CN110698142A - Antifouling corrosion-resistant marine cement and preparation method thereof - Google Patents
Antifouling corrosion-resistant marine cement and preparation method thereof 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
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- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2092—Resistance against biological degradation
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
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Abstract
The invention discloses antifouling corrosion-resistant marine cement and a preparation method thereof, wherein the marine cement is prepared from the following raw materials in parts by weight: 32-48 parts of marine Portland cement clinker, 1-1.5 parts of modified polycarboxylic acid water reducer, 5-15 parts of laver powder, 2-6 parts of garlic powder, 10-15 parts of acrylate, 1-5 parts of silane coupling agent microcapsule, 30-40 parts of basalt broken stone, 3-5 parts of nano silicon dioxide, 0.5-1 part of calcined attapulgite and 10-15 parts of clinker sea sand. The slurry structure prepared from the marine cement product has good compactness and volume stability, and the formed concrete has excellent impermeability, antibacterial property, antifouling property and crosslinking property, and has high chloride ion diffusion resistance and sulfate erosion resistance, thereby meeting the requirements of marine engineering construction.
Description
Technical Field
The invention relates to the technical field of marine engineering building materials, in particular to antifouling corrosion-resistant marine cement and a preparation method thereof.
Background
In recent years, all countries in the world pay attention to the development of ocean resources, and offshore engineering construction of ports, sea ponds, coastal protection, sea-crossing bridges, offshore gas stations and the like in China is developed quickly. The marine environment is a complex corrosive environment, in which seawater itself is a strong corrosive medium, and waves, tides and currents generate low-frequency reciprocating force and impact on building components, and pollutants such as marine microorganisms, attached organisms and metabolites thereof generate direct or indirect acceleration on the corrosion process. Therefore, in order to make the marine engineering construction have a longer service life, the mere improvement of the corrosion prevention effect of cement or concrete is weaker, and the improvement of the impact strength and the antifouling effect while preventing corrosion is also needed. The existing antifouling and corrosion-resistant engineering depends on coating antifouling paint on the outer surface of the building engineering, but people know that the coating is difficult to coat in water and can generate pollution to a certain degree even though the coating is coated, so that the method for coating the paint has certain limitation on the antifouling and corrosion-resistant effect of the marine engineering building, and the antifouling and corrosion-resistant effect of the marine engineering building which needs to be directly formed in water is difficult to realize.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the antifouling and corrosion-resistant marine engineering cement and the preparation method thereof.
The technical scheme of the invention is realized in the following mode:
the antifouling corrosion-resistant marine cement is prepared from the following raw materials in parts by weight: 32-48 parts of marine Portland cement clinker, 1-1.5 parts of modified polycarboxylic acid water reducer, 5-15 parts of laver powder, 2-6 parts of garlic powder, 10-15 parts of acrylate, 1-5 parts of silane coupling agent microcapsule, 30-40 parts of basalt broken stone, 3-5 parts of nano silicon dioxide, 0.5-1 part of calcined attapulgite and 10-15 parts of clinker sea sand.
The preparation method of the modified polycarboxylic acid water reducing agent comprises the following steps: placing a mixed aqueous solution of prenyl polyoxyethylene ether, (methyl) acrylamide carboxyl betaine and allyl trimethyl ammonium chloride in a reaction kettle, heating to 32-38 ℃, and adding hydrogen peroxide; meanwhile, slowly dropwise adding an acrylic acid aqueous solution for 2-3 h and a mixed solution of 2-mercaptopropanol and ferrous sulfate for 2-3 h, and preserving heat for 1-3 h after dropwise adding is finished; and (3) cooling to room temperature after the reaction is finished, and adjusting the pH of the reaction product to 6-7 by using a sodium hydroxide or potassium hydroxide aqueous solution to obtain the modified polycarboxylic acid water reducing agent. Wherein the mass ratio of the prenyl alcohol polyoxyethylene ether, the (methyl) acrylamide carboxyl betaine, the allyl trimethyl ammonium chloride, the acrylic acid, the hydrogen peroxide, the 2-mercaptopropanol and the ferrous sulfate is 10:3:2:42 (0.5-1): 0.25-0.5.
