CN108726953B - Freeze-thaw resistant concrete interface agent and preparation method thereof - Google Patents
Freeze-thaw resistant concrete interface agent and preparation method thereof Download PDFInfo
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- CN108726953B CN108726953B CN201810843820.5A CN201810843820A CN108726953B CN 108726953 B CN108726953 B CN 108726953B CN 201810843820 A CN201810843820 A CN 201810843820A CN 108726953 B CN108726953 B CN 108726953B
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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
- 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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Abstract
The invention provides a freeze-thaw resistant concrete interface agent and a preparation method thereof, wherein the interface agent comprises 350 parts of cementing material 150-100 parts, 40-100 parts of admixture, 300 parts of fine aggregate 150-1 part of thickening agent, 10-15 parts of composite regulator and 30-60 parts of water. The freeze-thaw resistance of the concrete interface agent can be greatly enhanced through the performance synergistic effect among the paraffin, the air entraining agent and the modified emulsion polymer, the concrete interface agent also has the excellent characteristics of low-temperature flexibility, low viscosity, high interface bonding force, aging resistance, water resistance, alkali resistance and the like, the concrete interface agent can realize the low-temperature setting and hardening process, and can be constructed at the temperature range of 5 ℃ and below.
Description
Technical Field
The invention relates to the field of concrete interface agents, in particular to a freeze-thaw resistant concrete interface agent and a preparation method thereof.
Background
The concrete interface agent is also called interface adhesive and interface agent. The interface agent used in the present national engineering mainly comprises cement paste, expansive cement paste, epoxy glue, polymer modified cement mortar and the like, wherein the polymer modified cement mortar is prepared from cement, aggregate, high polymer bonding material and various auxiliary agents, is a novel bonding layer processing material after high polymer modification, can form a high-strength hardening body with larger bonding force and certain toughness with concrete after hydration reaction, is a surface processing material applied to concrete surface repairing and reinforcing or concrete surface increasing functional material, can increase the bonding force between new and old concrete and between concrete and plastering mortar, can replace the traditional roughening process, accelerate the construction progress and the like, and the bonding strength of the new and old concrete is directly related to the quality of the repaired and reinforced concrete. At present, the base layers of the concrete interface treatment materials applied in China mainly comprise mortar base layers, concrete base layers, old wall and floor tile base layers, various wall material base layers, non-metal veneer and veneer base layers, heat-preservation polyphenyl board base layers and the like.
However, most concrete interface agents in practical engineering application have the problems of low bonding strength, poor erosion resistance, water resistance, durability and low-temperature flexibility, easy glue failure, cracking, falling off, hollowing and the like in a humid environment, are easy to freeze at the temperature below-5 ℃, even generate emulsion breaking phenomenon, and have poor freeze-thaw resistance, so that the application of the concrete interface agents in a freeze-thaw environment is greatly limited, particularly in cold regions, frozen storehouses and the like, and the examples of the influence of the freeze-thaw on the structural durability of the concrete are rare, and a large amount of capital is invested for the concrete interface agents to maintain and reinforce every year in China. When new concrete is adopted to maintain and reinforce the concrete, the repaired new and old concrete bonding surface and the new concrete or old concrete body are frequently subjected to freeze-thaw damage again. The reason for this is mainly because frozen water and supercooled water exist at a certain freezing temperature, the frozen water expands in volume, and the supercooled water migrates, so that osmotic pressure and ice expansion pressure are formed, and stress is generated in the concrete. When the generated tensile stress exceeds the tensile strength of the concrete, the interior of the concrete cracks, and along with the increase of the number of times of freeze-thaw cycles, pores and microcracks in the concrete gradually increase and expand and are communicated with each other, the strength gradually decreases, and the surface of the concrete peels off to cause the damage of the concrete. The new and old concrete bonding surfaces are made of the same materials and similar internal structures as the new and old concrete, macroscopically, the bonding surfaces are three-phase materials consisting of the old concrete, the new concrete and an interface agent, in the process of freeze-thaw cycle, due to the positive and negative alternate change of temperature, alternate tensile stress is generated around capillary holes, so that the bonding surfaces are damaged, when the tensile stress generated in certain times of freeze-thaw cycle reaches the bonding strength of the interface, the bonding surfaces can generate micro cracks, and the micro cracks are communicated with the development of the micro cracks, so that the bonding surfaces are damaged.
At present, the research on the bonding condition of the new and old concrete interface agents is more in China, the research mainly focuses on the directions of the types of the interface agents, interface treatment, interface parts, test methods, the performance of new concrete, the dry and wet state of the interface and the like, the research on improving the freeze-thaw resistance of the concrete interface agents is less, and the concrete interface agents with good freeze-thaw resistance are less.
Therefore, the research on the concrete interface agent focuses on improving the bonding strength, the erosion resistance and the water resistance, and the concrete interface agent with good freeze-thaw resistance is developed to adapt to more application places, improve the application engineering quality in a low-temperature environment and reduce the engineering maintenance cost.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention aims to provide a freeze-thaw resistant concrete interface agent and a preparation method thereof, which are used for solving the problems of poor freeze-thaw resistance and the like of the interface agent in the prior art.
