KR102220462B1 - Alkali metal liquid nano-composite-silicate-based permeable waterproofing agent and concrete structure penetration waterproofing method - Google Patents

Abstract

The present invention relates to a composite silicate waterproofing agent capable of self-healing (self-repairing) pores in concrete while simultaneously generating insoluble silicate metal hydrate and silicic acid by reacting with free metal ions in concrete as prepared by combining various kinds of alkali metal-silicate compounds, and a concrete structure penetration waterproofing method using the same. The present invention provides an alkali metal liquid nano-composite silicate-based permeable waterproofing agent comprising: a nanocomposite silicate sol composed of sodium silicate, lithium silicate, and potassium silicate; silane-based compounds; and an additive including silicon carbide, metal oxide, and carbon black.

Description

Alkali metal liquid nano-composite-silicate-based permeable waterproofing agent and concrete structure penetration waterproofing method}

The present invention relates to an alkali metal liquid nanocomposite silicate-based permeable waterproofing agent and a concrete structure spherical permeation waterproofing method, and more particularly, as it is manufactured by complexing various kinds of alkali metal-silicate compounds, it reacts with free metal ions in concrete and is insoluble. A composite silicate-based penetration waterproofing agent capable of generating silicate metal hydrate and silicic acid simultaneously and self-healing (self-repairing) micropores of concrete, and a concrete concrete penetration waterproofing method using the same.

Concrete is composed of aggregates such as water, cement, sand, and gravel, and is used to form building structures such as buildings, bridges, and tunnels by using a hydration reaction in which cement and water react and harden.

Concrete structures are divided into a basement layer buried in the ground and a surface layer exposed to the air. The basement layer is always in contact with moisture, and durability may decrease as contraction and expansion are repeated according to temperature changes. Deterioration of the durability of concrete is particularly affected by moisture, and water acts as a medium to deteriorate concrete, and dissolved sulfate, nitrate, carbonate, acid rain, etc. can accelerate damage to the concrete structure.

In order to prevent such moisture damage, various waterproofing materials have been researched and used, and a lot of research has been conducted on the development of eco-friendly waterproofing materials without emission of heavy metals or volatile organic compounds along with the global environmental protection trend today. Conventional organic waterproofing materials are deteriorated by the release of volatile organic compounds during curing and various environmental factors after curing, especially acid rain, nitrogen oxides, sulfur oxides, soot, and chlorine ions due to proportional salts of seawater. Due to the yellowing phenomenon, cracking, and swelling caused by ultraviolet rays, the service life is quickly reduced, and the difficulty of securing durability is seriously raised.

In particular, when concrete is exposed to the air, calcium hydroxide (Ca(OH) ₂ ), which is a _{cement hydrate, reacts with carbon dioxide (CO 2} ) in the air to produce carbonates (calcium carbonate, calcium hydrogen carbonate), and by this action, alkaline concrete As the deterioration proceeds from the surface to the inside, the concrete's alkalinity (PH 12.5~13) is neutralized to about 8.5~10, and the reinforcing bar blocks the passivation film in strong alkalinity. What was formed is destroyed under the influence of this, accelerating the corrosion of the reinforcing bar, and when the reinforcing bar is corroded, the volume expands, and the volume expansion of the reinforcing bar confined in the concrete accelerates the stress of the concrete structure, causing cracks and attaching the reinforcing bar. It degrades the physical performance of reinforced concrete structures such as decrease in strength, peeling of coated concrete, and decrease in strength of reinforcing bars, resulting in a crisis in the entire structure.

In addition, it is inevitable that voids are formed in the concrete during the hydration reaction, which is the process of curing concrete, and these internal voids become a path for moisture to penetrate into the concrete structure. When moisture penetrates through the internal voids, microcracks can occur, which can degrade the waterproof performance of concrete and at the same time corrode reinforcing bars, etc., and significantly affect the life of concrete structures.

Methods of imparting waterproofness to concrete include a method of forming a waterproofing membrane on the concrete surface, a method of infiltrating a waterproofing agent to a certain depth, and a method of making the concrete structure itself a waterproof structure by preventing the occurrence of voids and cracks inside the concrete structure. As in the third case, concrete waterproofing is called concrete waterproofing. The spherical waterproofing is implemented by a method of suppressing the occurrence of internal voids by reducing the mixing amount of water, a method of filling the internal voids with fine particles, and a method of preventing internal penetration of moisture by mixing a material having water repellency.

