the sacrificial carbonization component A is obtained by mixing and ball milling a lime-based component and triethanolamine;
the preparation method of the intercalation barrier component B on the inner surface of the concrete comprises the following steps: mixing hexagonal boron nitride with concentrated sulfuric acid and potassium permanganate for ultrasonic treatment, then carrying out heating reaction under protective atmosphere, centrifugally separating, cleaning, drying and cooling;
the preparation steps of the concrete inner layer microstructure regulating component C comprise: dispersing nano titanium dioxide and a superplasticizer, namely the multi-ammonium polyacrylate, in water, stirring and carrying out ultrasonic treatment to obtain a nano titanium dioxide suspension, then adding ethanol, uniformly mixing, adding alkali liquor to adjust the pH value to 8-10, and carrying out stirring reaction under the water bath condition;
the composite solvent D comprises the following components in parts by weight: 80-100 parts of polyacrylic emulsion, 1-3 parts of alcohol ester-12, 3-5 parts of hydrophilic fumed silica, 1-2 parts of polyvinylpyrrolidone, 2-4 parts of methanol and 200-210 parts of water;
the mass ratio of the sacrificial carbonization component A to the concrete inner surface intercalation blocking component B to the concrete inner layer microstructure regulating component C to the composite solvent D is (2-3): (1-2): (0.5-1): (15-20);
the lime-based component is calcium oxide or calcium hydroxide; the mass ratio of the triethanolamine to the triethanolamine is (8-10) 1;
the mass ratio of the hexagonal boron nitride to the concentrated sulfuric acid is 1 (100-120), and the addition amount of the potassium permanganate is 1-1.5% of the mass of the hexagonal boron nitride;
in the preparation process of the intercalation barrier component B on the inner surface of the concrete, the heating reaction step is carried out at 50-70 ℃ for 4-6 hours;
the mass ratio of the nano titanium dioxide to the water is 1 (13-40), and the dosage of the superplasticizer, namely the poly-ammonium polyacrylate, is 10-20% of the mass of the nano titanium dioxide; the mass ratio of the obtained nano titanium dioxide suspension to ethanol is 1 (8-12).
2. The method for preparing the concrete anti-carbonization coating according to claim 1, which is characterized by comprising the following steps:
(1) Preparation of sacrificial carbonization component A
Uniformly mixing the weighed triethanolamine with the lime-based component, and performing ball milling to obtain a sacrificial carbonization component A;
(2) Preparation of the intercalation barrier component B on the inner surface of the concrete
Adding potassium permanganate into the weighed hexagonal boron nitride and concentrated sulfuric acid, uniformly mixing, performing ultrasonic treatment, heating to 50-70 ℃ under protective atmosphere, and reacting for 4-6 hours; centrifuging to obtain solid substances at the bottom, washing with water to neutrality, drying, cooling, and sieving with 500 mesh sieve to obtain the intercalation blocking component B on the inner surface of the concrete;
(3) Preparing a concrete inner layer microstructure regulating component C;
adding super plasticizer multi-ammonium polyacrylate into nano titanium dioxide and water, and carrying out mechanical stirring and ultrasonic treatment to obtain nano titanium dioxide suspension; uniformly mixing the mixed solution with ethanol, dropwise adding an alkaline solution to adjust the pH value of the obtained mixed solution to 8-10, and stirring for reaction; obtaining a regulating component C of the inner layer microstructure of the concrete;
(4) Preparation of composite solvent D
Mixing the weighed polyacrylic emulsion, alcohol ester-12, hydrophilic fumed silica, polyvinylpyrrolidone, methanol and water, and mechanically stirring; obtaining the composite solvent D;
(5) Preparing a coating; and adding the composite solvent D, the sacrificial carbonization component A, the intercalation blocking component B on the inner surface of the concrete and the microstructure regulating component C on the inner surface layer of the concrete according to a proportion, and stirring at a speed of 800-900 r/min for 50-70 min to obtain the concrete carbonization resistant coating.
3. The preparation method of claim 2, wherein the nano titanium dioxide has a particle size of 20-30 nm; the particle size of the hexagonal boron nitride is 1-2 mu m.
4. The concrete anti-carbonization paint according to claim 1 or the application method of the concrete anti-carbonization paint prepared by the preparation method according to any one of claims 2 to 3, characterized by comprising the following steps: and (3) coating the concrete anti-carbonization coating on the surface of the concrete structure of which the demolding is just completed, covering a plastic film after coating, and standing for 1-2 d in a normal temperature environment to form the anti-carbonization coating on the surface of the concrete.
5. The application method according to claim 4, wherein the coating amount of the concrete anti-carbonization coating is 400-600 g/m 2 。
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