In order to achieve the purposes and other related purposes, the invention provides a freeze-thaw resistant concrete interface agent which comprises 350 parts of a cementing material, 40-100 parts of an admixture, 300 parts of a fine aggregate, 0.1-1 part of a thickener, 10-15 parts of a composite regulator and 30-60 parts of water.
In some embodiments of the present invention, the cementitious material is selected from at least one of cement, fly ash.
In some embodiments of the present invention, the cement is preferably ordinary portland cement, the grades of which include 42.5, 42.5R, 52.5R and the like, and the specific grade of the cement can be selected according to the strength requirement of the interface agent, the cement is easy to obtain, and the initial setting time of other special cements is short, the hydration heat is large, and the composite modifier is not beneficial to fully play.
In some embodiments of the present invention, the fly ash is selected from class II fly ash, and of course, class I fly ash and other classes of fly ash are also suitable for the present invention, and are reasonably selected according to the requirements of the interface agent in terms of overall strength, water demand and the like.
In some embodiments of the present invention, the admixture is selected from at least one of nanosilica, kaolin.
In some embodiments of the invention, the kaolin has a particle size of 400 mesh.
In some embodiments of the invention, the fine aggregate is selected from quartz sand.
In some embodiments of the present invention, the quartz sand has a particle size of 80 to 120 mesh.
In some embodiments of the invention, the thickening agent is selected from hydroxypropyl methyl cellulose ethers.
In some embodiments of the invention, the composite conditioner comprises a temperature conditioner, an anti-settling agent, an air entraining agent, an antifoaming agent, a dispersant, a modified emulsion polymer.
In some embodiments of the invention, the composite regulator comprises 20-40 parts of temperature regulator, 0.2-3 parts of anti-settling agent, 0.1-1 part of air entraining agent, 0.1-1 part of defoaming agent, 0.5-1 part of dispersing agent and 30-40 parts of modified emulsion polymer by weight.
In some embodiments of the invention, the temperature modifier is selected from paraffin.
In some embodiments of the present invention, the anti-settling agent is selected from at least one of amide modified hydrogenated castor oil, polyamide wax.
In some embodiments of the present invention, the weight ratio of the amide-modified hydrogenated castor oil to the polyamide wax in the anti-settling agent is 2: 1.
in some embodiments of the invention, the air entraining agent is selected from calcium lignosulfonate having the effects of improving freeze-thaw resistance, impermeability, and resistance to carbonization.
In some embodiments of the invention, the antifoaming agent is selected from at least one of DF849 antifoaming agent, KMT-2033 antifoaming agent, XHD103 antifoaming agent.
In some embodiments of the invention, the dispersant is selected from at least one of an SK-5040 dispersant (original nanotechnology Co., Ltd., Beijing), a TH-904 aqueous dispersant (Shandongtai and Water treatment science Co., Ltd.), and a HT5027 dispersant (break Tai chemical Co., Ltd., Nantong City).
The above-mentioned defoamers and dispersants are only partially listed and other defoamers and dispersants of the same type are also suitable for use in the present invention.
In some embodiments of the invention, the modified emulsion polymer comprises an emulsifier, an initiator, a modifier, a mixed monomer, a coupling agent.
In some embodiments of the present invention, the modified emulsion polymer comprises 1.5-4.5 parts by weight of emulsifier, 0.2-2 parts by weight of initiator, 30-40 parts by weight of modifier, 54-92 parts by weight of mixed monomer, and 0.5-1 part by weight of coupling agent.
In some embodiments of the present invention, the emulsifier is selected from at least one of sodium dodecyl sulfate and alkylphenol ethoxylates.
In some embodiments of the invention, the emulsifier comprises sodium dodecyl sulfate 0.5-1.5 parts, and alkylphenol ethoxylates 1.0-3.0 parts.
In some embodiments of the invention, the mass ratio of sodium dodecyl sulfate to alkylphenol ethoxylate in the emulsifier is 1: 2.
In some embodiments of the invention, the initiator is selected from at least one of sodium sulfate decahydrate, dibenzoyl peroxide.
In some embodiments of the present invention, the initiator comprises 0.1 to 1.0 parts by weight of sodium sulfate decahydrate and 0.1 to 1.0 parts by weight of dibenzoyl peroxide.
In some embodiments of the invention, the modifier is selected from at least one of diethylenetriamine, thiourea.
In some embodiments of the invention, the modifier comprises 15 to 20 parts by weight of diethylenetriamine and 15 to 20 parts by weight of thiourea.
In some embodiments of the invention, the mixed monomers include trimethylolpropane triacrylate, hydroxypropyl methacrylate, thiopropyl methyldimethoxysilane, epoxy E-44, butyl glycidyl ether, glycerol.
In some embodiments of the present invention, the mixed monomer comprises 5-10 parts by weight of trimethylolpropane triacrylate, 5-10 parts by weight of hydroxypropyl methacrylate, 5-10 parts by weight of thiopropyl methyldimethoxysilane, 5-10 parts by weight of epoxy resin E-445-10 parts by weight of butyl glycidyl ether, and 3-10 parts by weight of glycerol.