In the case of conventional waterproofing agents, most of them rely only on the waterproofing performance by water-repellent components, so there is a limit to the effect of improving the waterproofing performance, and the reduction of internal voids and the occurrence of cracks are not considered. There is a great need to develop a new liquid spherical waterproofing agent capable of self-healing (self-repairing) pores and cracks while this appears.

(0001) Korean Patent Registration No. 10-1579804 (0002) Korean Patent Application Publication No. 10-2009-0100885

In order to solve the above-described problem, the present invention is prepared by complexing a variety of alkali metal-silicate compounds, thereby simultaneously generating insoluble silicate metal hydrate and silicic acid by reacting with free metal ions in concrete, and creating micropores in concrete. We intend to provide a composite silicate waterproofing agent capable of self-healing (self-repairing) and a concrete concrete penetration waterproofing method using the same.

In order to solve the above problems, the present invention is a nanocomposite silicate sol composed of sodium silicate, lithium silicate, and potassium silicate; Silane compounds; And it provides an alkali metal liquid nanocomposite silicate-based permeable waterproofing agent comprising an additive including silicon carbide, metal oxide, and carbon black.

In one embodiment, the nanocomposite silicate sol may include 40 to 80 parts by weight of sodium silicate, 10 to 30 parts by weight of lithium silicate, and 30 to 50 parts by weight of potassium silicate.

In one embodiment, the nanocomposite silicate sol has a silicon dioxide solid content of 30 to 35 parts by weight, a metal oxide content of 25 to 30 parts by weight consisting of sodium oxide, lithium oxide and potassium oxide, and a pH of 3 to 6 days. I can.

In one embodiment, the nanocomposite silicate sol may include an aqueous colloidal nanocomposite silicate composed of sodium silicate, lithium silicate, and potassium silicate is dispersed in an alcohol-based solvent.

In one embodiment, the silane-based compound may include organo alkoxysilane or organo aminosilane.

In one embodiment, the organo alkoxysilane is tetramethoxysilane, methyltrimethoxysilane, trimethylmethoxysilane, dimethyldimethoxysilane, triethylmethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane In any one of, the organo aminosilane is N-2-(aminoethyl)-3-aminopropyl-trimethoxysilane, aminoethylaminopropyltriethoxysilane, N-2-(benzylamino)-ethyl- It may be any one of 3-aminopropyl-trimethoxysilane and N-2-(vinylbenzylamino)-ethyl-3-aminopropyl-trimethoxysilane.

In one embodiment, based on 100 parts by weight of the nanocomposite silicate sol, 5 to 15 parts by weight of aluminum oxide, 5 to 10 parts by weight of calcium carbonate, 1 to 5 parts by weight of titanium dioxide, and 0.1 to 1 parts by weight of carbon black I can.

The present invention also has a silicon dioxide solid content of 30 to 35 parts by weight, a particle size of 10 to 20 nm, a sodium oxide content of 25 to 30 parts by weight, and an aqueous colloidal nanometal oxide A 20 to 40 with a pH of 9.0 to 10.5. Part by weight, silicon dioxide solid content is 30 to 35 parts by weight, particle size is 10 to 20 nm, lithium oxide content is 25 to 30 parts by weight, pH 8.5 to 9.0 aqueous colloidal nanometal oxide B 10 to 15 parts by weight And silicon dioxide solid content is 30 to 35 parts by weight, particle size is 10 to 20 nm, potassium oxide content is 25 to 35 parts by weight, and 15 to 25 parts by weight of aqueous colloidal nanometal oxide C having a pH of 9.0 to 10.0 is mixed and stirred. Add a diluted solution consisting of potassium hydroxide and ethanol (potassium hydroxide: ethanol = 1:4 weight ratio) to the prepared composite so that the total pH of the composite solution is 12 to 13 and the metal oxide content is 25 to 35 parts by weight. A first step of preparing a composite colloidal nanometal oxide sol; With respect to 80 parts by weight of the composite colloidal nanometal oxide sol of the first step, 15 to 25 parts by weight of pure water, 10 to 18 parts by weight of potassium hydroxide, and 0.2 to 0.6 parts by weight of aluminum hydroxide are added and stirred, A second step of preparing an intermediate having a stable pH of 12 to 13 in terms of chemical structure by replacing aluminum ions and potassium ions with functional groups of nanoparticles of the sol; Alkali metal comprising a third step of reacting for 10 to 100 minutes by adding 3 to 7 parts by weight of organoalkoxysilane and 3 to 7 parts by weight of organoaminosilane to 100 parts by weight of the intermediate of the second step It provides a method of preparing a liquid nanocomposite silicate-based waterproofing agent.