The preparation method of the silane coupling agent microcapsule comprises the following steps: dissolving 20-30 parts by mass of soluble starch and 5-10 parts by mass of water-soluble polymer in 40-60 parts by mass of deionized water, adding 10-20 parts by mass of silane coupling agent, dispersing the mixed solution by a high-speed dispersion machine, and then carrying out spray drying to obtain the silane coupling agent microcapsule. The water-soluble polymer is a combination of polyvinyl alcohol, polyvinylpyrrolidone and polyacrylamide in any proportion; the silane coupling agent is a combination of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3-glycidyl ether propyl methyl diethoxy silane, gamma- (methacryloyloxy) propyl trimethoxy silane, vinyl trimethoxy silane and gamma-mercaptopropyl trimethoxy silane in any proportion.
The clinker sea sand is prepared by cleaning sea sand, drying, mixing the sea sand with rubber powder, ball-milling, treating at 160-180 ℃ for 2-5 h, and standing; then crushing and grinding to obtain particles with the average particle size of less than 100 mu m; mixing the obtained granules with EPS granules; and then ball milling is carried out for 4-8 h, thus obtaining the ball-milling ball.
The preparation method of the marine engineering cement comprises the following steps:
(1) grinding the marine portland cement clinker, the basalt broken stone, the calcined attapulgite and the clinker sea sand by using a cement mill, so that the passing rate of the clinker sea sand passing through a 100-mesh sieve reaches more than 95 percent;
(2) adding the raw materials obtained in the step (1), a modified polycarboxylic acid water reducing agent, laver powder, garlic powder and acrylic ester into a mixing mill, spraying atomized water into the mixing mill, controlling the temperature in the milling process to be 95-110 ℃, adding silane coupling agent microcapsules and nano-silica into the materials discharged from a grinding head of the mixing mill, and uniformly mixing to obtain a semi-finished marine cement product;
(3) conveying the semi-finished marine cement product into a finished product homogenizing silo by a lifter, and homogenizing by air generated at the bottom of the homogenizing silo to obtain the finished marine cement product.
The invention has the beneficial effects that:
the marine engineering portland cement clinker is used as a main body, is prepared by grinding the marine engineering portland cement clinker and a proper amount of natural gypsum, slag powder, fly ash, silica fume powder and the like, has the silica fume content of not more than 5 percent, and has stronger seawater erosion resistance. The modified polycarboxylate superplasticizer used in the invention introduces groups with antifouling and antibacterial functions into the molecular structure of the polycarboxylate superplasticizer, so that the self antibacterial effect of the polycarboxylate superplasticizer can be improved, and the marine cement can be endowed with the antifouling and antibacterial functions; in the antifouling and antibacterial polycarboxylate water reducer, the (methyl) acrylamide carboxyl betaine can inhibit the attachment and breeding of bacteria and microorganisms, the allyl trimethyl ammonium chloride can effectively kill the attached bacteria and microorganisms, the synergistic effect of the allyl trimethyl ammonium chloride and the allyl trimethyl ammonium chloride can simultaneously inhibit and kill the bacteria and the microorganisms, and the inhibition and killing efficiency is improved; the antifouling and antibacterial polycarboxylate superplasticizer is doped into cement, so that the surface of the prepared concrete keeps clean, corrosion of bacteria, microorganisms and metabolites thereof to the concrete can be prevented, and the antifouling and antibacterial performance of the surface of a marine engineering building is improved. The laver and the garlic are rich in polysaccharide, tannic acid, phenolic acid, garlicin and various terpenoids, have good growth inhibition effect on marine organisms, and therefore have good antifouling activity. The laver and the garlic are natural biological materials, are nontoxic, have no harm to marine environment by being used as antifouling functional auxiliary agents, are relatively environment-friendly, and can effectively inhibit marine organisms from climbing on marine engineering buildings. The modified polycarboxylate superplasticizer with antifouling and antibacterial properties is used in combination with the laver and the garlic, so that the cement has excellent antifouling and corrosion-resistant properties, and the surface of the marine engineering building prepared from the modified polycarboxylate superplasticizer has no bacteria and microorganism adhesion, no growth of marine organisms, cleanness and sterility.
