CN108689632B - Organic fluorine silicon and metakaolin concrete waterproof reinforcing agent, and preparation method and application thereof - Google Patents
Organic fluorine silicon and metakaolin concrete waterproof reinforcing agent, and preparation method and application thereof Download PDFInfo
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- CN108689632B CN108689632B CN201810501700.7A CN201810501700A CN108689632B CN 108689632 B CN108689632 B CN 108689632B CN 201810501700 A CN201810501700 A CN 201810501700A CN 108689632 B CN108689632 B CN 108689632B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/65—Water proofers or repellants
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- 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
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- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
- Sealing Material Composition (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses an organic fluorine-silicon and metakaolin concrete waterproof reinforcing agent, a preparation method and an application thereof, wherein the organic fluorine-silicon and metakaolin concrete waterproof reinforcing agent comprises the following components, by weight, 30-50% of metakaolin, 3-5% of alkali-soluble resin, 5-15% of organic fluorine-silicon hydrophobic component, 0.1-1.0% of emulsifier, 0.5-1.0% of pH value regulator and 30-50% of water, wherein metakaolin is prepared into metakaolin powder with an alkali-soluble protective adhesive film; mixing metakaolin powder with alkali-soluble protective adhesive film in organic fluorine-silicon oil-in-water emulsion with neutral pH value to prepare the organic fluorine-silicon and metakaolin concrete waterproof reinforcing agent. The concrete using the organic fluorosilicone and metakaolin concrete waterproof reinforcing agent as an additive has the advantages of obviously reducing the water absorption rate, obviously improving the chloride absorption reduction rate, the sulfate erosion resistance and the freeze-thaw cycle resistance of the concrete, and obviously improving the durability of the concrete.
Description
Technical Field
The invention relates to the field of concrete protection in civil engineering technology, in particular to an organic fluorine-silicon and metakaolin concrete waterproof reinforcing agent and a preparation method thereof.
Technical Field
The reinforced concrete is the most used building material in the world at present, and the concrete material has fine capillary pores, so that under a severe corrosion environment, harmful ions permeate into the concrete by taking water as a medium, the reinforced concrete and the concrete are corroded through physical and chemical actions, and finally the structure is failed. Wherein, the chloride ions lead the steel bar to be corroded and expanded by destroying the steel bar passive film; CO 23 2-And Ca (OH)2The combination causes the pH value of the concrete to be reduced; SO (SO)4 2-The ions cause the concrete to generate internal expansion damage through physical and chemical actions. These corrosion factors are not isolated from moisture, and in addition, concrete damage in the freeze-thaw environment in northern areas is directly related to moisture penetration. Therefore, the most effective measure for preventing corrosion of reinforced concrete is to prevent moisture from entering the concrete.
The concrete internal-mixing type waterproof agent obtains excellent waterproof effect by changing the surface tension of the capillary hole wall of the concrete, and the conventional waterproof agents generally comprise a metal soap waterproof agent, an organic silicon waterproof agent and the like. However, due to the waterproof effect of the waterproof agents, the waterproof agents are adsorbed on the surfaces of cement particles to influence the normal hydration of the cement, and inevitably cause the reduction of the strength of the concrete. Therefore, the internally doped waterproofing agent must be added with a plurality of components for improving the strength of the concrete so as to achieve the aim of improving the strength of the concrete without reducing the strength of the concrete.
Fluorine is the element with the strongest electronegativity, has high oxidation potential and ionization energy, can obviously reduce the surface tension of an aqueous solution at extremely low application concentration, and has extremely high surface activity. Therefore, the fluorine-containing waterproof agent can reduce the using amount of the waterproof agent to the maximum extent and achieve the optimal waterproof effect. The organic silicon is an organic silicon compound with a unique structure, has the performances of inorganic materials and organic materials, and can be perfectly combined with concrete. The organic fluorine-silicon compound obtained by introducing fluorine elements to carry out organic silicon modification has all the advantages of the fluorine elements and the organic fluorine-silicon compound, and is an ideal concrete waterproof agent.
Kaolin belongs to a layered silicate structure, and van der waals force exists between layers to be firmly bonded. When kaolin is heated to about 600 ℃, the layered structure of the kaolin breaks down, forming metakaolin, which has gelling activity under appropriate excitation conditions. The strength of the concrete can be obviously improved by proper mixing amount.
However, the reactive group of organofluorosilicone is easily reacted with SiO2The hydroxyl on the surface reacts, so that metakaolin cannot be directly mixed with the organic fluorine silicon, otherwise the shelf life of the product is seriously influenced.
Disclosure of Invention
The invention aims to provide a concrete waterproof reinforcing agent simultaneously containing organic fluorine silicon and metakaolin, which can stabilize a product and is convenient to use.