In some embodiments of the invention, the coupling agent is selected from isobutyltrimethoxysilane.
The second aspect of the invention provides a preparation method of the freeze-thaw resistant concrete interface agent, which comprises the following steps:
1) preparing an emulsifier A: dissolving emulsifier raw materials in water according to the formula amount to prepare an emulsifier A for later use;
2) preparing an initiator B: dissolving initiator raw materials in water according to the formula amount to prepare an initiator B for later use;
3) preparing a mixed monomer C: mixing the monomer raw materials according to the formula amount to prepare a mixed monomer C;
4) preparation of pre-emulsion D: mixing the mixed monomer C with the emulsifier A to prepare a pre-emulsion D;
5) preparation of solution E: mixing the pre-emulsion D with the initiator B to prepare a solution E;
6) preparation of modified emulsion polymer F: carrying out solid-liquid separation on the solution E, taking liquid, and adjusting the pH value to 7-8 to obtain a modified emulsion polymer F; the solid-liquid separation mode is usually filtration, and after the solution E is prepared, the feed liquid contains a small amount of particle impurities, and the particle impurities can be effectively separated and removed through filtration. The ammonia water is adopted to adjust the pH value, which is beneficial to the full play of the performance of the interface agent.
7) Preparing a composite regulator G: mixing a temperature regulator, an anti-settling agent, an air entraining agent, a defoaming agent and a dispersing agent with the modified emulsion polymer F according to the formula amount to prepare a composite regulator G;
8) preparing a freeze-thaw resistant concrete interface agent: and mixing a cementing material, an admixture, fine aggregate, a thickening agent, water and a composite regulator G according to the formula amount to prepare the freeze-thaw resistant concrete interface agent.
The above method is a semi-continuous seed-initiated emulsion polymerization.
In some embodiments of the present invention, in the step 4), the mixed monomer C is first mixed with a part of the composite emulsifier solution a, and then the rest of the composite emulsifier solution a is slowly added thereto to prepare the pre-emulsion D.
In some embodiments of the invention, in the step 5), the temperature of the pre-emulsion D is raised to 40 to 50 ℃, then a part of the initiator B is slowly added, then the temperature of the mixed solution is raised to 80 to 85 ℃, the heat preservation reaction is performed, after the reaction is finished, the rest of the initiator B is added into the mixed solution, the heat preservation reaction is performed, and after the reaction is finished, the temperature of the solution is lowered to 30 to 40 ℃ to prepare the solution E.
In some embodiments of the invention, in the step 5), the temperature of the mixed solution is raised to 80-85 ℃, and then the reaction is performed for 1.5-2.0h under the condition of heat preservation.
In some embodiments of the invention, in the step 5), after the rest of the initiator B is added to the mixed solution, the reaction is performed for 1 to 1.5 hours under a heat preservation condition.
In some embodiments of the present invention, in the step 6), ammonia is added dropwise to adjust the pH.
In some embodiments of the invention, in the step 6), the pH value of the solution is adjusted to 7-8.
In some embodiments of the invention, in the step 8), the mixed solution is stirred and dispersed at a high speed for 3min to 5min, and is mixed uniformly.
The third aspect of the invention provides the application of the freeze-thaw resistant concrete interface agent in repairing and reinforcing the concrete surface or diversifying the functions of the concrete surface.
As mentioned above, the freeze-thaw resistant concrete interface agent and the preparation method thereof have the following beneficial effects: (1) the concrete interface agent contains paraffin, an air entraining agent and a modified emulsion polymer, and under the condition of freeze thawing, the paraffin is solidified and releases heat, so that the osmotic pressure and the ice swelling pressure are reduced, and the tensile stress is reduced; the air entraining agent generates a large amount of uniform, stable, closed and non-communicated tiny bubbles on the interface agent of the bonding surfaces of new and old concrete, thereby avoiding the formation of capillary pipelines, reducing the water saturation of the bonding surfaces, absorbing frozen supercooled water in time in the freezing process, releasing the freezing pressure and avoiding the generation of damage stress; the modified emulsion polymer has the advantages of large cross-linking bond energy, strong bonding force and good low-temperature stability, can effectively defend the tensile stress under the freeze-thaw condition, and can greatly enhance the freeze-thaw resistance of the concrete interface agent through the performance synergistic effect of the modified emulsion polymer, the bonding force and the tensile stress under the freeze-thaw condition.
(2) The concrete interface agent also has the excellent characteristics of low-temperature flexibility, low viscosity, high interface bonding force, aging resistance, water resistance, alkali resistance and the like.
(3) The concrete interface agent can realize the low-temperature setting and hardening process and can be constructed in the temperature range of 5 ℃ and below.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It should be understood that the processing equipment or devices not specifically mentioned in the following examples are conventional in the art; all pressure values and ranges refer to absolute pressures.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
The preparation method of the freeze-thaw resistant concrete interface agent comprises the following steps:
1. raw material
Cement, fly ash, nano-silica, kaolin, quartz sand, diethylenetriamine, thiourea, trimethylolpropane triacrylate, hydroxypropyl methacrylate, thiopropyl methyldimethoxysilane, epoxy resin E-44, glycerol, sodium dodecyl sulfate, alkylphenol ethoxylates, sodium sulfate decahydrate, dibenzoyl peroxide, isobutyl trimethoxy silane, butyl glycidyl ether, hydroxypropyl methyl cellulose ether, amide modified hydrogenated castor oil, polyamide wax, dispersing agent SK-5040, calcium lignosulfonate, defoaming agent DF849 and paraffin.
