CN112939528A - Underwater low-bleeding concrete and preparation method thereof - Google Patents

Underwater low-bleeding concrete and preparation method thereof Download PDF

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Publication number
CN112939528A
CN112939528A CN202110094129.3A CN202110094129A CN112939528A CN 112939528 A CN112939528 A CN 112939528A CN 202110094129 A CN202110094129 A CN 202110094129A CN 112939528 A CN112939528 A CN 112939528A
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parts
concrete
water
underwater
bleeding
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梁国源
邬超友
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Guangzhou Honglei Concrete Co ltd
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Guangzhou Honglei Concrete Co ltd
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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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/08—Sulfonic acid halides; alpha-Hydroxy-sulfonic acids; Amino-sulfonic acids; Thiosulfonic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/10—Accelerators; Activators
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/44—Thickening, gelling or viscosity increasing agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/2092—Resistance against biological degradation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • 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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  • Engineering & Computer Science (AREA)
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  • Ceramic Engineering (AREA)
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  • Civil Engineering (AREA)
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  • Toxicology (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The application relates to the field of building materials, and particularly discloses underwater low-bleeding concrete and a preparation method thereof. The underwater low-bleeding concrete comprises the following components in parts by weight: 420 parts of cement in 370 portions, 700 parts of sand in 650 portions, 1100 parts of pebble in 1060 portions, 40-55 parts of fly ash, 190 parts of water in 140 portions, 60-80 parts of mineral powder, 5-10 parts of flocculating agent, 10-15 parts of water reducing agent and 18-30 parts of anti-dispersing agent; the anti-dispersing agent comprises an early strength agent, a tackifier and silica fume with the mass ratio of 1:2-3: 1-2; the tackifier comprises the following components: betaine, cetyltrimethylammonium bromide and 4-tributylmethylammonium bromide; the early strength agent comprises the following components: potassium bromide, sodium 2, 2' -dithiodibenzoate and sodium cinnamate. The underwater low-bleeding concrete has the advantages of small bleeding rate, high underwater cohesiveness, difficulty in dispersion and capability of effectively preventing algae from growing.

Description

Underwater low-bleeding concrete and preparation method thereof
Technical Field
The application relates to the technical field of building materials, in particular to underwater low-bleeding concrete and a preparation method thereof.
Background
The concrete in the underwater engineering is the most main building material with the largest using amount to be questioned, and the performance of the concrete directly influences the quality and the progress of the underwater engineering, so the engineering technical field increasingly pays more attention to the performance research of the underwater pouring concrete.
When the common concrete is used for pouring underwater engineering, the cement can be separated from the aggregate by water scouring, so that part of the cement is lost, the cement in the residual cement paste is in a suspended state in the water for a long time, and the cement is solidified when sinking and loses the capability of being cemented with the aggregate, so that the common concrete can be separated into two parts, namely a layer of aggregate and a layer of hardened cement paste when being poured underwater, and the engineering requirements cannot be met.
In order to solve the problems, in the underwater construction process, the construction method is mainly improved, and the contact between the concrete mixture and water is reduced or eliminated, so that the influence of water on the concrete mixture is avoided.
In view of the above-mentioned related technologies, the inventor believes that the need for underwater construction of concrete cannot be met by technically avoiding the influence of water on underwater concrete, and therefore, it is necessary to improve the performance of the underwater concrete material itself, thereby reducing the bleeding of concrete underwater.
Disclosure of Invention
In order to reduce the bleeding property of concrete under water and increase the underwater compressive strength of the concrete, the application provides the low-bleeding concrete for the underwater and the preparation method thereof.
In a first aspect, the present application provides an underwater low-bleeding concrete, which adopts the following technical scheme:
the underwater low-bleeding concrete comprises the following components in parts by weight: 420 parts of cement in 370 portions, 700 parts of sand in 650 portions, 1100 parts of pebble in 1060 portions, 40-55 parts of fly ash, 190 parts of water in 140 portions, 60-80 parts of mineral powder, 5-10 parts of flocculating agent, 10-15 parts of water reducing agent and 18-30 parts of anti-dispersing agent;
the anti-dispersing agent comprises an early strength agent, a tackifier and silica fume with the mass ratio of 1:2-3: 1-2;
the tackifier comprises the following components in parts by weight: 1.3-2 parts of betaine, 2.4-3.4 parts of hexadecyl trimethyl ammonium bromide and 1-2 parts of tributyl methyl ammonium bromide;
the early strength agent comprises the following components in parts by weight: 0.8-1.4 parts of potassium bromide, 1.2-2.2 parts of sodium 2, 2' -dithiodibenzoate and 0.8-1.6 parts of sodium cinnamate.
By adopting the technical scheme, as the flocculating agent, the water reducing agent and the anti-dispersing agent are added, the flocculating agent can increase the viscosity of a concrete mixture, and the molecules of the flocculating agent are mutually wound to form a net structure, so that cement and the anti-dispersing agent are wrapped, the friction resistance of water molecules is reduced when cement slurry falls in water, the water molecules are prevented from being washed and dispersed by the outside water molecules, the anti-dispersing capability is improved, the early strength agent, the tackifier and silica fume are mixed to be used as the anti-dispersing agent, the main active component of the silica fume is silica which is used as an auxiliary cementing material to be added into the cement slurry and the concrete, the hydration degree of the cement cannot be improved, the silica fume and the secondary hydration products thereof have high dispersibility, harmful holes in hardened cement slurry are filled, and the interface performance of the cement and aggregate in the concrete is improved, the compactness after hardening is improved; sodium cinnamate, potassium bromide and sodium 2, 2' -dithiodibenzoate are used as early strength agents, betaine, hexadecyl trimethyl ammonium bromide and 4-tributyl methyl ammonium bromide are used as tackifier, and an entangled micelle network can be formed by an aqueous solution of the betaine, so that the gel property is very strong.
Preferably, the silica fume is pretreated by the following steps: according to parts by weight, (1) calcining 1-2 parts of silica fume and 0.3-0.6 part of sodium carbonate at 900 ℃ under 800-; (2) mixing 1.5-2.5 parts of acrylamide, 0.2-0.5 part of gamma-methacryloxypropyltrimethoxysilane, 0.05-0.1 part of potassium persulfate, 0.24-0.5 part of tetramethylethylenediamine, 0.01-0.05 part of 20-30% tetramethylammonium hydroxide and 6-10 parts of water to prepare a mixed solution; (3) introducing supercritical carbon dioxide into the mixed solution in a closed environment, spraying the mixed solution onto the product obtained in the step (1), wherein the spraying pressure is 5-8MPa, and the mass ratio of the supercritical carbon dioxide to the mixed solution is 1: 0.05-0.2; (4) and (4) preserving the heat of the product obtained in the step (3) for 40-48h in water bath at the temperature of 25-30 ℃.