The second purpose of the invention is to provide a preparation method of the concrete waterproof reinforcing agent simultaneously containing the organic fluorine silicon and the metakaolin.
The third purpose of the invention is to provide an application method of the concrete waterproof reinforcing agent simultaneously containing the organic fluorine silicon and the metakaolin.
In order to achieve the first object, the invention adopts the following technical scheme: an organic fluorine silicon and metakaolin concrete waterproof reinforcing agent is characterized in that: 30-50% of metakaolin, 3-5% of alkali-soluble resin, 5-15% of organic fluorine-silicon hydrophobic component, 0.1-1.0% of emulsifier, 0.5-1.0% of pH value regulator and 30-50% of water, wherein the metakaolin is soaked by the alkali-soluble resin, so that the surface of metakaolin particles is coated with a layer of alkali-soluble resin film, and then a spray drying process is adopted to prepare metakaolin powder with an alkali-soluble protective adhesive film; the organic fluorine-silicon hydrophobic component is dispersed into the water solution of the emulsifier through a high-speed shearing emulsification process to prepare a stable organic fluorine-silicon oil-in-water emulsion; mixing metakaolin powder with alkali-soluble protective adhesive film in organic fluorine-silicon oil-in-water emulsion with neutral pH value to prepare the organic fluorine-silicon and metakaolin concrete waterproof reinforcing agent.
The organic fluorine-silicon hydrophobic component is one or a mixture of more than two of fluorine-containing organic silicon monomers or polymers, and is prepared into a neutral oil-in-water emulsion with the pH value of 7.0.
The organic fluorine-silicon hydrophobic component is one or a mixture of any two or more of fluorine-silicon resin, fluorine polysiloxane and fluorine silane, and is prepared into neutral oil-in-water emulsion with the pH value of 7.0.
The pH regulator is mixed phosphate with pH 6.86.
The emulsifier is a fluorinated surfactant, preferably fluorinated polyethylene glycol.
In order to achieve the second object, the invention adopts the following technical scheme: a method for preparing the organic fluorosilicone and metakaolin concrete waterproofing reinforcing agent as described in any one of the above, comprising the steps of:
(1) preparing materials;
(2) soaking metakaolin by using alkali-soluble resin to coat a layer of alkali-soluble resin film on the surface of metakaolin particles, and preparing metakaolin powder with an alkali-soluble protective adhesive film by adopting a spray drying process;
(3) dispersing the organic fluorine-silicon hydrophobic component into the aqueous solution of the emulsifier by a high-speed shearing emulsification process to prepare a stable organic fluorine-silicon oil-in-water emulsion;
(4) mixing metakaolin powder with alkali-soluble protective adhesive film in organic fluorine-silicon oil-in-water emulsion with neutral pH value to prepare the organic fluorine-silicon and metakaolin concrete waterproof reinforcing agent.
And (4) adjusting the pH value of the organic fluorine-silicon oil-in-water emulsion formed in the step (3) to be neutral by adopting an acid or alkali solution.
In order to achieve the third object, the invention adopts the following technical scheme: the application method of the organic fluorine silicon and metakaolin concrete waterproof reinforcing agent comprises the step of adding the mixture of the organic fluorine silicon and metakaolin concrete waterproof reinforcing agent and the mixing water of the concrete into the raw materials of the concrete at one time for mixing.
The organic fluorine-silicon and metakaolin concrete waterproof reinforcing agent is prepared by firstly preparing water-insoluble organic fluorine-silicon materials into oil-in-water emulsion which can be dispersed in water in any proportion by using an emulsification process, and then preparing the emulsion containing SiO2And the metakaolin material which is easy to cause the organic fluorine-silicon material to deteriorate is wrapped by alkali-soluble resin, so that the metakaolin material and the organic fluorine-silicon material can be mixed without reaction. When in use, the mixture of the organic fluorine silicon and the metakaolin concrete waterproof reinforcing agent and the mixing water of the concrete are added into the raw materials of the concrete at one time for mixing. Because the concrete mixture is alkaline, the alkali-soluble resin is dissolved firstly, and active metakaolin particles are released, and the metakaolin particles have gelling activity under the action of alkali excitation to participate in hydration reaction. As the concrete is hydrated and solidified, water is consumed, the emulsified organic fluorine-silicon material is demulsified and reacts with components of the concrete to form a hydrophobic film on the capillary wall, and the alkali-soluble resin is also cured again along with the disappearance of the water to block the capillary to form a embolism benefit, so that the concrete has excellent waterproof performance without reducing the strength.
