CN113548849A - Marine engineering self-protection concrete and preparation method thereof - Google Patents

Marine engineering self-protection concrete and preparation method thereof Download PDF

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CN113548849A
CN113548849A CN202110670649.4A CN202110670649A CN113548849A CN 113548849 A CN113548849 A CN 113548849A CN 202110670649 A CN202110670649 A CN 202110670649A CN 113548849 A CN113548849 A CN 113548849A
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parts
powder
concrete
mixing
calcium carbonate
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CN113548849B (en
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冯云龙
夏京亮
孟广成
肖瑶
王晶
周永祥
许贺
程晓来
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China Road and Bridge Corp
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China Road and Bridge Corp
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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
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/047—Zeolites
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/14—Minerals of vulcanic origin
    • C04B14/16—Minerals of vulcanic origin porous, e.g. pumice
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/26—Carbonates
    • C04B14/28—Carbonates of calcium
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08—Flue dust, i.e. fly ash
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C04B18/141—Slags
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C04B18/146—Silica fume
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02—Treatment
    • C04B20/023—Chemical treatment
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02—Treatment
    • C04B20/04—Heat treatment
    • 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
    • C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/67—Biocides
    • C—CHEMISTRY; METALLURGY
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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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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
    • C04B2111/24—Sea water resistance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Civil Engineering (AREA)
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  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention relates to a marine self-protection concrete and a preparation method thereof, comprising the following components of 200-cement 400kg/m380-150kg/m of fly ash340-80kg/m mineral powder3Micro silica fume 20-40kg/m3650-sand 850kg/m3900-3150-180kg/m water30.5-1.5kg/m of polycarboxylic acid water reducing agent3The compact improving material is 20-40kg/m310-20kg/m of super-hydrophobic harmful ion isolation material35-10kg/m of anti-pollution biological corrosive agent3. The compactness of the solidified concrete is effectively improved by adding the compact improving material into the concrete, the corrosion resistance of the concrete is favorably improved, harmful ions in a marine environment can be isolated from the concrete by adding the super-hydrophobic harmful ion isolating material, the additional corrosion damage caused by the harmful ions is reduced, the added anti-pollution biological corrosive agent avoids the biological corrosion caused by the marine environment, and the integral corrosion resistance and durability of the concrete are improved.

Description

Marine engineering self-protection concrete and preparation method thereof
Technical Field
The invention relates to functional concrete and a preparation method thereof, in particular to marine engineering self-protection concrete suitable for a marine engineering environment and a preparation method thereof.
Background
The durability of marine concrete is a problem generally concerned by people in nearly half a century, and the rot candle problem of marine concrete structural engineering is increasingly prominent due to the complex diversity of marine environments, such as seawater soaking, sea wave scouring and the intervention of various rot candle ions, and the safety and the durability of engineering facilities are seriously damaged. Therefore, the problem of corrosion protection of marine concrete structures is becoming increasingly important. In the marine concrete construction engineering, the organic external protective coating is the most common technical measure for improving the durability, however, the external protective coating only builds a protective layer on the surface of the concrete, the durability of the interior of the concrete is not essentially improved, and once the organic external protective coating is aged and damaged, the durability of the marine concrete is greatly challenged. Therefore, it is important to invent an internal protection concrete to improve the inherent corrosion protection capability of the concrete and enhance the durability of the concrete.
In view of the defects of the durability of the existing marine concrete, the inventor develops a marine self-protection concrete and a preparation method thereof by researching and innovating based on years of rich experience and professional knowledge of the materials and matching with theoretical analysis, and improves the durability of the concrete by improving the internal performance of the concrete.
Disclosure of Invention
The invention aims to provide marine self-protection concrete suitable for marine environment, which has inherent corrosion protection capability through component optimization.
The technical purpose of the invention is realized by the following technical scheme:
the invention provides a marine self-protection concrete which comprises the following components of 200-cement 400kg/m380-150kg/m of fly ash340-80kg/m mineral powder3Micro silica fume 20-40kg/m3650-sand 850kg/m3900-3150-180kg/m water30.5-1.5kg/m of polycarboxylic acid water reducing agent3The compact improving material is 20-40kg/m310-20kg/m of super-hydrophobic harmful ion isolation material35-10kg/m of anti-pollution biological corrosive agent3(ii) a In another scheme, the marine self-protective concrete provided by the invention is a mixture formed according to the scheme and formed by converting the components into weight ratios.
Preferably, wherein the compaction improving material is prepared by a process,
(1) selecting calcium carbonate powder, placing the calcium carbonate powder in an airflow type mixer, heating, spraying methacryloxypropyl trimethoxy silane, mixing at constant temperature, and carrying out surface modification on the calcium carbonate powder;
(2) selecting superfine pumice powder, mixing the surface modified calcium carbonate powder prepared in the step (1) with the superfine pumice powder, heating in the mixing process, and cooling to room temperature to obtain the compact and improved material.
Preferably, the specific steps for preparing the compaction improving material are as follows:
(1) calcium carbonate powder is selected, and the main components of the calcium carbonate powder are Ca 050-550 wt% and Fe2O3<2wt％，SO3<0.25 wt%, the fluidity ratio of 0.5-1.5 mu m of fineness is 110-120%, and the calcium carbonate powder has larger fineness, so that the calcium carbonate powder can play a good role in reducing water and improve the fluidity of slurry in the presence of a polycarboxylic acid water reducing agent;
(2) the method comprises the steps of placing calcium carbonate powder in an airflow type mixer, heating to 150-160 ℃, keeping for 5-6min, spraying methacryloxypropyl trimethoxysilane accounting for 0.3-6% of the mass of the calcium carbonate powder, mixing at a constant temperature for 10-15min, cooling at a cooling speed of 10-20 ℃/h, carrying out surface modification on the calcium carbonate powder, heating at 150-160 ℃ for 5-6min to well reduce the water content and impurities of the calcium carbonate powder, spraying the methacryloxypropyl trimethoxysilane at the temperature, enabling the methacryloxypropyl trimethoxysilane to be well attached to the surfaces of calcium carbonate particles, and when the powder is added into cement slurry, utilizing the hydrophobic property of the methacryloxypropyl trimethoxysilane to better disperse in the slurry, the calcium carbonate powder is not agglomerated due to the excessive fineness, so that the effect of the dense concrete is not influenced;
(3) selecting superfine pumice powder, wherein the main component control indexes comprise: SiO 2245～55wt％，Al2O315～25wt％，Fe2O35-15 wt%, CaO 3-8 wt%, and loss on ignition<4.5 percent, the fineness is 2.5-4.5 mu m, and the fluidity ratio is 100-110 percent; the pumice powder is a natural pozzolanic material with high activity, and meanwhile, the microstructure is porous, so that when the pumice powder is ground to the particle size of 2.5-4.5, the pumice powder can play a good role in pozzolanic activity and has a secondary hydration reaction with a cement hydration product calcium hydroxide, thereby generating hydrated calcium silicate and playing a role in compacting cement slurry; in addition, the microscopic structure of the pumice powderThe porous material can be well combined with calcium carbonate powder, and plays a role in coupling and superposition;
(4) mixing the modified calcium carbonate powder prepared in the step (2) with the superfine pumice powder prepared in the step (3) according to a mass ratio of 8: 2-6: 4, uniformly mixing in an airflow mixer, heating at the temperature of 200-260 ℃ in the mixing process, heating and mixing for 10-15min, and cooling to room temperature to obtain the compact and improved material.