The present invention also provides 10 to 15 parts by weight of aluminum oxide, 7 to 10 parts by weight of calcium carbonate, 3 to 5 parts by weight of titanium dioxide, 0.5 to 1 parts by weight of carbon black based on 100 parts by weight of the alkali metal liquid nanocomposite silicate-based permeable waterproofing agent. It provides a concrete structure concrete penetration waterproofing method, characterized in that after preparing a uniform waterproofing solution by adding it to the concrete surface.

The alkali metal liquid nanocomposite silicate-based permeable waterproofing agent and concrete structure spherical penetration waterproofing method according to the present invention are manufactured by complexing a variety of alkali metal-silicate compounds, and react with free metal ions in concrete to react with insoluble silicate metal hydrates and Silicic acid is simultaneously formed and gelled, and they fill the voids and deteriorated pores inside the concrete to improve waterproofness and strength, and can play a role in maintaining the pH of the concrete.

Hereinafter, a preferred embodiment of the present invention will be described in detail. In describing the present invention, when it is determined that a detailed description of a related known technology may obscure the subject matter of the present invention, a detailed description thereof will be omitted. Throughout the specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components, unless otherwise stated.

The present invention is intended to illustrate specific embodiments and to be described in detail in the detailed description, since various transformations can be applied and various embodiments can be provided. However, this is not intended to limit the present invention to a specific embodiment, it should be understood to include all conversions, equivalents, or substitutes included in the spirit and scope of the present invention.

The technology disclosed in the present specification is not limited to the embodiments described herein and may be embodied in other forms. However, the embodiments introduced herein are provided so that the disclosed content may be thorough and complete, and the technical idea of the present technology may be sufficiently transmitted to those skilled in the art. In the drawings, in order to clearly express the constituent elements of each device, the size of the constituent elements, such as width or thickness, is slightly enlarged. Overall, it was described at the observer's point of view when explaining the drawings, and if one element is referred to as being positioned on another element, this means that the one element is positioned directly on another element or that an additional element may be interposed between them. Include. In addition, those of ordinary skill in the relevant field will be able to implement the spirit of the present invention in various other forms without departing from the technical spirit of the present invention. In addition, the same reference numerals in the plurality of drawings refer to substantially the same elements.

The terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present invention, terms such as include or have are intended to designate the presence of features, numbers, steps, actions, components, parts, or a combination of them described in the specification, and one or more other features, numbers, and steps. It is to be understood that it does not preclude the possibility of the presence or addition of, operations, components, parts, or combinations thereof.

Meanwhile, the meaning of terms described in the present specification should be understood as follows. Terms such as “first” or “second” are used to distinguish one component from other components, and the scope of the rights is not limited by these terms. For example, a first component may be referred to as a second component, and similarly, a second component may be referred to as a first component.

In addition, expressions in the singular should be understood as including plural expressions unless clearly defined otherwise in the context, and terms such as “include” or “have” are described features, numbers, steps, actions, components, and parts. It is to be understood that it is intended to designate the existence of a combination of these and not to preclude the possibility of the presence or addition of one or more other features or numbers, steps, actions, components, parts, or combinations thereof. In addition, in performing the method or manufacturing method, each of the processes constituting the method may occur differently from the specified order unless a specific order is clearly stated in the context. That is, each process may occur in the same order as the specified order, may be performed substantially simultaneously, or may be performed in the reverse order.

The present invention is a nano-composite silicate sol consisting of sodium silicate, lithium silicate and potassium silicate; Silane compounds; And it relates to an alkali metal liquid nano-composite silicate-based permeable waterproofing agent comprising an additive including silicon carbide, metal oxide, and carbon black.