The invention adopts the organic fluorine silicon and metakaolin concrete waterproof reinforcing agent, utilizes the characteristic that the organic fluorine silicon hydrophobic material can obviously reduce the surface tension of the concrete so as to obtain the optimal waterproof effect, and utilizes the metakaolin to increase the strength of the concrete, thereby compensating the concrete strength loss caused by internally doping the waterproof agent and achieving the purpose of endowing the concrete with the waterproof effect on the premise of not reducing the concrete strength.
The material is prepared into slurry capable of being pumped, the material adopts an emulsification process to prepare the water-insoluble organic fluorine-silicon material into an oil-in-water emulsion capable of being dispersed in water in any proportion, and then the SiO-containing organic fluorine-silicon material is prepared into an oil-in-water emulsion2And the metakaolin material which is easy to cause the organic fluorine-silicon material to deteriorate is wrapped by alkali-soluble resin, so that the metakaolin material and the organic fluorine-silicon material can be mixed without reaction. The material is convenient for use, and has good fixationThe main component of the concrete is metakaolin, which equivalently replaces the cement component in the concrete mixing ratio; the balance of liquid components, the liquid components equally replace water in the concrete mixing ratio, and the liquid components are metered and mixed at one time in the concrete production process.
The concrete using the organic fluorosilicone and metakaolin concrete waterproof reinforcing agent as an additive has the advantages of obviously reducing the water absorption rate, obviously improving the chloride absorption reduction rate, the sulfate erosion resistance and the freeze-thaw cycle resistance of the concrete, and obviously improving the durability of the concrete.
Drawings
FIG. 1 is a process diagram of the present invention.
Detailed Description
For those skilled in the art to further understand the features and technical content of the present invention, refer to the following detailed description of the invention.
Example 1
40% of metakaolin; 4% of alkali-soluble resin; 5% of organic fluorine-silicon resin; 3% of organic fluorine siloxane; 2% of organic fluorosilane; 0.4 percent of emulsifier; 0.1 percent of pH value regulator; 45.5% of water: the alkali-soluble resin is alkali-soluble acrylic resin, the emulsifier is fluorinated polyethylene glycol, and the pH value regulator is mixed phosphate with the pH value of 6.86.
The concrete waterproof reinforcing agent is prepared by the following steps:
(1) preparing materials;
(2) soaking metakaolin by using alkali-soluble resin to coat a layer of alkali-soluble resin film on the surface of metakaolin particles, and preparing metakaolin powder with an alkali-soluble protective adhesive film by adopting a spray drying process;
(3) dispersing the organic fluorine-silicon hydrophobic component into the aqueous solution of the emulsifier by a high-speed shearing emulsification process to prepare a stable organic fluorine-silicon oil-in-water emulsion; adjusting the pH value to be neutral by adopting mixed phosphate with the pH value of 6.86;
(4) the metakaolin powder with alkali-soluble protective adhesive film is mixed in the organic fluorine-silicon oil-in-water emulsion with neutral pH value to prepare the organic fluorine-silicon and metakaolin concrete waterproof reinforcing agent with sample code FMK 1.
Example 2
50% of metakaolin; 5% of alkali soluble resin; 3% of organic fluorine-silicon resin; 2% of organic fluorine siloxane; 5% of organic fluorosilane; 0.3 percent of emulsifier; 0.2 percent of pH value regulator; 34.5% of water: the alkali-soluble resin is alkali-soluble acrylic resin, the emulsifier is fluorinated polyethylene glycol, and the pH value regulator is mixed phosphate with the pH value of 6.86.
The concrete waterproof reinforcing agent is prepared by the following steps:
(1) preparing materials;
(2) soaking metakaolin by using alkali-soluble resin to coat a layer of alkali-soluble resin film on the surface of metakaolin particles, and preparing metakaolin powder with an alkali-soluble protective adhesive film by adopting a spray drying process;
(3) dispersing the organic fluorine-silicon hydrophobic component into the aqueous solution of the emulsifier by a high-speed shearing emulsification process to prepare a stable organic fluorine-silicon oil-in-water emulsion; adjusting the pH value to be neutral by adopting mixed phosphate with the pH value of 6.86;
(4) the metakaolin powder with alkali-soluble protective adhesive film is mixed in the organic fluorine-silicon oil-in-water emulsion with neutral pH value to prepare the organic fluorine-silicon and metakaolin concrete waterproof reinforcing agent with sample code FMK 2.
Example 3
The samples FMK1 and FMK2 from example 1 and example 2 were incorporated into concrete and tested for water repellency and chloride absorption reduction and analyzed as follows:
TABLE 1 test mix proportions
Wherein, C35 is concrete strength grade, C35 group is blank comparison sample, C35-FMK1 group or C35-FMK2 group is to point to the concrete of C35 strength grade and is mixed with FMK1 or FMK 2.