By adopting the technical scheme, after the silica fume and the sodium carbonate are calcined, sodium oxide is generated, and the sodium oxide reacts with silicon dioxide in the silica fume to generate a porous substance, so that the specific surface area of the silica fume is increased, the flocculation precipitation capability is enhanced, after the fly ash, the zeolite and the silica fume are treated by acid, a compound which is generated by oxides such as silica and is easy to form a complex or a high molecular polymer can be dissolved, the compound can exchange with hydroxyl groups on the surface of the fly ash, the hydroxyl groups are eliminated, the polarity of the surface of the fly ash is reduced, the dispersibility and the activity of the fly ash are improved, and the acid treatment can eliminate impurities which block pores of the fly ash, the silica fume and the zeolite, increase the depth and the porosity of the pores, increase the specific surface area and; the components such as acrylamide, gamma-methacryloxypropyltrimethoxysilane and the like react to generate high-strength gel with good viscosity and toughness, the high-strength gel is attached to the surfaces of porous silica fume, fly ash and zeolite and is coated by supercritical carbon dioxide, when the high-strength gel is sprayed, the carbon dioxide in liquid drops is quickly gasified due to the rapid change of pressure intensity, and the remaining mixed solution is uniformly coated on the silica fume, the fly ash and the zeolite, so that the viscosity of the silica fume, the fly ash and the zeolite is increased, the adhesion between the silica fume and cement, sand, stone and the like is increased, and the cement slurry is prevented from being dispersed underwater.
Preferably, the water reducing agent is prepared from the following components in a mass ratio of 1: 1-2.4:0.4-2 of a beta-sodium naphthalenesulfonate formaldehyde condensate, a slump-retaining polycarboxylic acid water reducing agent and a high water-reducing polycarboxylic acid water reducing agent.
By adopting the technical scheme, the beta-sodium naphthalenesulfonate formaldehyde condensate is a naphthalene-based high-efficiency water reducing agent, has the advantages of high water reducing rate, good early strength effect and strong adaptability to cement, and can increase the fluidity of concrete, improve slump and improve workability; the slump-retaining type polycarboxylate superplasticizer and the high-water-reducing type polycarboxylate superplasticizer can effectively reduce the diffusion of concrete under water, so that the concrete can be quickly condensed under water.
Preferably, the flocculant is prepared by mixing polyacrylamide, sodium carboxymethylcellulose and polyaluminium chloride, wherein the mass ratio of the polyacrylamide to the carboxymethylcellulose to the polyaluminium chloride is 1:0.6-1: 1.3-2.
By adopting the technical scheme, the sodium carboxymethylcellulose has good anti-dispersion property, hydrogen on hydroxyl groups of the sodium carboxymethylcellulose is easy to etherify so as to achieve a flocculation effect, the polyacrylamide can be adsorbed on cement particles through active functional groups with long carbon chain length, and a plurality of cement particles are adsorbed by the same molecule, so that a bridge action is formed among the cement particles; the poly ferric chloride generates aluminum hydroxide colloid with good adsorbability in water, and can be adsorbed on the surfaces of cement particles, sand and stone, so that the binding force between the sand and the stone is increased, and the cement paste is prevented from being dispersed underwater.
Preferably, the average molecular weight of the polyacrylamide is 120-160 ten thousand.
By adopting the technical scheme, the polyamide has the advantages of large molecular weight, high polymerization degree, more branched chains and good flocculation effect, can increase the adsorbability among aggregates and prevent cement paste from dispersing in water.
Preferably, the cement is P.O42.5 Portland cement, the 3d compressive strength is 28.6MPa, and the 28d compressive strength is 48.7 MPa.
By adopting the technical scheme, the P.O42.5 portland cement is used, the early strength is high, the water cement ratio is small, the portland cement is not easy to bleed, and after hardening, the concrete has high density, few pores and stable later strength.
Preferably, the sand is graded sand in the II area, the fineness modulus is 2.5-2.7, and the apparent density is 2500-3The bulk density is 1400-1600kg/m3The mud content is 0.2-0.7%, and the mass percentage of chloride ions is 0.00015-0.00019%.
By adopting the technical scheme, the graded sand in the area II is used, the sand is proper in thickness and good in workability, construction and easiness are good, stirring is easy, no framework is formed between coarse sand, and the fine sand is filled in pores between the coarse sand, so that the compactness of concrete is improved, the segregation and bleeding of the concrete are reduced, and the workability is improved.
Preferably, the stones are pebbles with the particle size of 5-25mm, the content of needle-shaped particles is 4-6%, and the apparent density is 2500-3The bulk density is 1400-1600kg/m3The mud content is 0.1-0.3％。
By adopting the technical scheme, the contents of the needle-shaped particles in the broken stones are proper, the strength of the concrete can be effectively improved, the particle size of the broken stones is reasonable, the situation that the particles are large, the pores between the broken stones are large, the underwater strength of the concrete is low, and the underwater compressive strength of the concrete is improved is avoided.
In a second aspect, the present application provides a method for preparing a low-bleeding concrete for underwater use, which adopts the following technical scheme: a preparation method of low-bleeding concrete for underwater use comprises the following steps:
s1, mixing sand, gravel and 1/2 of water uniformly;
s2, mixing the residual water, the flocculating agent, the water reducing agent and the anti-dispersing agent uniformly, and then mixing the mixture and the substance obtained in the step S1 uniformly;
and S3, adding cement, mineral powder and fly ash into the product obtained in the step S2, and uniformly stirring.
By adopting the technical scheme, the preparation method is simple and easy to operate.
Preferably, 15-25 parts by weight of slow-release bactericide is also added into S3, and the preparation method of the slow-release bactericide is as follows: dissolving corn starch with water, dissolving chitosan with glacial acetic acid, mixing the two solutions according to the mass ratio of 1:0.9-1.1, gelatinizing at 90-95 ℃ for 0.5-1h, and uniformly mixing to obtain a film preparation; (2) uniformly mixing 1-2 parts by weight of tourmaline powder, 0.5-1 part by weight of jade powder and 0.5-1 part by weight of ethylicin to prepare a core material; (3) adding 0.4-0.7 part of cerium nitrate and 0.1-0.4 part of europium sulfate into 1-2 parts of the film preparation by weight, uniformly mixing, spraying the mixture on 0.6-1.2 parts of core material, and drying by hot air to obtain the slow-release bactericide.
By adopting the technical scheme, moss is easy to grow when the concrete is positioned in water for a long time after being formed, roots of moss plant bud spores can secrete trace hydrogen ions when growing, when the moss plant bud spores gradually grow and spread in a fishtable county, the hydrogen ions are converted to generate carbonic acid, humic acid and various organic acids, the pH value in the concrete is reduced, the surfaces of reinforcing steel bars are corroded and damaged, and the structural life of the concrete is shortened The ethylicin, calcium carbonate can excite some mineral components in the jade powder to release trace ions under the action of hydrogen ions, and the calcium ions penetrate through cell membranes of young plants of the moss plants and then are deposited and solidified in a calcium form so as to kill the moss cells; the cerium nitrate and the europium sulfate are added into the film preparation, so that the slow-release bactericide not only has long-acting bactericidal performance, but also has instant bactericidal effect.
In summary, the present application has the following beneficial effects:
1. the flocculant, the anti-dispersion agent formed by matching the early strength agent, the tackifier and the silica fume and the water reducing agent are equal to components of cement, sand, stone and the like to prepare the underwater low bleeding concrete, the cetyl trimethyl ammonium bromide in the tackifier and the potassium bromide, the sodium 2,2 '-dithiodibenzoate and the sodium cinnamate in the early strength agent have synergistic action and can generate worm-shaped micelles in the cement, the tributylmethyl ammonium bromide in the tackifier and the sodium 2, 2' -dithiodibenzoate in the reinforcer can generate worm-shaped micelles which have viscoelasticity and can reduce the resistance of particles such as the cement and the like when the particles fall in water, so that the cement slurry is prevented from being dispersed by the resistance of water molecules, and the anti-dispersion capacity and the bleeding prevention capacity of a concrete mixture in the water are improved.