The acrylic emulsion is added into the marine cement in a proper amount, so that the cement slurry can have excellent flexural strength, compressive strength and water resistance when the cement is hydrated, and has excellent waterproof performance.
The silane coupling agent microcapsule uses soluble starch and water-soluble polymers as wall materials, the water-soluble wall materials and an oily core material (silane coupling agent) are dispersed at a high speed to form an oil-in-water emulsion, the emulsion is atomized into tiny droplets through an atomizer of a spray dryer, the surface of the droplets is instantly dried to form a film under the action of high-temperature hot air, so that the oily core material is wrapped by the water-soluble wall materials on the surface, and a microcapsule structure is formed. The silane coupling agent microcapsule can be stably stored under the condition of normal-temperature drying, can be stably stored with cement as a part of the cement, when the cement is hydrated, the microcapsule meets water, and the surface water-soluble wall material is dissolved to release the core material silane coupling agent, so that the core material silane coupling agent can be crosslinked in concrete slurry, the inorganic material and the organic material are combined, the adhesion force among the materials is improved, the cement can be hydrated and formed at the same time, other additives are not required to be additionally added, and the construction time is shortened.
In the invention, the basalt broken stone is used as the coarse aggregate, and the basalt broken stone can play a role of a rigid framework and a role of blocking the expansion of micro cracks, thereby improving the strength and the elastic modulus of the concrete, enhancing the volume stability and the durability of the concrete, and the like. In addition, although the apparent density of the basalt is far lower than that of barite, the basalt has good shielding performance on rays due to the characteristics of very stable performance, very compact structure, high compressive strength, good broken stone grain composition and the like, and is not easy to cause phenomena such as segregation and the like when used in concrete. Therefore, the basalt macadam can also play a role in shielding alpha, beta, gamma, X and other rays, the radiation protection function of the ocean engineering building is improved, and the service life is prolonged.
The nano silicon dioxide can greatly improve the hydrophobic property of the cement slurry, so that the formed building engineering has better water resistance. The nanometer silicon dioxide is compounded with slag powder, fly ash, siliceous dust and the like in the marine Portland cement clinker, and the magnitude order difference of microscopic particle size exists, so that the step-by-step micro-filling effect can be exerted; the slurry structure is more compact, and the impermeability and the durability of the material are improved.
Calcined attapulgite is used as an anti-permeability auxiliary agent, and the calcined attapulgite has good adsorption performance and bonding performance due to a special structure, and has multiple purposes. As the crystal lattices in the calcined attapulgite are destroyed, a large amount of silicon oxide and aluminum oxide with volcanic ash activity are generated, the substances react with calcium hydroxide in cement hydration products, and the generated hydrated calcium silicate and hydrated calcium aluminate can fill the pores in the mortar, thereby improving the performance of the mortar, particularly the impermeability.
The sea sand clinker obtained by cleaning and drying the sea sand, and then mixing and grinding the sea sand with the rubber powder and the EPS particles overcomes the problem of high chloride ion concentration of the sea sand, improves the chloride ion permeation resistance of concrete, enables the marine engineering building to use local materials and saves cost.
The marine engineering cement prepared by the raw materials has excellent antifouling and corrosion resistant effects, and the marine engineering building formed by using the cement has the antifouling and corrosion resistant effects from the forming, so that the service life of the marine building is greatly prolonged, the antifouling and corrosion resistant coating does not need to be coated for the second time, and the marine engineering cement is more suitable for quick construction of the marine engineering building. And the building manufactured and molded by the marine cement has higher impermeability, crosslinking property, compactness, volume stability, water resistance and durability, and can still keep longer service life in marine environment.