TABLE 2 hardened concrete Performance test results
Wherein, C35 is concrete strength grade, C35 group is blank comparison sample, C35-FMK1 group or C35-FMK2 group is to point to the concrete of C35 strength grade and is mixed with FMK1 or FMK 2.
According to the concrete performance test results, the organic fluorosilicone and metakaolin concrete waterproof reinforcing agent provided by the invention can obviously improve the waterproof performance of concrete without reducing the strength of the concrete, and can improve the durability of the concrete.
However, the above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, so that equivalent structural changes made by using the content of the present specification are included in the scope of the present invention.
Claims (9)
1. An organic fluorine silicon and metakaolin concrete waterproof reinforcing agent is characterized in that: 30-50% of metakaolin, 3-5% of alkali-soluble resin, 5-15% of organic fluorine-silicon hydrophobic component, 0.1-1.0% of emulsifier, 0.5-1.0% of pH value regulator and 30-50% of water, wherein the metakaolin is soaked by the alkali-soluble resin, so that the surface of metakaolin particles is coated with a layer of alkali-soluble resin film, and then a spray drying process is adopted to prepare metakaolin powder with an alkali-soluble protective adhesive film; the organic fluorine-silicon hydrophobic component is dispersed into the water solution of the emulsifier through a high-speed shearing emulsification process to prepare a stable organic fluorine-silicon oil-in-water emulsion; mixing metakaolin powder with alkali-soluble protective adhesive film in organic fluorine-silicon oil-in-water emulsion with neutral pH value to prepare the organic fluorine-silicon and metakaolin concrete waterproof reinforcing agent.
2. The organic fluorosilicone and metakaolin concrete waterproofing reinforcing agent according to claim 1, characterized in that: the organic fluorine-silicon hydrophobic component is one or a mixture of more than two of fluorine-containing organic silicon monomers or polymers.
3. The organic fluorosilicone and metakaolin concrete waterproofing reinforcing agent according to claim 2, characterized in that: the organic fluorine-silicon hydrophobic component is one or a mixture of more than two of fluorine-silicon-containing resin, fluorine polysiloxane and fluorine silane.
4. The organic fluorosilicone and metakaolin concrete waterproofing reinforcing agent according to claim 1, characterized in that: the pH regulator is mixed phosphate with pH 6.86.
5. The organic fluorosilicone and metakaolin concrete waterproofing reinforcing agent according to claim 1, characterized in that: the emulsifier is a fluorinated surfactant.
6. The organic fluorosilicone and metakaolin concrete waterproofing reinforcing agent according to claim 5, characterized in that: the emulsifier is fluorinated polyethylene glycol.
7. A method for preparing the organic fluorosilicone and metakaolin concrete waterproof reinforcing agent as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:
(1) preparing materials;
(2) soaking metakaolin by using alkali-soluble resin to coat a layer of alkali-soluble resin film on the surface of metakaolin particles, and preparing metakaolin powder with an alkali-soluble protective adhesive film by adopting a spray drying process;
(3) dispersing the organic fluorine-silicon hydrophobic component into the aqueous solution of the emulsifier by a high-speed shearing emulsification process to prepare a stable organic fluorine-silicon oil-in-water emulsion;
(4) mixing metakaolin powder with alkali-soluble protective adhesive film in organic fluorine-silicon oil-in-water emulsion with neutral pH value to prepare the organic fluorine-silicon and metakaolin concrete waterproof reinforcing agent.
8. The method of organic fluorosilicone and metakaolin concrete waterproofing enhancer according to claim 7, characterized in that: and (4) adjusting the pH value of the organic fluorine-silicon oil-in-water emulsion formed in the step (3) to be neutral by adopting an acid or alkali solution.
9. The application method of the organic fluorosilicone and metakaolin concrete waterproof reinforcing agent as claimed in any one of claims 1 to 6, characterized in that: the organic fluorine silicon, the metakaolin concrete waterproof reinforcing agent and the concrete mixing water are added into the raw materials of the concrete at one time for mixing.
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| CN110204278B (en) * | 2019-06-10 | 2021-11-23 | 临沂市理想家园建材有限公司 | High strength waterproof concrete building structure |
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| CN114656190A (en) * | 2022-03-18 | 2022-06-24 | 中交四航工程研究院有限公司 | Fatty acid concrete hydrophobic pore suppository and preparation method thereof |
| CN116836572B (en) * | 2023-04-26 | 2024-04-26 | 长江水利委员会长江科学院 | Composite acid-resistant concrete protective coating material and preparation method and application thereof |
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