2. Description of the main materials
(1) Cement: ordinary portland cement grade 42.5.
(2) Fly ash: and (3) II grade ash.
(3) Diethylenetriamine: analytically pure, the purity is more than or equal to 98 percent and the reagent is purchased from the Daoyun chemical reagent factory in Tianjin.
(4) Thiourea: analytically pure, with purity not less than 98%, purchased from the Beichen Square reagent factory in Tianjin.
(5) Glycerol: the purity is more than or equal to 99 percent and is purchased from a Beichen Square reagent factory in Tianjin.
(6) Dispersant SK-5040: colorless or light yellow, purchased from Weifang chemical industry Dadong chemical industry Co., Ltd.
(7) DF849 antifoam agent: white powder, density 340g/L, pH (1% in distilled water) about 8.0, active parts: 100% from Defeng antifoam Co., Ltd, Dongguan.
(8) Quartz sand: 80-120 meshes.
(9) Kaolin: 400 meshes.
(10) Calcium lignosulfonate (C)20H24CaO10S2): tan powder, special additives for jin zhou quan limited.
(11) Isobutyl trimethoxy silane: a coupling agent.
(12) Amide-modified hydrogenated castor oil: an anti-settling agent.
(13) Polyamide wax: an anti-settling agent.
(14) Paraffin wax: a temperature regulator.
The weight parts of the raw materials are as follows: 100-250 parts of cement, 50-100 parts of fly ash, 20-50 parts of nano silicon dioxide, 20-50 parts of kaolin, 150 parts of quartz sand, 15-20 parts of diethylenetriamine, 15-20 parts of thiourea, 5-10 parts of trimethylolpropane triacrylate, 5-10 parts of hydroxypropyl methacrylate, 5-10 parts of thiopropyl methyl dimethoxysilane, E-445-10 parts of epoxy resin, 3-10 parts of glycerol, 0.5-1.5 parts of sodium dodecyl sulfate, 1.0-3.0 parts of alkylphenol polyoxyethylene, 0.1-1.0 part of sodium sulfate decahydrate, 0.1-1.0 part of dibenzoyl peroxide, 0.5-1.0 part of isobutyl trimethoxy silane, 0.5-1.0 part of butyl glycidyl ether, 0.1-1.0 part of hydroxypropyl methyl cellulose ether, 0.1-2 parts of amide modified hydrogenated castor oil, 0.1-1 part of polyamide wax, 0 part of sodium hydroxide, and sodium hydroxide, 0.5 to 1.0 portion of dispersant, 0.1 to 1.0 portion of calcium lignosulfonate, 0.1 to 1.0 portion of defoamer, 20 to 40 portions of paraffin and 130-260 portions of water.
3. Experimental procedure
The raw materials are proportioned according to the parts by weight:
1) preparing an emulsifier A: 0.5-1.5 parts of sodium dodecyl sulfate and 1.0-3.0 parts of alkylphenol polyoxyethylene are mixed according to the weight ratio of 1:2 is mixed and added into 100 to 200 parts of deionized water to obtain the emulsifier A. The control of the mass ratio of the sodium dodecyl sulfate to the alkylphenol polyoxyethylene is beneficial to achieving good emulsification effect.
2) Preparing an initiator B: 0.1-1.0 part of sodium sulfate decahydrate and 0.2-0.5 part of dibenzoyl peroxide are weighed and dissolved in 100-150 parts of deionized water to obtain an initiator B.
3) Preparing a mixed monomer C: respectively and quantitatively weighing 15-20 parts of diethylenetriamine, 15-20 parts of thiourea, 5-10 parts of thiopropyl methyldimethoxysilane, 5-10 parts of trimethylolpropane triacrylate, 5-10 parts of hydroxypropyl methacrylate, 5-10 parts of epoxy resin, 3-10 parts of glycerol, 0.5-1.0 part of isobutyl trimethoxy silane and 0.5-1.0 part of butyl glycidyl ether, and uniformly mixing to obtain a mixed monomer C.
4) Preparation of pre-emulsion D: adding the mixed monomer C and 1/2 volume dose of emulsifier A into a four-neck flask, stirring at 200 r/min for 30min, slowly adding the rest emulsifier A into a constant pressure dropping funnel, and continuously stirring for 30min to obtain pre-emulsion D.
5) Preparation of solution E: heating in water bath, slowly heating the pre-emulsion D to 40-50 ℃, slowly adding 1/2 volume of initiator B into the pre-emulsion D by using a constant-pressure dropping funnel, controlling the addition to be completed within 1-1.5 h, continuously and slowly heating to 80-85 ℃, carrying out heat preservation reaction for 1.5h, adding the rest initiator B, controlling the addition to be completed within 30min, carrying out heat preservation reaction for 1h, slowly cooling to 30-40 ℃, stopping heating and stirring to obtain a solution E.