The nanocomposite silicate sol may be composed of sodium silicate, lithium silicate, and potassium silicate. In the case of a waterproofing solution using a conventional silicate sol, a two-component silicate containing only sodium silicate or lithium silicate or potassium silicate in sodium silicate was used. In the case of the three-component silicate, the content of sodium silicate may be lowered in order to see the effects of lithium silicate and potassium silicate, excluding sodium silicate, which are the main components, thereby increasing the price and decreasing the performance. However, with only sodium silicate, it is difficult to cope with concrete leaks in various ways, and it is more preferable to supply various metal ions for pH recovery in concrete. Therefore, in the present invention, by combining sodium silicate, lithium silicate, and potassium silicate in an optimal component ratio, side effects caused by the reduction of sodium silicate can be minimized, and at the same time, it is possible to cope with various leaks. to provide. At this time, the sodium silicate, lithium silicate, and potassium silicate preferably contain 40 to 80 parts by weight of sodium silicate, 10 to 30 parts by weight of lithium silicate, and 30 to 50 parts by weight of potassium silicate. Within the above range, the nano-composite silicate-based waterproofing agent of the present invention may have an optimal effect, and if there are components included below the above range, the nano-composite silicate-based waterproofing agent has desired waterproofing properties or concrete self-healing (self-healing performance). May not appear. In addition, if there are components exceeding the above range, the price may increase, and metal salts may precipitate during concrete repair, resulting in deterioration of waterproof properties.

The sodium silicate, lithium silicate, and potassium silicate are included in the nanocomposite silicate waterproofing agent, and when the nanocomposite silicate waterproofing agent is used, it reacts with calcium hydroxide present in concrete to form calcium silicate gel and metal hydroxide, at which time the chemical mechanism of hydrate formation Is the same as in Chemical Formula 1 below.

[Formula 1]

Na ₂ SiO ₃ nH ₂ O + Ca(OH) ₂ + nH ₂ O -> CaSiO nH ₂ O +2NaOH

Li ₂ SiO ₃ nH ₂ O + Ca(OH) ₂ + nH ₂ O -> CaSiO nH ₂ O +2LiOH

K ₂ SiO ₃ nH ₂ O + Ca(OH) ₂ + nH ₂ O -> CaSiO nH ₂ O +2KOH

Calcium hydroxide present in concrete is derived from calcium carbonate in limestone among concrete raw materials, and plays a role of preventing corrosion of reinforcing bars contained in concrete by maintaining the pH of concrete above 11. However, the calcium hydroxide is combined with carbon dioxide in the air to form calcium carbonate, which decreases the pH in the concrete (concrete carbonation) and increases the voids, thereby reducing the strength of concrete, corrosion of reinforcing bars, and causing cracks. .

Sodium silicate, lithium silicate, and potassium silicate of the present invention are combined with calcium hydroxide to form calcium silicate gel, as shown in Chemical Formula 1, and the calcium silicate gel can fill the voids of concrete. In addition, secondary metal hydroxides (NaOH, LiOH, KOH) can prevent corrosion of reinforcing bars by maintaining and recovering (alkali maintenance, recovery) pH in concrete.

In Formula 1, water (nH ₂ O) may be water contained in the nanocomposite silicate waterproofing agent or water that has penetrated from the outside. The nanocomposite silicate waterproofing agent is applied by mixing with water or alcohol-based solvent for convenience of construction. Particularly, the water contained at this time acts as a moving medium for the waterproofing agent, so that the waterproofing agent can easily penetrate into the concrete. Therefore, when the nanocomposite silicate waterproofing agent is applied to the surface of a building, the reaction of Formula 1 can be performed using water used as the solvent, thereby filling the previously generated pores and simultaneously recovering the pH. . In addition, since an excessive amount of the nanocomposite silicate waterproofing agent is generally applied in order to maintain waterproofness, the waterproofing agent penetrates into the concrete and exists as an unreacted material, which can carry out a reaction as shown in Formula 1 upon penetration of moisture. Concrete self-repair and pH maintenance and recovery (alkali maintenance, recovery) are possible.

[Formula 2]