2. In the application, fly ash, zeolite, acrylamide, gamma-methacryloxypropyltrimethoxysilane and other components are preferably adopted to pre-treat silica fume, the surface porosity of the silica fume is increased after the silica fume and sodium carbonate are calcined, the silica fume is mixed with the fly ash and the zeolite after being pickled and then is calcined again, so that the adsorption force of the silica fume is enhanced, high-viscosity gel formed by the acrylamide and the gamma-methacryloxypropyltrimethoxysilane is attached to the surfaces of the silica fume, the zeolite and the fly ash, the viscosity of the silica fume is increased, cement particles are not easy to disperse when falling in water through the bonding effect of the silica fume, and the anti-dispersion capability of concrete is further improved.
3. According to the application, the slow-release bactericide which is prepared by adding corn starch and chitosan serving as a film preparation and tourmaline powder, jade powder and ethylicin serving as core materials into concrete can keep the bactericidal effect for a long time, so that the moss is prevented from being attached to the concrete for a long time under water, and the service life of the concrete is shortened.
Detailed Description
Preparation examples 1 to 6 of silica fume
The silica fume in preparation examples 1 to 6 was selected from Changxing Longfeng powder materials Co., Ltd; the fly ash is selected from limited science and technology company of Jiang building materials in Shijiazhuang, and the model is TJ-0015; the zeolite is selected from Ningbo and New materials science and technology Limited; acrylamide is selected from Zhengzhou Yaodi chemical products Co., Ltd; the gamma-methacryloxypropyltrimethoxysilane is selected from Shenzhen Jingbo trade Shang, and the model is Z6030; the tetramethylethylenediamine is selected from Henan Te Lai L chemical products, Inc., and the product number is industrial grade; the tetramethylammonium hydroxide is selected from Mytilus edulis Merchant, Guangzhou; the organosilicon modified acrylic emulsion is selected from Shangguan Longqin printing material Co., Ltd, and the model is 5000GJ 35.
Preparation example 1: (1) calcining 1kg of silica fume and 0.3kg of sodium carbonate at 800 ℃ for 3h, adding 0.5kg of fly ash and 0.6kg of zeolite into the calcined silica fume, performing acid treatment, calcining at 800 ℃ for 3h, taking out and cooling to room temperature after the calcination is finished, wherein the acid treatment solution is sulfuric acid with the concentration of 75%, the acid treatment time is 2h, and the density of the silica fume is 2.2g/cm3Bulk density of 200kg/m3The fly ash is II-grade fly ash, the mesh number is 200 meshes, and the density of the zeolite is 2.1g/cm3(ii) a (2) 1.5kg of acrylamide, 0.2kg of gamma-methacryloxypropyltrimethoxysilane, 0.05kg of potassium persulfate, 0.24kg of tetramethylethylenediamine and 0.01 kg ofkg of tetramethylammonium hydroxide with a concentration of 20% and 6kg of water were mixed to prepare a mixed solution; (3) introducing supercritical carbon dioxide with the pressure of 7MPa and the temperature of 50 ℃ into the mixed solution in a closed environment, and spraying the mixed solution onto the substance obtained in the step (1), wherein the spraying pressure is 5MPa, and the mass ratio of the supercritical carbon dioxide to the mixed solution is 1: 0.05; (4) and (4) preserving the product obtained in the step (3) for 48 hours in a water bath at the temperature of 25 ℃.
Preparation example 2: (1) calcining 1.5kg of silica fume and 0.5kg of sodium carbonate at 850 ℃ for 2.5h, adding 1kg of fly ash and 0.9kg of zeolite into the calcined silica fume, performing acid treatment, calcining again at 850 ℃ for 2.5h, taking out the calcined silica fume, cooling to room temperature, wherein the acid treatment solution is 75% sulfuric acid, the acid treatment time is 2h, and the density of the silica fume is 2.2g/cm3Bulk density of 230kg/m3The fly ash is II-grade fly ash, the mesh number is 200 meshes, and the density of the zeolite is 2.1g/cm3(ii) a (2) 2kg of acrylamide, 0.4kg of gamma-methacryloxypropyltrimethoxysilane, 0.08kg of potassium persulfate, 0.35kg of tetramethylethylenediamine, 0.03kg of 23% tetramethylammonium hydroxide and 8kg of water were mixed to prepare a mixed solution; (3) introducing supercritical carbon dioxide with the pressure of 8MPa and the temperature of 55 ℃ into the mixed solution in a sealed environment, and spraying the mixed solution onto the product obtained in the step (1), wherein the spraying pressure is 5MPa, and the mass ratio of the supercritical carbon dioxide to the mixed solution is 1: 0.1; (4) and (4) preserving the product obtained in the step (3) for 40h in a water bath at the temperature of 30 ℃.
Preparation example 3: (1) calcining 2kg of silica fume and 0.6kg of sodium carbonate at 900 ℃ for 2h, adding 1.5kg of fly ash and 1.2kg of zeolite into the calcined silica fume, performing acid treatment, calcining at 900 ℃ for 2h, taking out and cooling to room temperature after the calcination is finished, wherein the acid treatment solution is sulfuric acid with the concentration of 75%, the acid treatment time is 2h, and the density of the silica fume is 2.2g/cm3Having a bulk density of 250kg/m3The fly ash is II-grade fly ash, the mesh number is 200 meshes, and the density of the zeolite is 2.1g/cm3(ii) a (2) 2.5kg of acrylamide, 0.5kg of gamma-methacryloxypropyltrimethoxysilane, 0.1kg of potassium persulfate, 0.5kg of tetramethylethylenediamine, 0.05kg of 25% tetramethylammonium hydroxide and 10kg of water were mixed,preparing a mixed solution; (3) introducing supercritical carbon dioxide with the pressure of 10MPa and the temperature of 60 ℃ into the mixed solution in a sealed environment, and spraying the mixed solution onto the product obtained in the step (1), wherein the spraying pressure is 10MPa, and the mass ratio of the supercritical carbon dioxide to the mixed solution is 1: 0.2; (4) and (4) preserving the product obtained in the step (3) for 44 hours in a water bath at the temperature of 25 ℃.
Preparation example 4: the difference from preparation example 1 is that fly ash and zeolite are not added in step (1).
Preparation example 5: the difference from preparation example 1 is that a silicone-modified acrylic emulsion was used as a mixed solution in step (2).
Preparation example 6: the difference from preparation example 1 is that the mixed solution is uniformly mixed with step (1) in step (3).