Preferably, the super-hydrophobic harmful ion isolation material is prepared by the following method,
A1. preparing modified zeolite powder;
A2. adding 1-2 parts of sodium dodecyl sulfate and 1-2 parts of sodium bicarbonate into 80-85 parts of water, stirring for dissolving, adding 20-30 parts of 2-methyl methacrylate and 5-10 parts of methyl vinyl chlorosilane, and uniformly stirring to obtain an emulsion; the lauryl sodium sulfate is an anionic surfactant and is used as an emulsifier, the sodium bicarbonate is alkaline and can excite the activity of zeolite powder to compact the pore structure of concrete, the methyl vinyl chlorosilane can uniformly disperse the zeolite powder with fine fineness in concrete slurry and can simultaneously enable concrete micropores to present a hydrophobic effect, and the micropores are relatively dry and prevent harmful ions from permeating into the concrete through the micropores.
A3. Stirring 0.2-0.4 part of ammonium disulfate, 2-5 parts of sodium dodecyl sulfate, 10-15 parts of the emulsified emulsion obtained in the step A2 and 80-85 parts of the modified zeolite powder obtained in the step A1 together, heating and cooling to room temperature, and drying to obtain the super-hydrophobic harmful ion isolation material.
Preferably, the step A1 of preparing the modified zeolite powder comprises the specific steps of adding 100-150 parts of superfine zeolite powder into 100-120 parts of ethanol, and uniformly stirring to obtain an alcohol solution of the zeolite powder; adding 5-10 parts of silane coupling agent into 50-80 parts of distilled water and 5-8 parts of ethanol for dilution to obtain silane coupling agent hydrolysate; mixing 80-90 parts of alcoholic solution of zeolite powder and 10-20 parts of silane coupling agent hydrolysate in a container with a heating function, adding 0.3-0.5 part of aminoethanesulfinic acid and 0.3-0.8 part of saturated calcium hydroxide solution, heating to 80-85 ℃, mixing for 1-1.5 h, filtering, and drying to obtain the modified zeolite powder.
Preferably, the anti-fouling bioerodible agent is prepared by a process,
s1, uniformly mixing 40-50 parts of copper sulfate, 10-15 parts of nano silver powder, 5-10 parts of tetrapropylene sodium benzenesulfonate, 5-8 parts of naphthalene sulfonate formaldehyde condensate and 2-5 parts of dibenzoyl peroxide; the copper sulfate and the nano silver powder which can inhibit the growth of the microorganisms can be better dispersed in the concrete by mixing the tetrapropylene sodium benzenesulfonate, the naphthalenesulfonate formaldehyde condensate and the dibenzoyl peroxide with the copper sulfate and the nano silver powder, so that the growth of the microorganisms can be inhibited more favorably.
S2, performing pressure steaming on the powder uniformly mixed in the step S1 at 180-220 ℃ under 1.5-2 atmospheric pressures for 2-2.5 hours to obtain the anti-pollution biological corrosive agent, and enabling copper sulfate and nano silver powder to be mutually embedded and extruded through high temperature and high pressure to achieve a coupling strengthening effect.
Preferably, wherein the silica fume SiO is micro-silica fume2The content is more than 95 percent, and the specific surface area is 10000m2More than kg, has good volcanic ash activity and superfine filling effect, and improves the compactness of the concrete, thereby improving the corrosion resistance of the concrete.
Preferably, the sand in the area II is adopted, the fineness modulus is 2.5-3.2, the prepared concrete has good working performance, and the construction of the concrete is facilitated, so that the compact anti-corrosion effect is achieved.
Preferably, the macadam is graded in a 5-25 continuous mode, the particle shape is smooth, the crushing value is less than 10%, and the prepared concrete has good working performance, high mechanical property and good corrosion resistance.
Preferably, the cement is 42.5 maritime work Portland cement, cement C3S content less than 50%, C2The S content is more than 35 percent, the early strength is relatively slowly increased when the concrete is prepared, but the later strength is continuously increased, and the corrosion resistance of the concrete is good.
Preferably, the fly ash is high-quality fly ash with the fineness of less than 12%, the water demand ratio of less than 95% and the 28d activity index of more than 78%.
Preferably, the specific surface area of the ore powder is more than 600m2/kg, 28d activity index is more than 100 percent.
Preferably, the polycarboxylic acid water reducing agent is an ester polycarboxylic acid high-performance water reducing agent, the solid content is 25-30%, the water reducing rate is more than 30%, and the water consumption of the concrete can be reduced, so that harmful pores in the concrete are reduced, and the corrosion resistance of the concrete is improved.
The invention also aims to provide a preparation method of the marine self-protection concrete.
The technical effects of the invention are realized by the following technical scheme:
the preparation method of the marine self-protection concrete provided by the invention specifically comprises the following operation steps:
s1, firstly, weighing cement, fly ash, mineral powder and micro-silica ash, and then putting the materials into a forced mixer to mix for 30-45 seconds;
s2, simultaneously mixing the polycarboxylic water reducer, the compaction improving material, the super-hydrophobic harmful ion isolating material, the anti-pollution biological corrosive agent and water for 1.5-2min by using a small stirrer;
s3, injecting the liquid uniformly mixed with the S2 into the powder uniformly mixed with the S1, and mixing for 30-45 seconds to form a uniform suspension;
s4, injecting the weighed sand and gravel into the suspension mixed by the S3, and mixing for 30-45 seconds to form a marine self-protection concrete mixture;
s5, injecting the marine self-protection concrete mixture into the concrete template which is well lifted, and vibrating the concrete by adopting a vibrating rod or a flat vibrator to remove redundant air bubbles in the concrete;
s6, curing the poured and vibrated concrete with a mold for 2-4 days, then removing the mold, curing for more than 14 days by adopting a water-retaining curing film, and performing attention on heat preservation and moisture preservation in the process to ensure that the performance of the concrete is well developed.