6) Preparation of modified emulsion polymer F: and filtering the solution E, removing a small amount of particle impurities contained in the feed liquid, taking the obtained liquid, and adjusting the pH value to 7-8 by using ammonia water to obtain the final modified emulsion polymer F.
7) Preparing a composite regulator G: respectively and slowly adding 20-40 parts of paraffin, 0.1-2.0 parts of amide modified hydrogenated castor oil, 0.1-1.0 part of polyamide wax, 0.5-1.0 part of SK-5040, 0.1-1.0 part of calcium lignosulfonate and 0.1-1.0 part of defoaming agent DF849 into the modified emulsion polymer F, stirring at the temperature of 30-40 ℃ for 20min at the speed of 200 revolutions per minute, cooling to room temperature to obtain a composite regulator G, and controlling the mass ratio of the amide modified hydrogenated castor oil to the polyamide wax to be 2: 1.
8) preparing a freeze-thaw resistant concrete interface agent: weighing 250 parts of cement, 50-100 parts of fly ash, 20-50 parts of nano silicon dioxide, 20-50 parts of kaolin, 150 parts of quartz sand and 0.1-1.0 part of hydroxypropyl methyl cellulose ether, mixing, dispersing at the speed of 1000 revolutions per minute for 10min, adding 30-60 parts of water and 10-15 parts of composite regulator G, stirring at high speed for dispersing for 3 min-5 min, and preparing the freeze-thaw resistant concrete interface agent.
Example 1
The preparation steps of the freeze-thaw resistant concrete interface agent of the embodiment are as follows:
1) preparing an emulsifier A: 0.5g of sodium dodecyl sulfate and 1.0g of alkylphenol polyoxyethylene are mixed and added into deionized water to obtain the emulsifier A.
2) Preparing an initiator B: 0.5g of sodium sulfate decahydrate and 0.4g of dibenzoyl peroxide were weighed out and dissolved in 100g of deionized water to obtain initiator B.
3) Preparing a mixed monomer C: 20g of diethylenetriamine, 15g of thiourea, 8g of thiopropyl methyldimethoxysilane, 10g of trimethylolpropane triacrylate, 10g of hydroxypropyl methacrylate, 5g of epoxy resin, 3g of glycerol, 0.6g of isobutyl trimethoxy silane and 0.6g of butyl glycidyl ether are respectively weighed and mixed uniformly to obtain the mixed monomer C.
4) Preparation of pre-emulsion D: adding the mixed monomer C and 1/2 volume dose of emulsifier A into a four-neck flask, stirring at 200 r/min for 30min, slowly adding the rest emulsifier A into a constant pressure dropping funnel, and continuously stirring for 30min to obtain pre-emulsion D.
5) Preparation of solution E: heating in a water bath, slowly heating the pre-emulsion D to 40-50 ℃, slowly adding 1/2 volume of initiator B into the pre-emulsion D by using a constant-pressure dropping funnel, controlling the initiator B to be added within 1 hour, continuously and slowly heating to 80-85 ℃, carrying out heat preservation reaction for 1.5 hours, adding the rest initiator B, controlling the initiator B to be added within 30min, carrying out heat preservation reaction for 1 hour, slowly cooling to 30-40 ℃, stopping heating and stirring to obtain a solution E.
6) Preparation of modified emulsion polymer F: and filtering the solution E, taking the liquid, and dropwise adding ammonia water to adjust the pH value to 7-8 to obtain the modified emulsion polymer F.
7) Preparing a composite regulator G: respectively and slowly adding 20G of paraffin, 1.0G of amide modified hydrogenated castor oil, 0.5G of polyamide wax, 0.6G of SK-5040 dispersing agent, 0.6G of calcium lignosulfonate and 0.6G of DF849 defoaming agent into 30G of modified emulsion polymer F, stirring at the temperature of 30-40 ℃ at the speed of 200 revolutions per minute for 20min, and cooling to room temperature to obtain the compound regulator G.
8) Preparing a freeze-thaw resistant concrete interface agent: weighing 150G of cement, 70G of fly ash, 25G of nano silicon dioxide, 20G of kaolin, 200G of quartz sand and 0.3G of hydroxypropyl methyl cellulose ether, mixing, dispersing at the speed of 1000 rpm for 10min, then adding 30G of water and 12G of composite regulator G, and stirring at high speed for dispersing for 3min to obtain the freeze-thaw resistant concrete interface agent.
Example 2
The preparation steps of the freeze-thaw resistant concrete interface agent of the embodiment are as follows:
1) preparing an emulsifier A: 0.8g of sodium dodecyl sulfate and 1.6g of alkylphenol polyoxyethylene are mixed and added into deionized water to obtain the emulsifier A.
2) Preparing an initiator B: initiator B was obtained by weighing 0.8g of sodium sulfate decahydrate and 0.2g of dibenzoyl peroxide in 110g of deionized water.