Preparation examples 1 to 6 of Slow-Release Fungicide
The corn starch of preparation examples 1-6 is selected from the group consisting of 049 model number available from Dapinghua technology, Inc., of Foshan; the chitosan is selected from Qingdao Hevesen Biotechnology Co., Ltd, model number is 00123; the tourmaline powder is selected from processing factory of QINGSHOU county QIANGdong mineral products, with model number of qd-036 and mesh number of 800 mesh; the jade powder is selected from gold source mining processing factory in Lingshu county, with model of KL-002 and mesh number of 800 mesh; the ethylicin is selected from QINGDAINENNI pharmaceutical industry GmbH, model number is 46513; the cerium nitrate is selected from Manba commercial Inc. of Texas, for analytical purification, CAS number is 10294-41-4; europium sulfate is selected from Shandong Haoyao new material company, model number is HY654654, mesh number is 325 mesh; the organosilicon modified acrylic emulsion is selected from Shangguan Longqin printing material Co., Ltd, and the model is 5000GJ 35.
Preparation example 1: (1) dissolving 20g of corn starch with 500g of water, dissolving 20g of chitosan with 500g of glacial acetic acid, mixing the two solutions according to the mass ratio of 1:0.9, gelatinizing at 90 ℃ for 1h, and uniformly mixing to prepare a film preparation; (2) uniformly mixing 1kg of tourmaline powder, 0.5kg of jade powder and 0.5kg of ethylicin to prepare a core material; (3) 0.4kg of cerium nitrate and 0.1kg of europium sulfate were added to 1kg of the film preparation, and after uniform mixing, 0.6kg of the core material was sprayed with the mixed solution while stirring at a rotation speed of 600r/min, and dried with hot air at 50 ℃ for 30min to obtain a sustained-release bactericide, the spraying pressure being 3.4 MPa.
Preparation example 2: (1) dissolving 40g of corn starch with 600g of water, dissolving 30g of chitosan with 600g of glacial acetic acid, mixing the two solutions according to the mass ratio of 1:1, gelatinizing at 95 ℃ for 0.5h, and uniformly mixing to prepare a film preparation; (2) uniformly mixing 1.5kg of tourmaline powder, 0.8kg of jade powder and 0.8kg of ethylicin to prepare a core material; (3) 0.5kg of cerium nitrate and 0.3kg of europium sulfate were added to 1.5kg of the film preparation, and after uniform mixing, 0.9kg of the core material was sprayed with the mixed solution while stirring at a rotation speed of 700r/min, and hot air-dried at 60 ℃ for 25min to obtain a slow-release bactericide, the spraying pressure being 3.8 MPa.
Preparation example 3: (1) dissolving 50g of corn starch with 700g of water, dissolving 40g of chitosan with 700g of glacial acetic acid, mixing the two solutions according to the mass ratio of 1:1.1, gelatinizing at 95 ℃ for 0.5h, and uniformly mixing to prepare a film preparation; (2) uniformly mixing 2kg of tourmaline powder, 1kg of jade powder and 1kg of ethylicin to prepare a core material; (3) 0.7kg of cerium nitrate and 0.4kg of europium sulfate were added to 2kg of the film preparation, and after uniform mixing, 1.2kg of the core material was stirred at a rotation speed of 800r/min while the mixed solution was sprayed on the core material, and hot air-dried at 70 ℃ for 20min to obtain a slow-release bactericide, the spraying pressure being 4 MPa.
Preparation example 4: the difference from preparation example 1 is that in step (1), a silicone resin emulsion is used as a film preparation.
Preparation example 5: the difference from preparation example 1 is that cerium nitrate and europium sulfate were not added in step (3).
Preparation example 6: the difference from preparation example 1 was that 2kg of copper sulfate was used as a core material in step (2).
Examples
In the following examples, the polyacrylamide having a molecular weight of 120 million was selected from the group consisting of KJ-102, model number, environmental technologies, Inc., Like, Changzhou; the polyacrylamide with the molecular weight of 160 ten thousand is selected from the group consisting of the Zhengyu water purification materials Limited of the Guozi city, the product number is 2011121, and the mesh number is 100 meshes; the sodium carboxymethylcellulose is selected from Ningchu Zhongda chemical industry Co., Ltd, and has the model of ZD-002; the polyaluminum chloride is selected from chemical drip chemical company, Inc., with a product number of 3310; the beta-sodium naphthalenesulfonate formaldehyde condensate is selected from Jiangxi Simo limited Biochemical company with the model of UNF-2; the slump-retaining type polycarboxylate superplasticizer is selected from Yulong building materials of Shanxi sea Co., Ltd, and has the model of HYL-202; the high water-reducing polycarboxylic acid water reducing agent is selected from novel building materials of Zhechuan Zhejiang, Ltd; betaine is selected from Zuoxin, Suzhou, with model number 6136; the sodium cinnamate is selected from Shanghai Gaomi chemical Co., Ltd, with a product number of 16222; the hexadecyl trimethyl ammonium bromide is selected from Captain chemical products, Inc. of Henan, with a cargo number of 2-6; tributyl methyl ammonium bromide is selected from chemical technology ltd, Anhui Si and Pu; the polyoxyethylene-polybutadiene block copolymer 2, 2' -sodium dithiobenzoate is selected from Dongying polymer intensive refining chemical company, Inc.
Example 1: the preparation method of the underwater low-bleeding concrete comprises the following steps:
s1, pre-mixing sand, pebbles and 1/2 of water uniformly, wherein the sand is II-zone graded sand, the fineness modulus is 2.5, and the apparent density is 2500kg/m3Bulk density of 1400kg/m3The mud content is 0.2%, the mass percent of chloride ions is 0.00015%, the pebbles with the particle size of 5mm have the content of needle-shaped particles of 4% and the apparent density is 2500kg/m3Bulk density of 1400kg/m3The mud content is 0.1%;
s2, residual water, a flocculating agent, a water reducing agent and an anti-dispersing agent, wherein the flocculating agent is prepared by mixing polyacrylamide, sodium carboxymethylcellulose and polyaluminium chloride in a mass ratio of 1:0.6:1.3, the molecular weight of the polyacrylamide is 120 ten thousand, the water reducing agent is prepared by mixing a beta-sodium naphthalenesulfonate formaldehyde condensate in a mass ratio of 1:1:0.4, a slump-retaining polycarboxylic acid water reducing agent and a high water-reducing polycarboxylic acid water reducing agent, and the anti-dispersing agent comprises an early strength agent, a tackifier and silica fume in a mass ratio of 1:2: 1; the adhesion promoter included 1.3kg of betaine, 2.4kg of cetyltrimethylammonium bromide and 1kg of 4-tributylmethylammonium bromide; the early strength agent comprises 0.8kg of potassium bromide, 1.2kg of sodium 2, 2' -dithiodibenzoate and 0.8kg of sodium cinnamate;
s3, adding cement, mineral powder and fly ash into the product obtained in the step S2, and uniformly stirring, wherein the cement is P.O42.5 silicate waterThe 3d compressive strength of the mud is 28.6MPa, the 28d compressive strength is 48.7MPa, and the specific surface area of the mineral powder is 450m2The activity index is 95% in 28 days, the fluidity ratio is 99%, class F class II fly ash with the fineness (the residue of a 45 mu m square-hole sieve) of less than or equal to 12%, the water demand ratio is 98% and the ignition loss is less than or equal to 4.5%.
TABLE 1 raw material amounts of low-bleeding concrete for underwater use in examples 1 to 5
Figure BDA0002912941750000081
Examples 2 to 5: the dosage of the raw materials of the low bleeding concrete for underwater is shown in the table 1.