2Na ₂ SiO ₃ + nH ₂ O -> Na ₂ SiO ₂ O ₅ nH ₂ O + 2NaOH

Na ₂ SiO ₂ O ₅ nH ₂ O -> Na ₂ SiO ₃ nH ₂ O + SiO H ₂ O

Looking at this in detail, as shown in Chemical Formula 2, sodium silicate (Na ₂ SiO ₃ ) contained in the waterproofing agent is combined with water and hydrolyzed to form Na ₂ SiO ₂ O ₅ ·nH ₂ O, while simultaneously forming sodium hydroxide. Occurs. At this time, the sodium hydroxide may act as a strong base to restore the pH inside the concrete. In addition, Na ₂ SiO ₂ O ₅ ·nH ₂ O is converted to sodium silicate through natural decomposition, forming silicon oxide. Silicon oxide generated from the Na ₂ SiO ₂ O ₅ ·nH ₂ O is itself a main component of sand or glass, and it is a solid, so it can not only fill the voids of concrete, but also react with calcium ions or calcium hydroxide present inside the concrete. By generating calcium silicate (CaSiO·nH ₂ O), it is possible to repair voids or cracks inside concrete more strongly. The reaction of sodium silicate can be applied to lithium silicate and potassium silicate at the same time, and the metal silicate of the present invention releases a basic substance capable of recovering the pH in concrete and simultaneously generates silicon oxide or potassium silicate, thereby causing voids or cracks. You can continuously self-healing (self-repair).

_{In addition, the rust-preventing rebar used in concrete construction is a low-concentration water-soluble nitrous acid (HNO 2} ) mainly composed of amines that change from liquid or solid to gaseous phase, and when saturated, adsorb to the metal surface to form a rust-preventing film, and rebar. When corrosion occurs, neutralization (carbonic acid) and porosity of the surrounding concrete are already in progress, so if the nanocomposite silicate waterproofing agent penetrates into the concrete as described above, it is compensated, that is, in the alkaline region of pH 11 or higher that inhibits rebar corrosion. The resulting passive film can be regenerated.

The nanocomposite silicate sol may have a silicon dioxide solid content of 30 to 35 parts by weight, a metal oxide content of 25 to 30 parts by weight of sodium oxide, lithium oxide, and potassium oxide, and a pH of 3 to 6. The nanocomposite silicate sol may be separated into silicon dioxide and metal oxide, and the content thereof may be measured. At this time, the silicon dioxide solid content is preferably 30 to 50 parts by weight included. If it is contained in an amount of less than 30 parts by weight, the self-repairing ability of voids or cracks due to silicon dioxide may be deteriorated, and if it exceeds 35 parts by weight, silica may precipitate, thereby deteriorating waterproofing properties. The metal oxide is measured in the form of a mixture of sodium oxide, lithium oxide, and potassium oxide, and may be included in 25 to 30 parts by weight in the nanocomposite silicate sol. At this time, when the metal oxide is contained in an amount of less than 25 parts by weight, the pH is lowered, making it difficult to recover the pH (alkali recovery) in the concrete. If it exceeds 30 parts by weight, side reactions in which metal oxides and silica react, may result in poor self-healing (self-healing) ability for voids or cracks. In addition, the nanocomposite silicate sol may have a pH of 3-6. The nanocomposite silicate sol is a silica compound such as water glass and may be converted into a liquid and a solid according to a change in pH. When the pH of the nanocomposite silicate sol is less than 3, the formation of the sol is difficult because crystals of the silicate nanosol are grown and precipitated due to the aggregation of the silica sol contained, and when the pH exceeds 6, the silica changes to a liquid phase and thus nanocomposite silicate Since liquid is formed, it is difficult to expect waterproof properties.

The silane-based compound is added to increase the hardness of the alkali metal liquid nanocomposite silicate-based permeable waterproofing agent and to increase water resistance by forming a hydrophobic alignment layer and may include organo alkoxysilane or organo aminosilane.

_{The organo alkoxysilane is tetramethoxysilan (Tetramethoxysilan; Si(OCH 3} ) ₄ ), in accordance with the necessity of introducing a methyl group in order to increase the hardness of the alkali metal liquid nanocomposite silicate-based permeable waterproofing agent and form a heat-resistant coating film. Methyltrimethoxysilan (CH ₃ Si(OCH ₃ ) ₃ ), trimethylmethoxysilan ((CH ₃ ) ₃ SiOCH ₃ ), dimethyldimethoxysilane (CH ₃ ) ₂ Si(OCH ₃ ) ₂ ), triethylmethoxysilan (C ₂ H ₅ ) ₃ SiOCH ₃ ), ethyltrimethoxysilan (Ethyltrimethoxysilan; C ₂ H ₅ Si(OCH ₃ ) ₃ ), diethyldimethoxysilan ; (C ₂ H ₅ ) ₂ Si(OCH ₃ ) ₂ ) It is preferable to use in the group consisting of.