3) Preparing a mixed monomer C: respectively weighing and uniformly mixing 18g of diethylenetriamine, 16g of thiourea, 9g of thiopropyl methyldimethoxysilane, 9g of trimethylolpropane triacrylate, 6g of hydroxypropyl methacrylate, 8g of epoxy resin, 4g of glycerol, 0.5g of isobutyl trimethoxy silane and 0.8g of butyl glycidyl ether to obtain a mixed monomer C.
4) Preparation of pre-emulsion D: adding the mixed monomer C and 1/2 volume dose of emulsifier A into a four-neck flask, stirring at 200 r/min for 30min, slowly adding the rest emulsifier A into a constant pressure dropping funnel, and continuously stirring for 30min to obtain pre-emulsion D.
5) Preparation of solution E: heating in a water bath, slowly heating the pre-emulsion D to 40-50 ℃, slowly adding 1/2 volume of initiator B into the pre-emulsion D by using a constant-pressure dropping funnel, controlling the addition to be finished within 1h, continuously and slowly heating to 80-85 ℃, carrying out heat preservation reaction for 1.5h, adding the rest initiator B, controlling the addition to be finished within 30min, carrying out heat preservation reaction for 1h, slowly cooling to 30-40 ℃, stopping heating and stirring to obtain a solution E.
6) Preparation of modified emulsion polymer F: and filtering the solution E, taking the liquid, and dropwise adding ammonia water to adjust the pH value to 7-8 to obtain the modified emulsion polymer F.
7) Preparing a composite regulator G: respectively and slowly adding 25G of paraffin, 1.6G of amide modified hydrogenated castor oil, 0.8G of polyamide wax, 0.8G of SK-5040 dispersant, 0.5G of calcium lignosulfonate and 0.8G of DF849 defoamer into 35G of modified emulsion polymer F, stirring at the temperature of 30-40 ℃ at the speed of 200 revolutions per minute for 20min, and cooling to room temperature to obtain the compound regulator G.
8) Preparing a freeze-thaw resistant concrete interface agent: weighing 180G of cement, 60G of fly ash, 20G of nano silicon dioxide, 20G of kaolin, 250G of quartz sand and 0.2G of hydroxypropyl methyl cellulose ether, mixing, dispersing at the speed of 1000 rpm for 10min, then adding 35G of water and 14G of solution G, and stirring at high speed for dispersing for 4min to obtain the freeze-thaw resistant concrete interface agent.
Example 3
The preparation steps of the freeze-thaw resistant concrete interface agent of the embodiment are as follows:
1) preparing an emulsifier A: 1.0g of sodium dodecyl sulfate and 2.0g of alkylphenol polyoxyethylene are mixed and added into deionized water to obtain the emulsifier A.
2) Preparing an initiator B: 0.8g of sodium sulfate decahydrate and 0.5g of dibenzoyl peroxide were weighed out and dissolved in 150g of deionized water to obtain initiator solution B.
3) Preparing a mixed monomer C: respectively and quantitatively weighing 20g of diethylenetriamine, 15g of thiourea, 8g of thiopropyl methyldimethoxysilane, 8g of trimethylolpropane triacrylate, 10g of hydroxypropyl methacrylate, 10g of epoxy resin, 5g of glycerol, 0.8g of isobutyl trimethoxy silane and 0.7g of butyl glycidyl ether, and uniformly mixing to obtain the mixed monomer C.
4) Preparation of pre-emulsion D: adding the mixed monomer C and 1/2 volume dose of emulsifier A into a four-neck flask, stirring at 200 r/min for 30min, slowly adding the rest emulsifier A into a constant pressure dropping funnel, and continuously stirring for 30min to obtain pre-emulsion D.
5) Preparation of solution E: heating in a water bath, slowly heating the pre-emulsion D to 40-50 ℃, slowly adding 1/2 volume of initiator solution B into a constant-pressure dropping funnel, controlling the adding within 1.5h, continuously and slowly heating to 80-85 ℃, carrying out heat preservation reaction for 1.5h, adding the rest solution B, controlling the adding within 30min, carrying out heat preservation reaction for 1h, slowly cooling to 30-40 ℃, stopping heating and stirring, and obtaining the E.
6) Preparation of modified emulsion polymer F: and filtering the E, taking liquid, and adjusting the pH value to 7-8 by ammonia water to obtain the final modified emulsion polymer F.
7) Preparing a composite regulator G: 30G of paraffin, 2.0G of amide modified hydrogenated castor oil, 1.0G of polyamide wax, 0.9G of SK-5040 dispersant, 0.2G of calcium lignosulfonate and 0.6gDF 849G of defoamer are respectively and slowly added into 40G of modified emulsion polymer F, stirred at the temperature of 30-40 ℃ for 20min at the speed of 200 revolutions per minute, and cooled to room temperature to obtain the compound regulator G.
8) Preparing a freeze-thaw resistant concrete interface agent: weighing 200G of cement, 50G of fly ash, 25G of nano silicon dioxide, 25G of kaolin, 300G of quartz sand and 0.1G of hydroxypropyl methyl cellulose ether, mixing, dispersing at the speed of 1000 rpm for 10min, adding 40G of water and 15G of solution G, and stirring at a high speed for dispersing for 5min to obtain the freeze-thaw resistant concrete interface agent.