Example 6: a low bleeding concrete for underwater use, which is different from example 2 in that the preparation method of the low bleeding concrete for underwater use comprises the steps of:
s1, pre-mixing sand, pebbles and 1/2 of water uniformly, wherein the sand is II-zone graded sand, the fineness modulus is 2.6, and the apparent density is 2600kg/m3Bulk density of 1500kg/m3The content of mud is 0.5%, the mass percent of chloride ions is 0.00017%, pebbles with the particle size of 15mm have the content of needle-shaped particles of 5%, and the apparent density is 2600kg/m3Bulk density of 1500kg/m3The mud content is 0.2%;
s2, residual water, a flocculating agent, a water reducing agent and an anti-dispersing agent, wherein the flocculating agent is prepared by mixing polyacrylamide, sodium carboxymethylcellulose and polyaluminium chloride in a mass ratio of 1:0.8:1.5, the water reducing agent is prepared by mixing a beta-sodium naphthalenesulfonate formaldehyde condensate in a mass ratio of 1:1.7:1.2, a slump-retaining polycarboxylic acid water reducing agent and a high water-reducing polycarboxylic acid water reducing agent, and the anti-dispersing agent comprises an early strength agent, a tackifier and siliceous dust in a mass ratio of 1:2.5: 1.5; the tackifier comprises 1.3kg of betaine, 2.4kg of hexadecyl trimethyl ammonium bromide and 1kg of 4-tributyl methyl ammonium bromide; the early strength agent comprises 0.8kg of potassium bromide, 1.2kg of sodium 2, 2' -dithiodibenzoate and 0.8kg of sodium cinnamate;
s3, adding cement, mineral powder and fly ash into the product obtained in the step S2, and uniformly stirringThe cement is P.O42.5 Portland cement, the 3d compressive strength is 28.6MPa, the 28d compressive strength is 48.7MPa, and the specific surface area of the mineral powder is 450m2The activity index is 95% in 28 days, the fluidity ratio is 99%, class F class II fly ash with the fineness (the residue of a 45 mu m square-hole sieve) of less than or equal to 12%, the water demand ratio is 98% and the ignition loss is less than or equal to 4.5%.
Example 7: a low bleeding concrete for underwater use, which is different from example 2 in that the preparation method of the low bleeding concrete for underwater use comprises the steps of:
s1, pre-mixing sand, pebbles and 1/2 of water uniformly, wherein the sand is graded sand in a zone II, the fineness modulus is 2.7, and the apparent density is 2700kg/m3Bulk density of 1600kg/m3The mud content is 0.7%, the mass percent of chloride ions is 0.00019%, pebbles with the particle size of 25mm, the content of needle-shaped particles is 6%, and the apparent density is 2700kg/m3Bulk density of 1600kg/m3The mud content is 0.3%;
s2, residual water, a flocculating agent, a water reducing agent and an anti-dispersing agent, wherein the flocculating agent is prepared by mixing polyacrylamide, sodium carboxymethylcellulose and polyaluminium chloride in a mass ratio of 1:1:2, the water reducing agent is prepared by mixing a beta-sodium naphthalenesulfonate formaldehyde condensation compound, a slump-retaining polycarboxylic acid water reducing agent and a high water-reducing polycarboxylic acid water reducing agent in a mass ratio of 1:2.4:2, and the anti-dispersing agent comprises an early strength agent, a tackifier and siliceous dust in a mass ratio of 1:2.5: 1.5; the tackifier comprises 1.3kg of betaine, 2.4kg of hexadecyl trimethyl ammonium bromide and 1kg of 4-tributyl methyl ammonium bromide; the early strength agent comprises 0.8kg of potassium bromide, 1.2kg of sodium 2, 2' -dithiodibenzoate and 0.8kg of sodium cinnamate;
s3, adding cement, mineral powder and fly ash into the product obtained in the step S2, and uniformly stirring, wherein the cement is P.O42.5 Portland cement, the 3d compressive strength is 28.6MPa, the 28d compressive strength is 48.7MPa, and the specific surface area of the mineral powder is 450m2The activity index is 95% in 28 days, the fluidity ratio is 99%, class F class II fly ash with the fineness (the residue of a 45 mu m square-hole sieve) of less than or equal to 12%, the water demand ratio is 98% and the ignition loss is less than or equal to 4.5%.
Example 8: a low bleeding concrete for underwater use, which is different from example 2 in that the tackifier comprises 1.6kg of betaine, 2.9kg of cetyltrimethylammonium bromide and 1.5kg of 4-tributylmethylammonium bromide; the early strength agent comprises 1.1kg of potassium bromide, 1.7kg of sodium 2, 2' -dithiodibenzoate and 1.2kg of sodium cinnamate.
Example 9: a low bleeding concrete for underwater use, which is different from example 2 in that the tackifier comprises 2kg of betaine, 3.4kg of cetyltrimethylammonium bromide and 2kg of 4-tributylmethylammonium bromide; the early strength agent comprises 1.4kg of potassium bromide, 2.2kg of sodium 2, 2' -dithiodibenzoate and 1.6kg of sodium cinnamate.
Example 10: a low-bleeding concrete for underwater use, which is different from example 2 in that silica fume is prepared from preparation example 1 of silica fume.
Example 11: a low-bleeding concrete for underwater use, which is different from example 2 in that silica fume is prepared from preparation example 2 of silica fume.
Example 12: a low-bleeding concrete for underwater use, which is different from example 2 in that silica fume is prepared from preparation example 3 of silica fume.
Example 13: a low-bleeding concrete for underwater use, which is different from example 2 in that silica fume is prepared from preparation example 4 of silica fume.
Example 14: a low-bleeding concrete for underwater use, which is different from example 2 in that silica fume is prepared from preparation example 5 of silica fume.
Example 15: a low-bleeding concrete for underwater use, which is different from example 2 in that silica fume is prepared from preparation example 6 of silica fume.
Example 16: the underwater low-bleeding concrete is different from the concrete in the embodiment 10 in that 15kg/m is added in the step (3)3The slow-release bactericide of (1), which is prepared by preparation example 1 of the slow-release bactericide.
Example 17: the underwater low-bleeding concrete is different from the concrete in the embodiment 10 in that 20kg/m is added in the step (3)3The slow-release bactericide of (1) is prepared by preparation example 2 of the slow-release bactericide.
Example 18: underwater low-bleeding coagulationThe difference between the soil and the soil in example 10 is that 25kg/m was added in step (3)3The sustained-release bactericide of (1), which is prepared by preparation example 3 of the sustained-release bactericide.
Example 19: the underwater low-bleeding concrete is different from the concrete in the embodiment 10 in that 15kg/m is added in the step (3)3The slow-release bactericide of (1), which is prepared by preparation example 4 of the slow-release bactericide.
Example 20: the underwater low-bleeding concrete is different from the concrete in the embodiment 10 in that 15kg/m is added in the step (3)3The sustained-release bactericide of (1), which is prepared by preparation example 5 of the sustained-release bactericide.
Example 21: the underwater low-bleeding concrete is different from the concrete in the embodiment 10 in that 15kg/m is added in the step (3)3The slow-release bactericide of (1), which is prepared by preparation example 6 of the slow-release bactericide.
Comparative example
Comparative example 1: the concrete with low bleeding for underwater is different from the concrete in the embodiment 1 in that the potassium bromide is not added in the early strength agent.