Preferably, wherein the cement is 200-400kg/m380-150kg/m of fly ash340-80kg/m mineral powder3Micro silica fume 20-40kg/m3650-sand 850kg/m3900-3150-180kg/m water30.5-1.5kg/m of polycarboxylic acid water reducing agent3The compact improving material is 20-40kg/m310-20kg/m of super-hydrophobic harmful ion isolation material35-10kg/m of anti-pollution biological corrosive agent3。
Preferably, wherein the compaction improving material is a self-made material, prepared by a process,
(1) selecting calcium carbonate powder, placing the calcium carbonate powder in an airflow type mixer, heating, spraying methacryloxypropyl trimethoxy silane, mixing at constant temperature, and carrying out surface modification on the calcium carbonate powder;
(2) selecting superfine pumice powder, mixing the surface modified calcium carbonate powder prepared in the step (1) with the superfine pumice powder, heating in the mixing process, and cooling to room temperature to obtain the compact and improved material.
Preferably, the specific steps for preparing the compaction improving material are as follows:
(1) calcium carbonate powder is selected, and the main components of the calcium carbonate powder are Ca 050-550 wt% and Fe2O3<2wt％，SO3<0.25 wt%, the fluidity ratio of 0.5-1.5 mu m of fineness is 110-120%, and the calcium carbonate powder has larger fineness, so that the calcium carbonate powder can play a good role in reducing water and improve the fluidity of slurry in the presence of a polycarboxylic acid water reducing agent;
(2) the method comprises the steps of placing calcium carbonate powder in an airflow type mixer, heating to 150-160 ℃, keeping for 5-6min, spraying methacryloxypropyl trimethoxysilane accounting for 0.3-6% of the mass of the calcium carbonate powder, mixing at a constant temperature for 10-15min, cooling at a cooling speed of 10-20 ℃/h, carrying out surface modification on the calcium carbonate powder, heating at 150-160 ℃ for 5-6min to well reduce the water content and impurities of the calcium carbonate powder, spraying the methacryloxypropyl trimethoxysilane at the temperature, enabling the methacryloxypropyl trimethoxysilane to be well attached to the surfaces of calcium carbonate particles, and when the powder is added into cement slurry, utilizing the hydrophobic property of the methacryloxypropyl trimethoxysilane to better disperse in the slurry, the calcium carbonate powder is not agglomerated due to the excessive fineness, so that the effect of the dense concrete is not influenced;
(3) selecting superfine pumice powder, wherein the main component control indexes comprise: SiO 2245～55wt％，Al2O315～25wt％，Fe2O35-15 wt%, CaO 3-8 wt%, and loss on ignition<4.5 percent, the fineness is 2.5-4.5 mu m, and the fluidity ratio is 100-110 percent; the pumice powder is a natural pozzolanic material with high activity, and meanwhile, the microstructure is porous, so that when the pumice powder is ground to the particle size of 2.5-4.5, the pumice powder can play a good role in pozzolanic activity and has a secondary hydration reaction with a cement hydration product calcium hydroxide, thereby generating hydrated calcium silicate and playing a role in compacting cement slurry; in addition, because the pumice powder is micro-porous, the pumice powder can be well combined with calcium carbonate powder, and a coupling and overlapping effect is achieved;
(4) mixing the modified calcium carbonate powder prepared in the step (2) with the superfine pumice powder prepared in the step (3) according to a mass ratio of 8: 2-6: 4, uniformly mixing in an airflow mixer, heating at the temperature of 200-260 ℃ in the mixing process, heating and mixing for 10-15min, and cooling to room temperature to obtain the compact and improved material.
Preferably, the super-hydrophobic harmful ion isolation material is a self-made material, and is prepared by the following method,
A1. preparing modified zeolite powder;
A2. adding 1-2 parts of sodium dodecyl sulfate and 1-2 parts of sodium bicarbonate into 80-85 parts of water, stirring for dissolving, adding 20-30 parts of 2-methyl methacrylate and 5-10 parts of methyl vinyl chlorosilane, and uniformly stirring to obtain an emulsion; the lauryl sodium sulfate is an anionic surfactant and is used as an emulsifier, the sodium bicarbonate is alkaline and can excite the activity of zeolite powder to compact the pore structure of concrete, the methyl vinyl chlorosilane can uniformly disperse the zeolite powder with fine fineness in concrete slurry and can simultaneously enable concrete micropores to present a hydrophobic effect, and the micropores are relatively dry and prevent harmful ions from permeating into the concrete through the micropores.
A3. Stirring 0.2-0.4 part of ammonium disulfate, 2-5 parts of sodium dodecyl sulfate, 10-15 parts of the emulsified emulsion obtained in the step A2 and 80-85 parts of the modified zeolite powder obtained in the step A1 together, heating and cooling to room temperature, and drying to obtain the super-hydrophobic harmful ion isolation material.
Preferably, the step A1 of preparing the modified zeolite powder comprises the specific steps of adding 100-150 parts of superfine zeolite powder into 100-120 parts of ethanol, and uniformly stirring to obtain an alcohol solution of the zeolite powder; adding 5-10 parts of silane coupling agent into 50-80 parts of distilled water and 5-8 parts of ethanol for dilution to obtain silane coupling agent hydrolysate; mixing 80-90 parts of alcoholic solution of zeolite powder and 10-20 parts of silane coupling agent hydrolysate in a container with a heating function, adding 0.3-0.5 part of aminoethanesulfinic acid and 0.3-0.8 part of saturated calcium hydroxide solution, heating to 80-85 ℃, mixing for 1-1.5 h, filtering, and drying to obtain the modified zeolite powder.
Preferably, the anti-fouling biological corrosive agent is a self-made material and is prepared by the following method,
s1, uniformly mixing 40-50 parts of copper sulfate, 10-15 parts of nano silver powder, 5-10 parts of tetrapropylene sodium benzenesulfonate, 5-8 parts of naphthalene sulfonate formaldehyde condensate and 2-5 parts of dibenzoyl peroxide; the copper sulfate and the nano silver powder which can inhibit the growth of the microorganisms can be better dispersed in the concrete by mixing the tetrapropylene sodium benzenesulfonate, the naphthalenesulfonate formaldehyde condensate and the dibenzoyl peroxide with the copper sulfate and the nano silver powder, so that the growth of the microorganisms can be inhibited more favorably.
S2, performing pressure steaming on the powder uniformly mixed in the step S1 at 180-220 ℃ under 1.5-2 atmospheric pressures for 2-2.5 hours to obtain the anti-pollution biological corrosive agent, and enabling copper sulfate and nano silver powder to be mutually embedded and extruded through high temperature and high pressure to achieve a coupling strengthening effect.