Detailed Description
In order to describe the present invention in more detail, the present invention will be further described with reference to the following examples.
Example 1
The antifouling corrosion-resistant marine cement is prepared from the following raw materials in parts by weight: 32 parts of marine Portland cement clinker, 1 part of modified polycarboxylic acid water reducing agent, 5 parts of laver powder, 2 parts of garlic powder, 10 parts of acrylate, 1 part of silane coupling agent microcapsule, 30 parts of basalt macadam, 3 parts of nano silicon dioxide, 0.5 part of calcined attapulgite and 10 parts of clinker sea sand.
The preparation method of the modified polycarboxylic acid water reducing agent comprises the following steps: placing a mixed aqueous solution of prenyl polyoxyethylene ether, (methyl) acrylamide carboxyl betaine and allyl trimethyl ammonium chloride in a reaction kettle, heating to 32 ℃, and adding hydrogen peroxide; meanwhile, slowly dripping an aqueous solution of acrylic acid for 3 hours and a mixed solution of 2-mercaptopropanol and ferrous sulfate for 3 hours, and preserving heat for 1 hour after finishing dripping; and (3) cooling to room temperature after the reaction is finished, and adjusting the pH of the reaction product to 6-7 by using a sodium hydroxide or potassium hydroxide aqueous solution to obtain the modified polycarboxylic acid water reducing agent. Wherein the mass ratio of the prenyl alcohol polyoxyethylene ether, the (methyl) acrylamide carboxyl betaine, the allyl trimethyl ammonium chloride, the acrylic acid, the hydrogen peroxide, the 2-mercaptopropanol and the ferrous sulfate is 10:3:2:42:0.5:0.25: 0.25.
The preparation method of the silane coupling agent microcapsule comprises the following steps: dissolving 20 parts by mass of soluble starch and 5 parts by mass of water-soluble polymer in 40 parts by mass of deionized water, adding 10 parts by mass of silane coupling agent, dispersing the mixed solution by a high-speed dispersion machine, and then carrying out spray drying to obtain the silane coupling agent microcapsule. The water-soluble polymer is a combination of polyvinyl alcohol, polyvinylpyrrolidone and polyacrylamide in any proportion; the silane coupling agent is a combination of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3-glycidyl ether propyl methyl diethoxy silane, gamma- (methacryloyloxy) propyl trimethoxy silane, vinyl trimethoxy silane and gamma-mercaptopropyl trimethoxy silane in any proportion.
The clinker sea sand is prepared by cleaning sea sand, drying, mixing the sea sand with rubber powder, ball-milling, treating at 160 ℃ for 5 hours, and standing; then crushing and grinding to obtain particles with the average particle size of less than 100 mu m; mixing the obtained granules with EPS granules; then ball milling is carried out for 4 hours, and the ball milling is obtained.
The preparation method of the marine engineering cement comprises the following steps:
(1) grinding the marine portland cement clinker, the basalt broken stone, the calcined attapulgite and the clinker sea sand by using a cement mill, so that the passing rate of the clinker sea sand passing through a 100-mesh sieve reaches more than 95 percent;
(2) adding the raw materials obtained in the step (1), a modified polycarboxylic acid water reducing agent, laver powder, garlic powder and acrylic ester into a mixing mill, spraying atomized water into the mixing mill, controlling the temperature in the milling process at 95 ℃, adding silane coupling agent microcapsules and nano-silica into the materials discharged from a grinding head of the mixing mill, and uniformly mixing to obtain a semi-finished marine cement product;
(3) conveying the semi-finished marine cement product into a finished product homogenizing silo by a lifter, and homogenizing by air generated at the bottom of the homogenizing silo to obtain the finished marine cement product. The screen allowance of the finished product, namely a 1.18mm screen, is 0.1 percent.