Comparative example 2: the concrete with low bleeding for underwater is different from the concrete in the embodiment 1 in that the sodium 2, 2' -dithiodibenzoate is not added in the early strength agent.
Comparative example 3: the underwater low-bleeding concrete is different from the concrete in example 1 in that trans-o-hydroxycinnamic acid is not added in the early strength agent.
Comparative example 4: a low bleeding concrete for underwater use, which is different from example 1 in that cetyltrimethylammonium bromide was not added to the tackifier.
Comparative example 5: a low bleeding concrete for underwater use, which is different from example 1 in that tributylmethylammonium bromide is not added to the tackifier.
Comparative example 6: the concrete with low bleeding for underwater is different from the concrete in the embodiment 1 in that the 2, 2' -dithio-diphenyl sodium formate is not added in the early strength agent, and the 4-tributyl methyl ammonium bromide is not added in the tackifier.
Comparative example 7: the concrete with low bleeding for underwater is different from the concrete in the embodiment 1 in that potassium bromide is not added in the early strength agent and hexadecyl trimethyl ammonium bromide is not added in the tackifier.
Comparative example 8: the concrete with low bleeding for underwater is different from the concrete in the embodiment 1 in that hexadecyl trimethyl ammonium bromide is not added in the tackifier and sodium 2, 2' -dithiodibenzoate is not added in the early strength agent.
Comparative example 9: the concrete with low bleeding for underwater is different from the concrete in the embodiment 1 in that hexadecyl trimethyl ammonium bromide is not added in the tackifier and trans-o-hydroxy cinnamic acid is not added in the early strength agent.
Comparative example 10: the preparation process of the underwater undispersed concrete comprises the following steps: step one, 590kg of sand and 840kg of stone are added into a stirring kettle to be pre-stirred for 30 s; step two: adding 320kg of cement, 5kg of carboxymethyl cellulose, 4kg of triethanolamine and 8.25kg of sodium chloride into a new stirrer, stirring, uniformly mixing, pouring into the mixture obtained in the first step, simultaneously adding 97.5kg of water and 10kg of nano silicon powder, and stirring for 1 min; step three: and (3) uniformly mixing 10kg of fatty alcohol-polyoxyethylene ether sodium sulfate, 30kg of fly ash and 2.75kg of sodium chloride, adding the mixture into the mixture obtained in the third step, and stirring for 30 s.
Performance test
Concrete for underwater use is prepared according to the examples and the respective proportions, and performance testing is carried out according to the following method:
1. cement loss: detecting according to DL/T5117-2000 'test procedure for non-dispersive underwater concrete', and recording the detection result in table 2;
2. slump and spread: detecting according to DL/T5117-2000 'test procedure for non-dispersive underwater concrete', and recording the detection result in table 2;
3. bleeding rate: detecting according to a bleeding and pressure bleeding test in GB/T50080-2002 Standard of Performance test methods of common concrete mixtures;
4. land-water strength ratio: (1) preparation of test blocks: the underwater concrete test block is prepared according to the method of 7.1 in DL/T5117-2000, when the test block formed on land is poured, the surface of a test mold is covered by a plastic film to prevent the water of the concrete from evaporating, and then the test mold is placed at 25 ℃ and stands for 2 days and then is removed; (2) and (3) maintaining the test block: maintaining the test blocks formed on land and under water in a standard curing room with the temperature of 22 ℃ and the humidity of 95 percent, removing wiping the test blocks after the test blocks are maintained for testing the corresponding performance; (3) and (3) mechanical property detection: the test is carried out according to GB/T50081-2002 standard of mechanical property test method of common concrete, cube test blocks of 100mm multiplied by 100mm are selected as mechanical property test blocks, the strength of land concrete and underwater concrete in 7 days and 28 days is respectively measured, the land-water strength ratio is calculated, and the test results are recorded in a table 3.
TABLE 2 Performance testing of underwater low-bleeding concrete
Figure BDA0002912941750000121
Figure BDA0002912941750000131
As can be seen from the data in examples 1-9 and Table 2, the anti-dispersant prepared by using the early strength agent and the tackifier can effectively reduce the cement loss of the concrete for underwater use, the cement loss is within 0.5%, the cement loss meets the regulation of the cement loss in DL/T5117-2000, the slump of the concrete is more than 200mm at 0h, the expansion degree is more than 400-mm, and the anti-dispersant has good self-leveling and self-compacting effects, the slump and expansion loss of the concrete is small at 2h, no time loss exists, the concrete has good fluidity, the bleeding rate is within 2.5%, the bleeding amount is small, and the anti-bleeding effect is good.
In examples 10 to 12, silica fume pretreated with fly ash, zeolite, etc. was used, and it is understood from the results of the tests that the cement loss and bleeding rate of the concrete prepared in examples 10 to 12 were significantly reduced as compared with those of examples 1 to 9, indicating that the pretreated silica fume was effective in reducing the cement loss of the concrete under water and increasing the bleeding performance.
In example 13, since zeolite and fly ash are not added, the cement loss is increased to 0.479%, and the bleeding rate is 2.3%, compared with example 10, the cement loss is increased, and the bleeding rate is increased, which shows that zeolite and fly ash can effectively increase the viscosity of concrete and reduce the cement loss and the bleeding amount.
In example 14, the silicone-modified acrylic emulsion was used as a mixed solution to be atomized on the surface of silica fume, and in example 15, the mixed solution and silica fume were simply mixed, and it was found from the results of the tests that the concrete cements prepared in examples 14 to 15 had increased loss and increased bleeding rate.
The concrete prepared in examples 16 to 21 showed no significant change in cement loss, bleeding rate and loss with time as compared with example 10.
In comparative example 1, potassium bromide is not added in the early strength agent, in comparative example 2, sodium 2' -dithiodibenzoate is not added in the early strength agent, in comparative example 3, trans-o-hydroxycinnamic acid is not added in the early strength agent, so that the loss and bleeding rate of the concrete cement prepared in comparative examples 1-3 are increased compared with those of example 1.
Comparative example 4 in which cetyltrimethylammonium bromide was not added to the thickener, and comparative example 5 in which tributylmethylammonium bromide was not added to the thickener, the cement loss of concrete increased, the bleeding rate increased, and the slump loss increased with time.
Comparative example 6 because the early strength agent is not added with the sodium 2,2 '-dithio-phthalate and the tackifier is not added with the 4-tributyl methyl ammonium bromide, compared with comparative examples 2 and 5, the cement loss in comparative example 6 is increased, and the slump loss is increased, which shows that the sodium 2, 2' -dithio-phthalate and the 4-tributyl methyl ammonium bromide have synergistic effect, can reduce the cement loss of concrete under water and improve the bleeding performance.
Comparative example 7 because no potassium bromide was added to the early strength agent and no cetyltrimethylammonium bromide was added to the tackifier, it can be seen from the combination of comparative example 1 and comparative example 4 that potassium bromide and cetyltrimethylammonium bromide have a synergistic effect, increasing the viscosity of the concrete and improving the loss of cement underwater.
Comparative example 8 because hexadecyl trimethyl ammonium bromide is not added in the tackifier, and 2,2 '-dithio sodium dibenzoate is not added in the early strength agent, compared with the detection results of comparative example 2 and comparative example 4, it can be known that cement loss of concrete in comparative example 8 is increased, and slump loss is increased with time, which shows that hexadecyl trimethyl ammonium bromide and 2, 2' -dithio sodium dibenzoate have good synergistic effect, and can effectively improve the underwater anti-dispersion performance of concrete.