Preferably, wherein the silica fume SiO is micro-silica fume2The content is 95 percentUpper, specific surface area 10000m2More than kg, has good volcanic ash activity and superfine filling effect, and improves the compactness of the concrete, thereby improving the corrosion resistance of the concrete.
Preferably, the sand in the area II is adopted, the fineness modulus is 2.5-3.2, the prepared concrete has good working performance, and the construction of the concrete is facilitated, so that the compact anti-corrosion effect is achieved.
Preferably, the macadam is graded in a 5-25 continuous mode, the particle shape is smooth, the crushing value is less than 10%, and the prepared concrete has good working performance, high mechanical property and good corrosion resistance.
Preferably, the cement is 42.5 maritime work Portland cement, cement C3S content less than 50%, C2The S content is more than 35 percent, the early strength is relatively slowly increased when the concrete is prepared, but the later strength is continuously increased, and the corrosion resistance of the concrete is good.
Preferably, the fly ash is high-quality fly ash with the fineness of less than 12%, the water demand ratio of less than 95% and the 28d activity index of more than 78%.
Preferably, the specific surface area of the ore powder is more than 600m2/kg, 28d activity index is more than 100 percent.
Preferably, the polycarboxylic acid water reducing agent is an ester polycarboxylic acid high-performance water reducing agent, the solid content is 25-30%, the water reducing rate is more than 30%, the water consumption of the concrete can be reduced, harmful pores in the concrete are reduced, and the corrosion resistance of the concrete is improved:
in conclusion, the invention has the following beneficial effects:
1. the powder part in the marine self-protection concrete consists of cement, fly ash, mineral powder and micro-silica fume, wherein the specific surface area of the cement is 300m2About one kilogram of fly ash, the fly ash is 400m2About 500m of mineral powder per kg2About/kg, and micro silica fume over 10000m2Kg, the particles with smaller particle size fill the pores between large particles, the powder with different particle sizes fill each other to form effective particle size grading superposition, and in additionOn one hand, cement hydration generates a large amount of calcium hydroxide, and fly ash, mineral powder and silica fume with volcanic ash activity can generate secondary hydration reaction with the cement, so that calcium hydroxide is consumed, and calcium silicate hydrate and calcium aluminate hydrate are generated, thereby further compacting the pore structure of the concrete, improving the compactness of the concrete, and enhancing the capability of the concrete for resisting harmful ions entering the concrete to erode the concrete.
2. The concrete compaction improving material researched and developed on the basis of calcium carbonate powder has larger fineness, can play a good role in reducing water in the presence of a polycarboxylic acid water reducing agent, and improves the fluidity of slurry; the water content and impurities of the calcium carbonate powder can be well reduced by heating at 150-160 ℃ for 5-6min, methacryloxypropyltrimethoxysilane is sprayed at the temperature, the methacryloxypropyltrimethoxysilane can be well attached to the surface of calcium carbonate particles, when the powder is added into cement slurry, the powder can be better dispersed in the slurry by utilizing the hydrophobic property of the methacryloxypropyltrimethoxysilane, and the calcium carbonate powder cannot be agglomerated due to overlarge fineness, so that the effect of dense concrete is influenced; the pumice powder is a natural pozzolanic material with high activity, and meanwhile, the microstructure is porous, so that when the pumice powder is ground to the particle size of 2.5-4.5, the pumice powder can play a good role in pozzolanic activity and has a secondary hydration reaction with a cement hydration product calcium hydroxide, thereby generating hydrated calcium silicate and playing a role in compacting cement slurry; in addition, because the pumice powder is micro-porous, the pumice powder can be well combined with calcium carbonate powder, and a coupling and overlapping effect is achieved.
3. The super-hydrophobic harmful ion isolation material is prepared from zeolite powder with high volcanic ash activity, an alkaline activator sodium bicarbonate, an anionic surfactant sodium dodecyl sulfate, 2-methyl methacrylate and methyl vinyl chlorosilane, wherein the sodium dodecyl sulfate is used as the anionic surfactant and is used as an emulsifier, the sodium bicarbonate is alkaline and can activate the activity of the zeolite powder, the pore structure of concrete is compacted, the methyl vinyl chlorosilane can uniformly disperse the zeolite powder with fine fineness in concrete slurry, simultaneously can enable concrete micropores to have a hydrophobic effect, and the micropores are relatively dry, so that harmful ions are prevented from permeating into the concrete through the micropores.
4. The anti-pollution biological corrosive agent utilizes the inhibition effect of copper sulfate and nano silver powder on the growth of microorganisms to make the microorganisms difficult to produce on the surface of concrete quickly, so as to protect the concrete. In addition, copper sulfate and nano silver powder can be mutually embedded and extruded through high temperature and high pressure, so that the coupling strengthening effect is achieved.
5. According to the maritime work self-protection concrete and the preparation method thereof provided by the invention, the compactness improving material is added into the concrete to effectively improve the compactness of the concrete after being cured, so that the corrosion resistance of the concrete is favorably improved, meanwhile, the super-hydrophobic harmful ion isolation material is added to isolate harmful ions in a maritime work environment from the concrete, the additional corrosion damage caused by the harmful ions is reduced, meanwhile, the added anti-pollution biological corrosive agent avoids biological corrosion caused by the maritime work environment, and the overall corrosion resistance and durability of the concrete are improved.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the concrete for marine engineering and the preparation method thereof according to the present invention, the specific embodiments, the characteristics and the effects thereof are described in detail as follows.