Example 2
The antifouling corrosion-resistant marine cement is prepared from the following raw materials in parts by weight: 40 parts of marine Portland cement clinker, 1.2 parts of modified polycarboxylic acid water reducing agent, 10 parts of laver powder, 4 parts of garlic powder, 12 parts of acrylate, 3 parts of silane coupling agent microcapsule, 35 parts of basalt macadam, 4 parts of nano silicon dioxide, 0.8 part of calcined attapulgite and 12 parts of clinker sea sand.
The preparation method of the modified polycarboxylic acid water reducing agent comprises the following steps: placing a mixed aqueous solution of prenyl polyoxyethylene ether, (methyl) acrylamide carboxyl betaine and allyl trimethyl ammonium chloride in a reaction kettle, heating to 35 ℃, and adding hydrogen peroxide; meanwhile, slowly dripping the aqueous solution of acrylic acid for 2.5h and the mixed solution of 2-mercaptopropanol and ferrous sulfate for 2.5h, and preserving heat for 2h after finishing dripping; and (3) cooling to room temperature after the reaction is finished, and adjusting the pH of the reaction product to 6-7 by using a sodium hydroxide or potassium hydroxide aqueous solution to obtain the modified polycarboxylic acid water reducing agent. Wherein the mass ratio of the prenyl alcohol polyoxyethylene ether, the (methyl) acrylamide carboxyl betaine, the allyl trimethyl ammonium chloride, the acrylic acid, the hydrogen peroxide, the 2-mercaptopropanol and the ferrous sulfate is 10:3:2:42:0.8:0.38: 0.38.
The preparation method of the silane coupling agent microcapsule comprises the following steps: dissolving 25 parts by mass of soluble starch and 8 parts by mass of water-soluble polymer in 50 parts by mass of deionized water, adding 15 parts by mass of silane coupling agent, dispersing the mixed solution by a high-speed dispersion machine, and then carrying out spray drying to obtain the silane coupling agent microcapsule. The water-soluble polymer is a combination of polyvinyl alcohol, polyvinylpyrrolidone and polyacrylamide in any proportion; the silane coupling agent is a combination of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3-glycidyl ether propyl methyl diethoxy silane, gamma- (methacryloyloxy) propyl trimethoxy silane, vinyl trimethoxy silane and gamma-mercaptopropyl trimethoxy silane in any proportion.
The clinker sea sand is prepared by cleaning sea sand, drying, mixing the sea sand with rubber powder, ball-milling, treating at 170 ℃ for 4 hours, and standing; then crushing and grinding to obtain particles with the average particle size of less than 100 mu m; mixing the obtained granules with EPS granules; then ball milling is carried out for 6 hours, and the ball milling is obtained. The screen allowance of the finished product, namely a 1.18mm screen, is 0.1 percent.
The preparation method of the marine engineering cement comprises the following steps:
(1) grinding the marine portland cement clinker, the basalt broken stone, the calcined attapulgite and the clinker sea sand by using a cement mill, so that the passing rate of the clinker sea sand passing through a 100-mesh sieve reaches more than 95 percent;
(2) adding the raw materials obtained in the step (1), a modified polycarboxylic acid water reducing agent, laver powder, garlic powder and acrylic ester into a mixing mill, spraying atomized water into the mixing mill, controlling the temperature in the milling process at 102 ℃, adding silane coupling agent microcapsules and nano-silica into the materials discharged from a grinding head of the mixing mill, and uniformly mixing to obtain a semi-finished marine cement product;
(3) conveying the semi-finished marine cement product into a finished product homogenizing silo by a lifter, and homogenizing by air generated at the bottom of the homogenizing silo to obtain the finished marine cement product.
Example 3
The antifouling corrosion-resistant marine cement is prepared from the following raw materials in parts by weight: 48 parts of marine Portland cement clinker, 1.5 parts of modified polycarboxylic acid water reducing agent, 15 parts of laver powder, 6 parts of garlic powder, 15 parts of acrylate, 5 parts of silane coupling agent microcapsule, 40 parts of basalt macadam, 5 parts of nano silicon dioxide, 1 part of calcined attapulgite and 15 parts of clinker sea sand.