Performance detection
Making a standard test piece according to a standard method of JC/T907-:
alkali treatment: after the test piece is maintained for 7 days in a standard mode, the test piece is completely immersed in a saturated calcium hydroxide solution at the temperature of 23 +/-2 ℃, after 6 days, the test piece is taken out, the surface water stain is wiped off by cloth, a drawing joint is bonded by a proper high-strength bonding agent, after 7 hours, the test piece is immersed in a saturated calcium hydroxide solution at the temperature of 23 +/-2 ℃, the test piece is taken out after 24 hours, and the tensile bonding strength is detected after the surface water stain is wiped off.
And (3) freeze-thaw cycle treatment: and (3) after the test piece is subjected to standard maintenance for 7d, immersing the test piece in water of 23 +/-2 ℃ for 1d, taking out the test piece, and performing freeze-thaw cycle for 25 times. Each freeze-thaw cycle comprises the following steps: taking out the test piece from the water, wiping the surface water stain with a cloth, and keeping the temperature at minus 20 plus or minus 3 ℃ for 2h plus or minus 20 min. After the last cycle, the test piece is placed under the standard test condition for 4 hours, the joint is pulled by using proper high-strength bonding, and the tensile bonding strength is detected after 24 hours.
Soaking treatment: the test method is carried out by treating with alkali and replacing the alkali solution with water.
Through detection, the 3 concrete interface agents prepared in the embodiments 1-3 of the invention have good freezing and thawing resistance, high bonding strength, no freezing at the temperature of minus 20 ℃, 7d shear bonding strength of more than 3.0MPa, and tensile bonding strength of more than 2.5MPa (under the condition that the test piece is not processed). The tensile bonding strength of the test piece after freeze-thaw cycle treatment is more than 2.2 MPa.
The main properties are shown in table 1 below.
TABLE 1 interfacial agent Performance test results
Construction method
Firstly, chiseling, repairing and polishing treatment are carried out on loose and cracked parts of the surface of a concrete structure, so that a base surface is solid and flat, floating ash is cleaned by a steel wire brush or a broom, and the floating ash on the surface can also be cleaned by water, so that the interface does not drop water. For oil stains, the residual liquid is washed clean with clear water and dried after being washed clean with 10 wt% NaOH aqueous solution. Under the conditions that the ambient temperature is 5 ℃ and the relative humidity is 65%, the freeze-thaw resistant concrete interface agent prepared by the method is uniformly coated on a base surface by using a roller, the coating thickness is controlled to be 1-1.2 mm preferably without flowing, and the subsequent procedures can be carried out after natural curing is carried out for 24 hours. In summary, the concrete interface agent contains paraffin, an air entraining agent and a modified emulsion polymer, and under the condition of freeze thawing, the paraffin is solidified and releases heat, so that the osmotic pressure and the ice swelling pressure are reduced, and the tensile stress is reduced; the air entraining agent generates a large amount of uniform, stable, closed and non-communicated tiny bubbles on the bonding surfaces of new and old concrete, thereby avoiding the formation of capillary pipelines, reducing the water saturation of the bonding surfaces, absorbing frozen supercooled water in time in the freezing process, releasing the frozen ice pressure and avoiding generating damage stress; the emulsion polymer has large cross-linking bond energy, strong bonding force and good low-temperature stability, can effectively defend the tensile stress under the freeze-thaw condition, and can greatly enhance the freeze-thaw resistance of the concrete interface agent through the performance synergistic effect among the paraffin, the air entraining agent and the modified emulsion polymer. The concrete interface agent also has the excellent characteristics of low-temperature flexibility, low viscosity, higher interface bonding force, aging resistance, water resistance, alkali resistance and the like. The concrete interface agent can realize the low-temperature setting and hardening process and can be constructed in the temperature range of 5 ℃ and below.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. The freeze-thaw resistant concrete interface agent is characterized by comprising, by weight, 150-350 parts of a cementing material, 40-100 parts of an admixture, 150-300 parts of a fine aggregate, 0.1-1 part of a thickener, 10-15 parts of a composite regulator and 30-60 parts of water, wherein the cementing material is selected from at least one of cement and fly ash;
the composite regulator comprises, by weight, 20-40 parts of temperature regulator, 0.2-3 parts of anti-settling agent, 0.1-1 part of air entraining agent, 0.1-1 part of defoaming agent, 0.5-1 part of dispersing agent and 30-40 parts of modified emulsion polymer;
the temperature regulator is selected from paraffin, the air entraining agent is selected from calcium lignosulfonate, and the anti-settling agent is selected from at least one of amide modified hydrogenated castor oil and polyamide wax;
the modified emulsion polymer comprises 1.5-4.5 parts by weight of emulsifier, 0.2-2 parts by weight of initiator, 30-40 parts by weight of modifier, 54-92 parts by weight of mixed monomer and 0.5-1 part by weight of coupling agent; the emulsifier is selected from at least one of sodium dodecyl sulfate and alkylphenol polyoxyethylene, the initiator is selected from at least one of sodium sulfate decahydrate and dibenzoyl peroxide, and the modifier is selected from at least one of diethylenetriamine and thiourea;
the mixed monomer comprises, by weight, 5-10 parts of trimethylolpropane triacrylate, 5-10 parts of hydroxypropyl methacrylate, 5-10 parts of thiopropyl methyldimethoxysilane, 5-10 parts of epoxy resin E-445, 0.5-1.0 part of butyl glycidyl ether and 3-10 parts of glycerol.