The commercial sources of materials employed in the present invention are as follows:
cement: zhejiang san Shi group Special Cement Co Ltd
Fly ash: jian and Jian building materials Co Ltd
Mineral powder: jian and Jian building materials Co Ltd
Micro silica fume: jian and Jian building materials Co Ltd
Sand: jian and Jian building materials Co Ltd
Crushing stone: jian and Jian building materials Co Ltd
Polycarboxylic acid water reducing agent: jian and Jian building materials Co Ltd
Calcium carbonate powder: jian and Jian building materials Co Ltd
Methacryloxypropyl trimethoxysilane: jian and Jian building materials Co Ltd
Ultrafine pumice powder: jian and Jian building materials Co Ltd
Ethanol: jian and Jian building materials Co Ltd
Silane coupling agent: jian and Jian building materials Co Ltd
Distilled water: self-made
Aminoethanesulfinic acid: beijing Jianyankunlun technologies, Inc
Saturated calcium hydroxide solution: beijing Jianyankunlun technologies, Inc
Sodium lauryl sulfate: beijing Jianyankunlun technologies, Inc
Sodium bicarbonate: beijing Jianyankunlun technologies, Inc
2-methyl methacrylate: beijing Jianyankunlun technologies, Inc
Methyl vinyl chlorosilane: beijing Jianyankunlun technologies, Inc
Ammonium disulfate: beijing Jianyankunlun technologies, Inc
Copper sulfate: beijing Jianyankunlun technologies, Inc
Nano silver powder: jian and Jian building materials Co Ltd
Sodium tetrapropylene benzenesulfonate: jian and Jian building materials Co Ltd
Naphthalene sulfonate formaldehyde condensate: jian and Jian building materials Co Ltd
Dibenzoyl peroxide: jian and Jian building materials Co Ltd
Example 1
The marine self-protection concrete comprises the following components of 200kg/m of cement380kg/m of fly ash360kg/m of mineral powder3Micro silica fume 25kg/m3650kg/m of sand31000kg/m of crushed stone3150kg/m of water30.5kg/m of polycarboxylic acid water reducing agent3Compaction improving material 30kg/m3Super-hydrophobic harmful ion isolation material12kg/m38kg/m of anti-pollution biological corrosive agent3。
The specific preparation method of the marine self-protection concrete comprises the following steps:
firstly, preparing a compaction improving material
(1) Weighing 24kg of calcium carbonate powder, placing the calcium carbonate powder in an airflow type mixer, heating to 150 ℃ for 5min, then spraying methacryloxypropyl trimethoxy silane accounting for 6% of the mass of the calcium carbonate powder, mixing at constant temperature for 15min, then cooling at the cooling speed of 20 ℃/h, and carrying out surface modification on the calcium carbonate powder.
(2) Weighing 6kg of superfine pumice powder, and mixing the modified calcium carbonate powder obtained in the step (1) with the weighed superfine pumice powder according to a mass ratio of 8: 2, uniformly mixing in an airflow mixer, heating to 200 ℃ in the mixing process, heating and mixing for 10min, and cooling to room temperature to obtain the compact and improved material.
Secondly, preparing the super-hydrophobic harmful ion isolation material
A1. Adding 100 parts of superfine zeolite powder into 100 parts of ethanol, and uniformly stirring to obtain an alcohol solution of the zeolite powder; adding 6 parts of silane coupling agent into 60 parts of distilled water and 5 parts of ethanol for dilution to obtain silane coupling agent hydrolysate; mixing 80 parts of alcoholic solution of zeolite powder and 10 parts of silane coupling agent hydrolysate in a container with a heating function, adding 0.3 part of aminoethanesulfinic acid and 0.3 part of saturated calcium hydroxide solution, heating to 85 ℃, mixing for 1h, filtering, and drying to obtain modified zeolite powder;
A2. adding 2 parts of sodium dodecyl sulfate and 1 part of sodium bicarbonate into 80 parts of water, stirring for dissolving, adding 25 parts of 2-methyl methacrylate and 6 parts of methyl vinyl chlorosilane, and uniformly stirring to obtain an emulsion;
A3. mixing 0.2 part of ammonium dithionate, 2 parts of sodium dodecyl sulfate, 11 parts of emulsion and 80 parts of modified zeolite powder, heating at 80 ℃ for 1.5 hours, cooling to room temperature, and drying to obtain the super-hydrophobic harmful ion isolation material.
Thirdly, preparing the anti-pollution biological corrosive
S1, uniformly mixing 41 parts of copper sulfate, 11 parts of nano silver powder, 6 parts of tetrapropylene sodium benzenesulfonate, 5 parts of naphthalene sulfonate formaldehyde condensate and 2 parts of dibenzoyl peroxide.
S2, carrying out autoclaving on the uniformly mixed powder at 180 ℃ under 1.5 atmospheric pressures for 2.5h to obtain the anti-pollution biological corrosive agent.
Fourthly, preparing marine protective concrete:
s1, weighing 200kg/m380kg/m of cement360kg/m of fly ash3Mineral powder and 25kg/m3Putting the micro silica fume into a forced mixer and then stirring for 30-45 seconds;
s2, mixing 0.5kg/m in a stirrer3Polycarboxylic acid type water reducing agent, 30kg/m3Compaction improving Material, 12kg/m38kg/m of super-hydrophobic harmful ion isolation material3Anti-fouling bioerosion and 150kg/m3Mixing with water for 1.5-2 min;
s3, injecting the liquid uniformly mixed with the S2 into the powder uniformly mixed with the S1, and mixing for 30-45 seconds to form a uniform suspension;
s4, weighing 650kg/m3Sand and 1000kg/m3Pouring the crushed stone into the suspension mixed by the S3, and mixing for 30-45 seconds to form a marine self-protection concrete mixture;
s5, injecting the marine self-protection concrete mixture prepared in the step S4 into a concrete template, and vibrating the concrete by adopting a vibrating rod or a flat vibrator to remove redundant air bubbles in the concrete;
and S6, removing the mold after the poured and vibrated concrete is subjected to mold curing, and curing for more than 14 days by adopting a water-retaining curing film to obtain a target product.
Example 2
The marine self-protection concrete comprises the following components of 300kg/m of cement3110kg/m of fly ash340kg/m of mineral powder330kg/m of micro silica fume3700kg/m of sand31100kg/m of crushed stone380kg/m of water31kg/m of polycarboxylic acid water reducing agent3Compaction improving material 25kg/m312kg/m of super-hydrophobic harmful ion isolation material36kg/m of anti-pollution biological corrosive agent3。
The specific preparation method of the marine self-protection concrete comprises the following steps:
secondly, preparing a compaction improving material
(1) Weighing 15kg of calcium carbonate powder, placing the calcium carbonate powder in an airflow mixer, heating to 155 ℃ for 5min, then spraying methacryloxypropyl trimethoxy silane accounting for 2% of the mass of the calcium carbonate powder, mixing at constant temperature for 10min, then cooling at the cooling speed of 15 ℃/h, and carrying out surface modification on the calcium carbonate powder.
(2) Weighing 10kg of superfine pumice powder, and mixing the modified calcium carbonate powder obtained in the step (1) with the weighed superfine pumice powder according to a mass ratio of 3: 2, uniformly mixing in an airflow mixer, heating to 220 ℃ in the mixing process, heating and mixing for 10min, and cooling to room temperature to obtain the compact and improved material.