The preparation method of the modified polycarboxylic acid water reducing agent comprises the following steps: placing a mixed aqueous solution of prenyl polyoxyethylene ether, (methyl) acrylamide carboxyl betaine and allyl trimethyl ammonium chloride in a reaction kettle, heating to 38 ℃, and adding hydrogen peroxide; meanwhile, slowly dripping the aqueous solution of acrylic acid for 2 hours and the mixed solution of 2-mercaptopropanol and ferrous sulfate for 2 hours, and preserving heat for 3 hours after finishing dripping; and (3) cooling to room temperature after the reaction is finished, and adjusting the pH of the reaction product to 6-7 by using a sodium hydroxide or potassium hydroxide aqueous solution to obtain the modified polycarboxylic acid water reducing agent. Wherein the mass ratio of the prenyl alcohol polyoxyethylene ether, the (methyl) acrylamide carboxyl betaine, the allyl trimethyl ammonium chloride, the acrylic acid, the hydrogen peroxide, the 2-mercaptopropanol and the ferrous sulfate is 10:3:2:42: 1: 0.5: 0.5.
The preparation method of the silane coupling agent microcapsule comprises the following steps: dissolving 30 parts by mass of soluble starch and 10 parts by mass of water-soluble polymer in 60 parts by mass of deionized water, adding 20 parts by mass of silane coupling agent, dispersing the mixed solution by a high-speed dispersion machine, and then carrying out spray drying to obtain the silane coupling agent microcapsule. The water-soluble polymer is a combination of polyvinyl alcohol, polyvinylpyrrolidone and polyacrylamide in any proportion; the silane coupling agent is a combination of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3-glycidyl ether propyl methyl diethoxy silane, gamma- (methacryloyloxy) propyl trimethoxy silane, vinyl trimethoxy silane and gamma-mercaptopropyl trimethoxy silane in any proportion.
The clinker sea sand is prepared by cleaning sea sand, drying, mixing the sea sand with rubber powder, ball-milling, treating at 180 ℃ for 2 hours, and standing; then crushing and grinding to obtain particles with the average particle size of less than 100 mu m; mixing the obtained granules with EPS granules; then ball milling is carried out for 8 hours, and the ball milling is obtained.
The preparation method of the marine engineering cement comprises the following steps:
(1) grinding the marine portland cement clinker, the basalt broken stone, the calcined attapulgite and the clinker sea sand by using a cement mill, so that the passing rate of the clinker sea sand passing through a 100-mesh sieve reaches more than 95 percent;
(2) adding the raw materials obtained in the step (1), a modified polycarboxylic acid water reducing agent, laver powder, garlic powder and acrylic ester into a mixing mill, spraying atomized water into the mixing mill, controlling the temperature in the milling process at 110 ℃, adding silane coupling agent microcapsules and nano-silica into the materials discharged from a grinding head of the mixing mill, and uniformly mixing to obtain a semi-finished marine cement product;
(3) conveying the semi-finished marine cement product into a finished product homogenizing silo by a lifter, and homogenizing by air generated at the bottom of the homogenizing silo to obtain the finished marine cement product. The screen allowance of the finished product, namely a 1.18mm screen, is 0.2 percent.
Concrete is prepared by using the marine cement finished products obtained in the embodiments 1 to 3, and performance test is carried out, wherein the test results are as follows:
the test results show that the marine sulphoaluminate cement has short coagulation time, high early strength, continuously increased later strength, excellent impermeability, durability and corrosion resistance, and is suitable for the seawater chlorine corrosion resistant environment. The concrete prepared by the method has long-term antifouling effect, has high inhibition rate on green moss and hypha, and can effectively prevent corrosion caused by growth of marine organisms and microorganisms on the surface of a marine engineering building.
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.