2. The freeze-thaw resistant concrete interface agent of claim 1, wherein: the cement is selected from ordinary portland cement;
and/or the admixture is selected from at least one of nano silicon dioxide and kaolin;
and/or the fine aggregate is selected from quartz sand, and the particle size of the quartz sand is 80-120 meshes;
and/or, the thickener is selected from hydroxypropyl methyl cellulose ether.
3. The freeze-thaw resistant concrete interface agent of claim 1, wherein: the mass ratio of the amide modified hydrogenated castor oil to the polyamide wax in the anti-settling agent is 2: 1;
and/or the defoaming agent is selected from at least one of DF849 defoaming agent, KMT-2033 defoaming agent and XHD103 defoaming agent;
and/or the dispersant is selected from at least one of SK-5040 dispersant, TH-904 aqueous dispersant and HT5027 dispersant.
4. The freeze-thaw resistant concrete interface agent of claim 1, wherein: the emulsifier comprises 0.5-1.5 parts of sodium dodecyl sulfate and 1.0-3.0 parts of alkylphenol polyoxyethylene by weight;
and/or the initiator comprises 0.1-1.0 part by weight of sodium sulfate decahydrate and 0.1-1.0 part by weight of dibenzoyl peroxide;
and/or the modifier comprises 15-20 parts of diethylenetriamine and 15-20 parts of thiourea by weight;
and/or the coupling agent is selected from isobutyl trimethoxy silane.
5. The freeze-thaw resistant concrete interface agent of claim 4, wherein: the mass ratio of the sodium dodecyl sulfate to the alkylphenol polyoxyethylene in the emulsifier is 1: 2.
6. The method for preparing the freeze-thaw resistant concrete interfacial agent according to any one of claims 1 to 5, wherein: the method comprises the following steps:
1) preparing an emulsifier A: dissolving emulsifier raw materials in water according to the formula amount to prepare an emulsifier A for later use;
2) preparing an initiator B: dissolving initiator raw materials in water according to the formula amount to prepare an initiator B for later use;
3) preparing a mixed monomer C: mixing the mixed monomer raw materials according to the formula amount to prepare a mixed monomer C;
4) preparation of pre-emulsion D: mixing the mixed monomer C with the emulsifier A to prepare a pre-emulsion D;
5) preparation of solution E: mixing the pre-emulsion D with the initiator B to prepare a solution E;
6) preparation of modified emulsion polymer F: carrying out solid-liquid separation on the solution E, taking liquid, and adjusting the pH value to obtain a modified emulsion polymer F;
7) preparing a composite regulator G: mixing a temperature regulator, an anti-settling agent, an air entraining agent, a defoaming agent and a dispersing agent with the modified emulsion polymer F according to the formula amount to prepare a composite regulator G;
8) preparing a freeze-thaw resistant concrete interface agent: and mixing a cementing material, an admixture, fine aggregate, a thickening agent, water and a composite regulator G according to the formula amount to prepare the freeze-thaw resistant concrete interface agent.
7. The method of claim 6, wherein: in the step 4), the mixed monomer C is mixed with a part of the emulsifier A, and then the rest of the emulsifier A is slowly added into the mixed monomer C to prepare the pre-emulsion D;
and/or in the step 5), heating the pre-emulsion D to 40-50 ℃, slowly adding part of the initiator B, heating the mixed solution to 80-85 ℃, carrying out heat preservation reaction, adding the rest of the initiator B into the mixed solution, carrying out heat preservation reaction, and cooling the solution to 30-40 ℃ after the reaction is finished to obtain the solution E;
and/or, in the step 6), ammonia water is dripped to adjust the pH value;
and/or, in the step 6), the pH value of the solution is adjusted to 7-8;
and/or in the step 8), stirring and dispersing the mixed solution at a high speed for 3-5 min, and mixing uniformly.
8. The method of claim 7, wherein: in the step 5), heating the mixed solution to 80-85 ℃, and then carrying out heat preservation reaction for 1.5-2.0 h;
and/or, in the step 5), after the rest of the initiator B is added into the mixed solution, the reaction is carried out for 1.0 to 1.5 hours under the condition of heat preservation.
9. The use of the freeze-thaw resistant concrete interface agent according to any one of claims 1 to 5 for repairing and reinforcing concrete surface or diversifying the function of concrete surface.
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| CN111116133A (en) * | 2019-12-25 | 2020-05-08 | 三一筑工科技有限公司 | Concrete interface agent and surface treatment method of laminated member |
| CN113550514B (en) * | 2021-07-24 | 2022-09-09 | 深圳市中弘建设工程有限公司 | Construction process for preventing outer wall tile from hollowing and falling off |
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| CN103193432A (en) * | 2013-03-13 | 2013-07-10 | 浙江建设职业技术学院 | Antifreezing concrete |
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