Secondly, preparing the super-hydrophobic harmful ion isolation material
A1. Adding 120 parts of superfine zeolite powder into 110 parts of ethanol, and uniformly stirring to obtain an alcohol solution of the zeolite powder; adding 8 parts of silane coupling agent into 65 parts of distilled water and 5 parts of ethanol for dilution to obtain silane coupling agent hydrolysate; mixing 85 parts of alcoholic solution of zeolite powder and 12 parts of silane coupling agent hydrolysate in a container with a heating function, adding 0.4 part of aminoethanesulfinic acid and 0.5 part of saturated calcium hydroxide solution, heating to 82 ℃, mixing for 1h, filtering, and drying to obtain modified zeolite powder;
A2. adding 1 part of sodium dodecyl sulfate and 1 part of sodium bicarbonate into 80 parts of water, stirring for dissolving, adding 20 parts of 2-methyl methacrylate and 8 parts of methyl vinyl chlorosilane, and uniformly stirring to obtain an emulsion;
A3. mixing 0.3 part of ammonium dithionate, 3 parts of sodium dodecyl sulfate, 12 parts of emulsion and 82 parts of modified zeolite powder, heating at 85 ℃ for 1.5 hours, cooling to room temperature, and drying to obtain the super-hydrophobic harmful ion isolation material.
Thirdly, preparing the anti-pollution biological corrosive
S1, uniformly mixing 45 parts of copper sulfate, 12 parts of nano silver powder, 8 parts of tetrapropylene sodium benzenesulfonate, 6 parts of naphthalene sulfonate formaldehyde condensate and 4 parts of dibenzoyl peroxide.
S2, carrying out autoclaving on the uniformly mixed powder at 200 ℃ under 1.5 atmospheric pressures for 2.5h to obtain the anti-pollution biological corrosive agent.
Fourthly, preparing marine protective concrete:
s1, weighing 300kg/m3110kg/m of cement340kg/m of fly ash3Mineral powder and 30kg/m3Putting the micro silica fume into a forced mixer and then stirring for 30-45 seconds;
s2, mixing 1kg/m in a stirrer3Polycarboxylic acid type water reducing agent, 25kg/m3Compaction improving Material, 12kg/m36kg/m of super-hydrophobic harmful ion isolation material3Anti-fouling bioerosion and 80kg/m3Mixing with water for 1.5-2 min;
s3, injecting the liquid uniformly mixed with the S2 into the powder uniformly mixed with the S1, and mixing for 30-45 seconds to form a uniform suspension;
s4, weighing the weighed 700kg/m3Sand and 1100kg/m3Pouring the crushed stone into the suspension mixed by the S3, and mixing for 30-45 seconds to form a marine self-protection concrete mixture;
s5, injecting the marine self-protection concrete mixture prepared in the step S4 into a concrete template, and vibrating the concrete by adopting a vibrating rod or a flat vibrator to remove redundant air bubbles in the concrete;
and S6, removing the mold after the poured and vibrated concrete is subjected to mold curing, and curing for more than 14 days by adopting a water-retaining curing film to obtain a target product.
Example 3
The marine self-protection concrete comprises the following components of cement 350kg/m3120kg/m of fly ash355kg/m of mineral powder328kg/m of microsilica ash3800kg/m of sand31100kg/m of crushed stone3180kg/m of water31.2kg/m of polycarboxylic acid water reducing agent3Compaction improving material 40kg/m320kg/m of super-hydrophobic harmful ion isolation material38kg/m of anti-pollution biological corrosive agent3。
The specific preparation method of the marine self-protection concrete comprises the following steps:
thirdly, preparing the material with improved compactness
(1) Weighing 32kg of calcium carbonate powder, placing the calcium carbonate powder in an airflow type mixer, heating to 160 ℃, keeping for 5min, then spraying methacryloxypropyl trimethoxy silane accounting for 4% of the mass of the calcium carbonate powder, mixing at constant temperature for 15min, then cooling at the cooling speed of 20 ℃/h, and carrying out surface modification on the calcium carbonate powder.
(2) Weighing 8kg of superfine pumice powder, and mixing the modified calcium carbonate powder obtained in the step (1) with the weighed superfine pumice powder according to a mass ratio of 4: 1, uniformly mixing in an airflow mixer, heating to 240 ℃ in the mixing process, heating and mixing for 10min, and cooling to room temperature to obtain the compact and improved material.
Secondly, preparing the super-hydrophobic harmful ion isolation material
A1. Adding 140 parts of superfine zeolite powder into 120 parts of ethanol, and uniformly stirring to obtain an alcohol solution of the zeolite powder; adding 8 parts of silane coupling agent into 70 parts of distilled water and 7 parts of ethanol for dilution to obtain silane coupling agent hydrolysate; mixing 90 parts of alcoholic solution of zeolite powder and 20 parts of silane coupling agent hydrolysate in a container with a heating function, adding 0.5 part of aminoethanesulfinic acid and 0.6 part of saturated calcium hydroxide solution, heating to 85 ℃, mixing for 1h, filtering, and drying to obtain modified zeolite powder;
A2. adding 2 parts of sodium dodecyl sulfate and 2 parts of sodium bicarbonate into 85 parts of water, stirring for dissolving, adding 28 parts of 2-methyl methacrylate and 8 parts of methyl vinyl chlorosilane, and uniformly stirring to obtain an emulsion;
A3. mixing 0.4 part of ammonium dithionate, 5 parts of sodium dodecyl sulfate, 14 parts of emulsion and 86 parts of modified zeolite powder, heating at 90 ℃ for 1.5 hours, cooling to room temperature, and drying to obtain the super-hydrophobic harmful ion isolation material.
Thirdly, preparing the anti-pollution biological corrosive
S1, uniformly mixing 46 parts of copper sulfate, 12 parts of nano silver powder, 8 parts of tetrapropylene sodium benzenesulfonate, 7 parts of naphthalene sulfonate formaldehyde condensate and 5 parts of dibenzoyl peroxide.
S2, carrying out autoclaving on the uniformly mixed powder at 220 ℃ under 1.5 atmospheric pressures for 2.5h to obtain the anti-pollution biological corrosive agent.
Fourthly, preparing marine protective concrete:
s1, weighing 350kg/m3120kg/m of cement3Fly ash, 55kg/m3Mineral powder and 28kg/m3Putting the micro silica fume into a forced mixer and then stirring for 30-45 seconds;
s2, mixing 1.2kg/m in a stirrer340kg/m of polycarboxylic acid water reducing agent3Compaction improving Material, 20kg/m38kg/m of super-hydrophobic harmful ion isolation material3Anti-fouling bioerosion and 180kg/m3Mixing with water for 1.5-2 min;
s3, injecting the liquid uniformly mixed with the S2 into the powder uniformly mixed with the S1, and mixing for 30-45 seconds to form a uniform suspension;
s4, weighing 800kg/m3Sand and 1100kg/m3Pouring the crushed stone into the suspension mixed by the S3, and mixing for 30-45 seconds to form a marine self-protection concrete mixture;
s5, injecting the marine self-protection concrete mixture prepared in the step S4 into a concrete template, and vibrating the concrete by adopting a vibrating rod or a flat vibrator to remove redundant air bubbles in the concrete;
and S6, removing the mold after the poured and vibrated concrete is subjected to mold curing, and curing for more than 14 days by adopting a water-retaining curing film to obtain a target product.