Comparative example 9 because hexadecyl trimethyl ammonium bromide is not added in the tackifier and trans-o-hydroxycinnamic acid is not added in the early strength agent, compared with the detection results in comparative example 3 and comparative example 4, the concrete prepared in comparative example 9 has large cement loss and is easy to bleed when underwater, which shows that hexadecyl trimethyl ammonium bromide and trans-o-hydroxycinnamic acid have better synergistic effect.
Comparative example 10 is an underwater undispersed concrete prepared by the prior art, the cement loss is 0.498% and the water bleeding rate is 2.5% under water, and the anti-dispersion property and the water bleeding property are inferior compared with the present application.
TABLE 3 land-water strength ratio of concrete
Figure BDA0002912941750000151
Figure BDA0002912941750000161
It can be seen from table 3 and examples 1 to 9 that the concrete prepared in examples 1 to 9 has higher compressive strength under water and compressive strength on land, the land-water strength ratio of 7d reaches 80.6 to 82.3 percent, and the land-water strength ratio of 28d is 88.6 to 89.3 percent, which indicates that the concrete with low bleeding under water has better anti-dispersion performance.
The concrete prepared in examples 10 to 12, in which the pretreated silica fume was added, had an increased compressive strength ratio of 7d and an increased compressive strength ratio of 28d as compared with example 1, indicating that the dispersion resistance of the concrete was further improved by the addition of the pretreated silica fume.
Example 13 since no zeolite and fly ash were added during the silica fume treatment, it can be seen from the data in table 3 that the compressive strength of concrete prepared in example 13 was reduced in the 7-day and 28-day underwater and road and the land-water strength ratio was significantly reduced compared to example 10, which indicates that the zeolite and fly ash added during the silica fume pretreatment can not only increase the underwater compressive strength of concrete, reduce the difference between the underwater compressive strength and the land-water compressive strength, and increase the land-water compressive strength ratio.
Example 14, which uses the silicone-modified acrylic emulsion, shows a decrease in adhesion, and a decrease in underwater compressive strength, although the onshore compressive strength is not much changed from example 10.
Example 15 when silica fume was pretreated, the mixed solution was mixed with silica fume, zeolite and fly ash, and the mixed solution was unevenly coated, and the viscosity and adsorption force of silica fume were reduced, resulting in easy water dispersion of concrete and reduced underwater compressive strength.
In the examples 16 to 18, the slow-release bactericide is added on the basis of the addition of the pretreated silica fume, and compared with the examples 10 to 12, the underwater compressive strength of the concrete is increased, and the hydraulic strength ratio has no obvious change, which indicates that the underwater compressive strength of the concrete can be enhanced by adding the slow-release bactericide.
In example 19, using the silicone-modified acrylic emulsion as a film formulation, the underwater and on-road compressive strength of the concrete was not greatly changed and the land-water compressive strength ratio was not greatly changed, as compared with examples 16 to 18.
In example 20, cerium nitrate and europium sulfate were not added to the film formulation, and the underwater compressive strength and the onshore compressive strength of the concrete were reduced as compared with example 16, indicating that cerium nitrate and europium sulfate can increase the underwater compressive strength of the concrete.
Example 21 the concrete prepared in example 21 has the same performance as example 16 when the slow release bactericide prepared by using copper sulfate as the core material is added into the concrete.
Comparative example 1 because potassium bromide was not added to the early strength agent, comparative example 2 because sodium 2, 2' -dithiodibenzoate was not added to the early strength agent, and comparative example 3 because trans-o-hydroxycinnamic acid was not added to the early strength agent, the concrete prepared in comparative examples 1 to 3 had a reduced compressive strength under water and on land at 7d as compared with example 1, and the compressive strength ratio under water and on land at 7d was reduced, and at 28d, the compressive strength under water and on land was reduced, and the compressive strength ratio on water and on land was reduced.
Comparative example 4 since cetyltrimethylammonium bromide was not added to the tackifier, it can be seen from the data in table 3 that the concrete prepared in comparative example 4 has a compression strength on land that is not much different from that of example 1, but the underwater compression strength is reduced, and the land-water compression strength ratio is obviously reduced.
In comparative example 5, because tributyl methyl ammonium bromide is not added in the tackifier, the land and water compressive strength ratio of the concrete is reduced, and the underwater compressive strength is obviously reduced.
In comparative example 6, because the sodium 2,2 '-dithio-xylene sulfonate is not added in the early strength agent and the 4-tributyl methyl ammonium bromide is not added in the tackifier, compared with comparative examples 2 and 5, the ratio of the underwater compressive strength to the amphibious compressive strength in comparative example 6 is obviously reduced, which shows that the sodium 2, 2' -dithio-xylene sulfonate and the 4-tributyl methyl ammonium bromide have stronger synergistic effect.
Comparative example 7 because no potassium bromide was added to the early strength agent and no cetyltrimethylammonium bromide was added to the tackifier, it can be seen from the combination of comparative example 1 and comparative example 4 that potassium bromide and cetyltrimethylammonium bromide have a synergistic effect, and can effectively improve the underwater compressive strength of concrete and increase the land-water compressive strength ratio.
Comparative example 8 because hexadecyl trimethyl ammonium bromide is not added in the tackifier and sodium 2,2 '-dithiodibenzoate is not added in the early strength agent, compared with the detection results of comparative example 2 and comparative example 4, the amphibious compression strength ratio in comparative example 8 is obviously reduced, which shows that hexadecyl trimethyl ammonium bromide and sodium 2, 2' -dithiodibenzoate have good synergistic effect.
Comparative example 9 because hexadecyl trimethyl ammonium bromide is not added in the tackifier and trans-o-hydroxycinnamic acid is not added in the early strength agent, compared with the detection results in comparative example 3 and comparative example 4, the concrete prepared in comparative example 9 has small compressive strength and is easy to disperse under water, and the land-water compressive strength ratio is reduced, which shows that hexadecyl trimethyl ammonium bromide and trans-o-hydroxycinnamic acid have better synergistic effect.
Comparative example 10 is a prior art prepared underwater undispersed concrete, the land-water compressive strength ratio of 7d is only 77%, and the land-water compressive strength ratio of 28d is 82%, which is a great difference from the present application.
Secondly, detecting the moss preventing effect of the concrete:
the concrete prepared in example 1, example 10, comparative example 10 and examples 16 to 21 was added to example 1 in an amount of 15kg/m3The commercially available moss removing inhibitor (Baifu artistic building materials Co., Ltd., Chongqing, model azx-A + B) is used as a control group, after casting and forming, moss seed solution is inoculated on a concrete test block by a spraying method, the inoculated concrete test block is placed in a constant-temperature and constant-humidity illumination incubator (the temperature is 25 +/-2 ℃, the relative humidity is 85%, and the illumination intensity is 1000-.