Claims (6)
1. The antifouling corrosion-resistant marine cement is characterized by being prepared from the following raw materials in parts by weight: 32-48 parts of marine Portland cement clinker, 1-1.5 parts of modified polycarboxylic acid water reducer, 5-15 parts of laver powder, 2-6 parts of garlic powder, 10-15 parts of acrylate, 1-5 parts of silane coupling agent microcapsule, 30-40 parts of basalt broken stone, 3-5 parts of nano silicon dioxide, 0.5-1 part of calcined attapulgite and 10-15 parts of clinker sea sand.
2. The antifouling corrosion-resistant marine cement as claimed in claim 1, wherein the modified polycarboxylic acid water reducing agent is prepared by the following steps: placing a mixed aqueous solution of prenyl polyoxyethylene ether, (methyl) acrylamide carboxyl betaine and allyl trimethyl ammonium chloride in a reaction kettle, heating to 32-38 ℃, and adding hydrogen peroxide; meanwhile, slowly dropwise adding an acrylic acid aqueous solution for 2-3 h and a mixed solution of 2-mercaptopropanol and ferrous sulfate for 2-3 h, and preserving heat for 1-3 h after dropwise adding is finished; and (3) cooling to room temperature after the reaction is finished, and adjusting the pH of the reaction product to 6-7 by using a sodium hydroxide or potassium hydroxide aqueous solution to obtain the modified polycarboxylic acid water reducing agent.
3. The antifouling corrosion-resistant marine cement as claimed in claim 2, wherein the modified polycarboxylate water reducer comprises prenyl polyoxyethylene ether, (meth) acrylamide carboxyl betaine, allyl trimethyl ammonium chloride, acrylic acid, hydrogen peroxide, 2-mercaptopropanol and ferrous sulfate in a mass ratio of 10:3:2:42 (0.5-1): 0.25-0.5).
4. The antifouling corrosion-resistant marine cement according to claim 1, wherein said silane coupling agent microcapsule is prepared by the following steps: dissolving 20-30 parts by mass of soluble starch and 5-10 parts by mass of water-soluble polymer in 40-60 parts by mass of deionized water, adding 10-20 parts by mass of silane coupling agent, dispersing the mixed solution by using a high-speed dispersion machine, and then carrying out spray drying to obtain silane coupling agent microcapsules; the water-soluble polymer is a combination of polyvinyl alcohol, polyvinylpyrrolidone and polyacrylamide in any proportion; the silane coupling agent is a combination of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3-glycidyl ether propyl methyl diethoxy silane, gamma- (methacryloyloxy) propyl trimethoxy silane, vinyl trimethoxy silane and gamma-mercaptopropyl trimethoxy silane in any proportion.
5. The antifouling corrosion-resistant marine cement as claimed in claim 1, wherein the clinker sea sand is prepared by washing sea sand, drying, mixing the sea sand with rubber powder, ball-milling, treating at 160-180 ℃ for 2-5 h, and standing; then crushing and grinding to obtain particles with the average particle size of less than 100 mu m; mixing the obtained granules with EPS granules; and then ball milling is carried out for 4-8 h, thus obtaining the ball-milling ball.
6. The antifouling corrosion-resistant marine cement according to claim 1, wherein the preparation method of the marine cement comprises the following steps:
(1) grinding the marine portland cement clinker, the basalt broken stone, the calcined attapulgite and the clinker sea sand by using a cement mill, so that the passing rate of the clinker sea sand passing through a 100-mesh sieve reaches more than 95 percent;
(2) adding the raw materials obtained in the step (1), a modified polycarboxylic acid water reducing agent, laver powder, garlic powder and acrylic ester into a mixing mill, spraying atomized water into the mixing mill, controlling the temperature in the milling process to be 95-110 ℃, adding silane coupling agent microcapsules and nano-silica into the materials discharged from a grinding head of the mixing mill, and uniformly mixing to obtain a semi-finished marine cement product;
(3) conveying the semi-finished marine cement product into a finished product homogenizing silo by a lifter, and homogenizing by air generated at the bottom of the homogenizing silo to obtain the finished marine cement product.
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