Example 4
The marine self-protection concrete comprises 380kg/m of cement3150kg/m of fly ash340kg/m of mineral powder3Micro silica fume 22kg/m3700kg/m of sand31050kg/m of crushed stone3170kg/m of water30.9kg/m of polycarboxylic acid water reducing agent3Compaction improving material 30kg/m318kg/m of super-hydrophobic harmful ion isolation material38kg/m of anti-pollution biological corrosive agent3。
The specific preparation method of the marine self-protection concrete comprises the following steps:
fourthly, preparing the material for improving the compactness
(1) Weighing 18kg of calcium carbonate powder, placing the calcium carbonate powder in an airflow type mixer, heating to 160 ℃, keeping for 5min, then spraying methacryloxypropyl trimethoxy silane accounting for 2% of the mass of the calcium carbonate powder, mixing at constant temperature for 15min, then cooling at the cooling speed of 15 ℃/h, and carrying out surface modification on the calcium carbonate powder.
(2) Weighing 12kg of superfine pumice powder, and mixing the modified calcium carbonate powder obtained in the step (1) with the weighed superfine pumice powder according to a mass ratio of 3: 2, uniformly mixing in an air flow type mixer, heating to 260 ℃ in the mixing process, heating and mixing for 15min, and cooling to room temperature to obtain the compact and improved material.
Secondly, preparing the super-hydrophobic harmful ion isolation material
A1. Adding 130 parts of superfine zeolite powder into 105 parts of ethanol, and uniformly stirring to obtain an alcohol solution of the zeolite powder; adding 7 parts of silane coupling agent into 65 parts of distilled water and 7 parts of ethanol for dilution to obtain silane coupling agent hydrolysate; mixing 85 parts of alcoholic solution of zeolite powder and 16 parts of silane coupling agent hydrolysate in a container with a heating function, adding 0.3 part of aminoethanesulfinic acid and 0.5 part of saturated calcium hydroxide solution, heating to 85 ℃, mixing for 1.5h, filtering, and drying to obtain modified zeolite powder;
A2. adding 1 part of sodium dodecyl sulfate and 1 part of sodium bicarbonate into 85 parts of water, stirring for dissolving, adding 30 parts of 2-methyl methacrylate and 8 parts of methyl vinyl chlorosilane, and uniformly stirring to obtain an emulsion;
A3. mixing 0.4 part of ammonium dithionate, 5 parts of sodium dodecyl sulfate, 14 parts of emulsion and 85 parts of modified zeolite powder, heating at 90 ℃ for 1.5 hours, cooling to room temperature, and drying to obtain the super-hydrophobic harmful ion isolation material.
Thirdly, preparing the anti-pollution biological corrosive
S1, uniformly mixing 50 parts of copper sulfate, 10 parts of nano silver powder, 6 parts of tetrapropylene sodium benzenesulfonate, 8 parts of naphthalene sulfonate formaldehyde condensate and 4 parts of dibenzoyl peroxide.
S2, carrying out autoclaving on the uniformly mixed powder at 210 ℃ under 2 atmospheric pressures for 2.5h to obtain the anti-pollution biological corrosive agent.
Fourthly, preparing marine protective concrete:
s1, weighing 380kg/m3150kg/m of cement340kg/m of fly ash3Ore powder and 22kg/m3Putting the micro silica fume into a forced mixer and then stirring for 30-45 seconds;
s2, mixing 0.9kg/m in a stirrer3Polycarboxylic acid type water reducing agent, 30kg/m3Densification improving material, 18kg/m38kg/m of super-hydrophobic harmful ion isolation material3Anti-fouling bioerosion and 170kg/m3Mixing with water for 1.5-2 min;
s3, injecting the liquid uniformly mixed with the S2 into the powder uniformly mixed with the S1, and mixing for 30-45 seconds to form a uniform suspension;
s4, weighing the weighed 700kg/m3Sand and 1050kg/m3Pouring the crushed stone into the suspension mixed by the S3, and mixing for 30-45 seconds to form a marine self-protection concrete mixture;
s5, injecting the marine self-protection concrete mixture prepared in the step S4 into a concrete template, and vibrating the concrete by adopting a vibrating rod or a flat vibrator to remove redundant air bubbles in the concrete;
and S6, removing the mold after the poured and vibrated concrete is subjected to mold curing, and curing for more than 14 days by adopting a water-retaining curing film to obtain a target product.
Comparative example 1
The marine self-protection concrete comprises the following components of cement 400kg/m350kg/m of fly ash350kg/m of mineral powder3750kg/m of sand31050kg/m of crushed stone3170kg/m of water35kg/m of polycarboxylic acid water reducing agent3。
Comparative example 2
The marine self-protection concrete comprises the following components of cement 350kg/m380kg/m of fly ash370kg/m of mineral powder3800kg/m of sand3960kg/m of crushed stone3175kg/m of water34.5kg/m of polycarboxylic acid water reducing agent3。
And (3) performance testing: testing RCM chloride ion permeability, electric flux and dry-wet cycle sulfate erosion performance of the concrete by a method of 'test method standard for long-term performance and durability of common concrete' GB/T50082-2009; the anti-algae effect of the concrete surface is represented by the fluorescence intensity value, and the higher the maximum fluorescence intensity value is, the more algae growth quantity on the concrete surface is. The longer the occurrence time of the maximum fluorescence relative value is, the slower the growth speed of the alga, and the results of the maximum fluorescence intensity value and the occurrence time of the maximum fluorescence relative value are obtained.