TABLE 4 detection of the effect of the concrete in inhibiting the growth of lichen
Figure BDA0002912941750000181
In the control group in which the commercially available moss removing inhibitor was added to the concrete, the growing area of the moss on the concrete was 25% at week 3 and reached 95% at week 6 when the commercially available moss removing inhibitor was added to the concrete, as can be seen from table 4 and examples 1, 10 and 16 to 21, respectively, whereby the commercially available moss removing inhibitor had a good immediate moss removing effect, but the moss removing effect of the commercially available moss removing inhibitor was decreased and the growing area of the moss was increased significantly after 6 weeks.
Example 1 is the concrete prepared in this application, in which no desmearing product was added, the area of the concrete where moss was grown reached 45% by week 1 and 94% by week 6, and example 10, in which pretreated silica fume was used, the area of the concrete where moss was grown was not much different from example 1 by weeks 1 and 6.
After the slow-release bactericide is added in the examples 16 to 18, the growth area of the moss on the concrete is only 5% or less at the 1 st week, and the growth area of the moss on the concrete is not greatly changed compared with the 1 st week when the moss grows to the 6 th week, which indicates that the concrete prepared in the examples 16 to 18 has a strong instant moss inhibiting effect and a strong long-term moss inhibiting effect.
In example 19, since the silicone modified acrylic emulsion was used as a film formulation in the slow-release bactericide, the concrete had a good moss-inhibiting effect in the first week, but the moss grew rapidly in the 6 th week with a growth area of 85%, indicating that the silicone resin emulsion did not have a slow-release effect.
In example 20, since cerium nitrate and europium sulfate were not added to the film preparation, it can be seen from the data in table 4 that the growth area of moss on the concrete surface reached 41% in week 1, which is not much different from that in examples 1 and 10, and the inhibition effect on moss was poor, and at week 6, the growth area of moss was decreased to 13%, indicating that tourmaline powder and the like in the film preparation was released over time, and the long-acting moss removing effect was achieved.
In example 21, the results in Table 4 show that the green moss growth in week 1 is not much different from examples 16 to 18, and example 21 shows that the green moss has a better short-term green moss inhibiting effect, and the green moss growth area increases with time at week 6, so that the green moss is less inhibited by copper sulfate than the tourmaline powder, jade powder and ethylicin in the present application.
Comparative example 10 is a concrete prepared according to the prior art, and similar to examples 1 and 10, the concrete prepared according to comparative example 10 has a poor effect of suppressing moss.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (10)

1. The underwater low-bleeding concrete is characterized by comprising the following components in parts by weight: 420 parts of cement in 370 portions, 700 parts of sand in 650 portions, 1100 parts of pebble in 1060 portions, 40-55 parts of fly ash, 190 parts of water in 140 portions, 60-80 parts of mineral powder, 5-10 parts of flocculating agent, 10-15 parts of water reducing agent and 18-30 parts of anti-dispersing agent;
the anti-dispersing agent comprises an early strength agent, a tackifier and silica fume with the mass ratio of 1:2-3: 1-2;
the tackifier comprises the following components in parts by weight: 1.3-2 parts of betaine, 2.4-3.4 parts of hexadecyl trimethyl ammonium bromide and 1-2 parts of tributyl methyl ammonium bromide;
the early strength agent comprises the following components in parts by weight: 0.8-1.4 parts of potassium bromide, 1.2-2.2 parts of sodium 2, 2' -dithiodibenzoate and 0.8-1.6 parts of sodium cinnamate.
2. The underwater low-bleeding concrete according to claim 1, wherein the silica fume is pretreated by: calcining 1-2 parts of silica fume and 0.3-0.6 part of sodium carbonate at the temperature of 900 ℃ under 800-; (2) mixing 1.5-2.5 parts of acrylamide, 0.2-0.5 part of gamma-methacryloxypropyltrimethoxysilane, 0.05-0.1 part of potassium persulfate, 0.24-0.5 part of tetramethylethylenediamine, 0.01-0.05 part of 20-30% tetramethylammonium hydroxide and 6-10 parts of water to prepare a mixed solution; (3) introducing supercritical carbon dioxide into the mixed solution in a closed environment, spraying the mixed solution onto the product obtained in the step (1), wherein the spraying pressure is 5-8MPa, and the mass ratio of the supercritical carbon dioxide to the mixed solution is 1: 0.05-0.2; (4) and (4) preserving the heat of the product obtained in the step (3) for 40-48h in water bath at the temperature of 25-30 ℃.
3. The underwater low-bleeding concrete according to claim 1, wherein the water reducing agent is a mixture of water reducing agent and water reducing agent in a mass ratio of 1: 1-2.4:0.4-2 of a beta-sodium naphthalenesulfonate formaldehyde condensate, a slump-retaining polycarboxylic acid water reducing agent and a high water-reducing polycarboxylic acid water reducing agent.
4. The underwater low-bleeding concrete according to claim 1, wherein the flocculant is prepared by mixing polyacrylamide, sodium carboxymethylcellulose and polyaluminium chloride, and the mass ratio of the polyacrylamide to the carboxymethylcellulose to the polyaluminium chloride is 1:0.6-1: 1.3-2.
5. The underwater low-bleeding concrete according to claim 4, wherein the polyacrylamide has an average molecular weight of 120-160 ten thousand.
6. The underwater low-bleeding concrete according to claim 1, wherein the cement is p.o42.5 portland cement, the 3d compressive strength is 28.6MPa, and the 28d compressive strength is 48.7 MPa.
7. The underwater low-bleeding concrete as claimed in claim 1, wherein the sand is a graded sand in zone II, the fineness modulus is 2.5-2.7, and the apparent density is 2500-3The bulk density is 1400-1600kg/m3The mud content is 0.2-0.7%, and the mass percentage of chloride ions is 0.00015-0.00019%.
8. The underwater low-bleeding concrete as claimed in claim 1, wherein the stones are pebbles having a particle size of 5-25mm, a needle-flake particle content of 4-6%, and an apparent density of 2500-3The bulk density is 1400-1600kg/m3The mud content is 0.1-0.3%.
9. The method for preparing the low bleeding concrete for underwater use according to any one of claims 1 to 8, comprising the steps of:
s1, mixing sand, gravel and 1/2 of water uniformly;
s2, mixing the residual water, the flocculating agent, the water reducing agent and the anti-dispersing agent uniformly, and then mixing the mixture and the substance obtained in the step S1 uniformly;
and S3, adding cement, mineral powder and fly ash into the product obtained in the step S2, and uniformly stirring.
10. The preparation method of the underwater low-bleeding concrete according to claim 9, wherein 15 to 25 parts by weight of slow-release bactericide is further added to S3, and the preparation method of the slow-release bactericide is as follows: (1) dissolving corn starch with water, dissolving chitosan with glacial acetic acid, mixing the two solutions according to the mass ratio of 1:0.9-1.1, gelatinizing at 90-95 deg.C for 0.5-1h, and mixing well to obtain film preparation; (2) uniformly mixing 1-2 parts by weight of tourmaline powder, 0.5-1 part by weight of jade powder and 0.5-1 part by weight of ethylicin to prepare a core material; (3) adding 0.4-0.7 part of cerium nitrate and 0.1-0.4 part of europium sulfate into 1-2 parts of the film preparation by weight, uniformly mixing, spraying the mixture on 0.6-1.2 parts of core material, and drying by hot air to obtain the slow-release bactericide.
CN202110094129.3A 2021-01-23 2021-01-23 Underwater low-bleeding concrete and preparation method thereof Pending CN112939528A (en)

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