The concrete performance data for examples 1-4 and comparative examples 1-2 are shown in Table 1 below:
table 1 results of performance testing
Figure BDA0003119098010000231
Figure BDA0003119098010000241
By testing the chlorophyll fluorescence intensity thermal imaging of each group of surfaces, it can be seen that the maritime work self-protection concrete prepared by the method of the invention in the embodiment 1-4 has lower maximum fluorescence intensity value and longer maximum fluorescence relative value occurrence time, which indicates that the growth quantity of the algae moss on the surface of the concrete is less and the growth is slower. The permeability coefficient of chloride ions is far lower than that of a comparative example in 56 days, the dry-wet cycle sulfate corrosion resistance is higher, and experiments prove that the marine self-protection concrete prepared by the method has better compactness, corrosion resistance and durability.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. The utility model provides a maritime work is from protection concrete which characterized in that: comprises the following components of 200-400kg/m cement380-150kg/m of fly ash340-80kg/m mineral powder3Micro silica fume 20-40kg/m3650-sand 850kg/m3900-3150-180kg/m water30.5-1.5kg/m of polycarboxylic acid water reducing agent3The compact improving material is 20-40kg/m310-20kg/m of super-hydrophobic harmful ion isolation material35-10kg/m of anti-pollution biological corrosive agent3。
2. The marine self-protective concrete according to claim 1, wherein: the compaction improving material is prepared by a method comprising,
(1) selecting calcium carbonate powder, placing the calcium carbonate powder in an airflow type mixer, heating, spraying methacryloxypropyl trimethoxy silane, mixing at constant temperature, and carrying out surface modification on the calcium carbonate powder;
(2) selecting superfine pumice powder, mixing the surface modified calcium carbonate powder prepared in the step (1) with the superfine pumice powder, heating in the mixing process, and cooling to room temperature to obtain the compact and improved material.
3. The marine self-protective concrete according to claim 2, wherein: the fineness of the calcium carbonate powder in the step (1) is 0.5-1.5 ㎛, and the fluidity ratio is 110-120%.
4. Marine engineering self-protecting concrete according to claim 2 or 3, wherein: the ultrafine pumice powder comprises the following components: SiO 2245～55wt%，Al2O315～ 25wt%，Fe2O35～15wt%，CaO3-8 wt%; loss on ignition of the ultrafine pumice powder<4.5%, fineness of 2.5-4.5 ㎛, and fluidity ratio of 100-110%.
5. The marine self-protective concrete according to claim 1, wherein: the super-hydrophobic harmful ion isolation material is prepared by the following method,
A1. preparing modified zeolite powder;
A2. adding 1-2 parts of sodium dodecyl sulfate and 1-2 parts of sodium bicarbonate into 80-85 parts of water, stirring for dissolving, adding 20-30 parts of 2-methyl methacrylate and 5-10 parts of methyl vinyl chlorosilane, and uniformly stirring to obtain an emulsion;
A3. stirring 0.2-0.4 part of ammonium disulfate, 2-5 parts of sodium dodecyl sulfate, 10-15 parts of the emulsified emulsion obtained in the step A2 and 80-85 parts of the modified zeolite powder obtained in the step A1 together, heating and cooling to room temperature, and drying to obtain the super-hydrophobic harmful ion isolation material.
6. Marine engineering self-protecting concrete according to claim 5, wherein: the preparation method of the modified zeolite powder in the step A1 comprises the following specific steps of adding 100-150 parts of superfine zeolite powder into 100-120 parts of ethanol, and uniformly stirring to obtain an alcohol solution of the zeolite powder; adding 5-10 parts of silane coupling agent into 50-80 parts of distilled water and 5-8 parts of ethanol for dilution to obtain silane coupling agent hydrolysate; mixing 80-90 parts of alcoholic solution of zeolite powder and 10-20 parts of silane coupling agent hydrolysate in a container with a heating function, adding 0.3-0.5 part of aminoethanesulfinic acid and 0.3-0.8 part of saturated calcium hydroxide solution, heating to 80-85 ℃, mixing for 1-1.5 h, filtering, and drying to obtain the modified zeolite powder.
7. The marine self-protective concrete according to claim 1, wherein: the anti-fouling bioerodible agent is prepared by a process,
s1, uniformly mixing 40-50 parts of copper sulfate, 10-15 parts of nano silver powder, 5-10 parts of tetrapropylene sodium benzenesulfonate, 5-8 parts of naphthalene sulfonate formaldehyde condensate and 2-5 parts of dibenzoyl peroxide;
s2, performing pressure steaming on the powder uniformly mixed in the step S1 at 180-220 ℃ under 1.5-2 atmospheric pressures for 2-2.5 hours to obtain the anti-pollution biological corrosive agent.
8. The method for preparing the marine self-protective concrete according to claim 1, wherein the method comprises the following steps: the method specifically comprises the following operation steps of,
s1, weighing cement, fly ash, mineral powder and micro-silica ash, putting into a forced mixer, and stirring for 30-45 seconds;
s2, mixing the polycarboxylic acid water reducer, the compaction improving material, the super-hydrophobic harmful ion isolation material, the anti-pollution biological corrosive agent and water in a stirrer for 1.5-2 min;
s3, injecting the liquid mixed uniformly with the S2 into the powder mixed uniformly with the S1, and mixing for 30-45 seconds to form a uniform suspension;
s4, injecting the weighed sand and gravel into the suspension mixed by the S3, and mixing for 30-45 seconds to form a marine self-protection concrete mixture;
s5, injecting the marine self-protection concrete mixture prepared in the step S4 into a concrete template, and vibrating the concrete by adopting a vibrating rod or a flat vibrator to remove redundant air bubbles in the concrete;
and S6, removing the mold after the poured and vibrated concrete is cured, and curing for more than 14 days by adopting a water-retaining curing film to obtain a target product.
9. The method for preparing marine self-protective concrete according to claim 8, wherein the method comprises the following steps: the compaction improving material is prepared by a method comprising,
(1) selecting calcium carbonate powder, placing the calcium carbonate powder in an airflow type mixer, heating, spraying methacryloxypropyl trimethoxy silane, mixing at constant temperature, and carrying out surface modification on the calcium carbonate powder;
(2) selecting superfine pumice powder, mixing the surface modified calcium carbonate powder prepared in the step (1) with the superfine pumice powder, heating in the mixing process, and cooling to room temperature to obtain the compact and improved material.
10. The method for preparing marine self-protective concrete according to claim 8 or 9, wherein the method comprises the following steps: the super-hydrophobic harmful ion isolation material is prepared by the following method,
A1. preparing modified zeolite powder;
A2. adding 1-2 parts of sodium dodecyl sulfate and 1-2 parts of sodium bicarbonate into 80-85 parts of water, stirring for dissolving, adding 20-30 parts of 2-methyl methacrylate and 5-10 parts of methyl vinyl chlorosilane, and uniformly stirring to obtain an emulsion;
A3. stirring 0.2-0.4 part of ammonium disulfate, 2-5 parts of sodium dodecyl sulfate, 10-15 parts of the emulsified emulsion obtained in the step A2 and 80-85 parts of the modified zeolite powder obtained in the step A1 together, heating and cooling to room temperature, and drying to obtain the super-hydrophobic harmful ion isolation material.
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