Organo Aminosilane is used to improve the chemical coupling between the hydrophobic alignment film and the concrete substrate and the coating film in order to increase the water resistance of the alkali metal liquid nanocomposite silicate-based permeable waterproofing agent that forms a coating film on the concrete surface. Ethyl)-3-aminopropyl-trimethoxysilane (CH ₃ O) SiCH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ , Aminoethylaminopropyltriethoxysilane NH ₂ (CH ₂ ) ₂ NHC ₃ H ₆ Si (OCH ₂ CH ₃ ) ₃ , N-2-(benzylamino)-ethyl-3-aminopropyl-trimethoxysilane (CH ₃ O) ₃ Si(CH ₂ ) ₃ NHCH ₂ NH ₂ , N-2-( Vinylbenzylamino)-ethyl-3-aminopropyl-trimethoxysilane (CH ₃ O) ₃ Si(CH ₂ ) ₃ NH(CH ₂ ) ₂ It is preferable to use in NHCH ₂

Alkali metal liquid nanocomposite silicate-based waterproofing agent is aluminum oxide 5 to 15 parts by weight, calcium carbonate 5 to 10 parts by weight, titanium dioxide 1 to 5 parts by weight based on 100 parts by weight of the nanocomposite silicate sol to improve the durability of concrete structures. , 0.1 to 1 part by weight of carbon black may be further included.

The aluminum oxide (Al ₂ O ₃ ) is for the purpose of introducing a function as an antistatic film because it improves the adhesion of the waterproofing coating film to the substrate (e.g., concrete) and improves the top coat property (top coating workability), and the coating film becomes positively charged after the film is formed. As an addition, in the range of less than 5 parts by weight and more than 15 parts by weight per 100 parts by weight of the nanocomposite silicate sol, there is a problem that the film strength decreases, so it is preferable to add 5 to 15 parts by weight, and calcium carbonate (CaCO ₃ ) is sieving As a pigment, it is added for the role of a filler, and in the range of less than 5 parts by weight and more than 10 parts by weight per 100 parts by weight of the nanocomposite silicate sol, there is a problem that the film strength decreases when it is exceeded as an extender pigment. It is preferable to do, and titanium dioxide (TiO ₂ ) is added to impart hiding power to the concrete base.If it is less than 1 part by weight based on 100 parts by weight of the nanocomposite silicate sol, the hiding power for the concrete base decreases and 5 parts by weight In the excess range, the effect of improving the hiding power on the concrete base is insignificant, so it is preferable to add 1 to 5 parts by weight, and carbon black is added for the toning effect of the coating film and is 0.1 per 100 parts by weight of the nanocomposite silicate sol. If it is less than part by weight, the toning effect is insignificant, and in the range of more than 1 part by weight, the phenomenon of fading the entire color of the coating film occurs, and it is preferable to add 0.1 to 1 part by weight.

Hereinafter, the present invention will be described in detail according to a method of manufacturing an alkali metal liquid nanocomposite silicate-based permeable waterproofing agent.

The present invention

i) Silicon dioxide solid content is 30 to 35 parts by weight, particle size is 10 to 20 nm, sodium oxide content is 25 to 30 parts by weight, pH 9.0 to 10.5 aqueous colloidal nanometal oxide A 20 to 40 parts by weight ;

ii) 10 to 15 parts by weight of an aqueous colloidal nanometal oxide B having a silicon dioxide solid content of 30 to 35 parts by weight, a particle size of 10 to 20 nm, a lithium oxide content of 25 to 30 parts by weight, and a pH of 8.5 to 9.0; And

iii) 15 to 14 parts by weight of aqueous colloidal nanometal oxide C having a silicon dioxide solid content of 30 to 35 parts by weight, a particle size of 10 to 20 nm, a potassium oxide content of 25 to 35 parts by weight, and a pH of 9.0 to 10.0; A mixture of potassium hydroxide and ethanol (potassium hydroxide: ethanol = 1:4 weight ratio) was added to the prepared composite, so that the total pH of the composite solution was 12 to 13 and the metal oxide content was 25 to 35 parts by weight. A first step of preparing a composite colloidal nano-metal oxide sol using a mix;

With respect to 80 parts by weight of the composite colloidal nanometal oxide sol of the first step, 15 to 25 parts by weight of pure water, 10 to 18 parts by weight of potassium hydroxide, and 0.2 to 0.6 parts by weight of aluminum hydroxide are added and stirred, A second step of preparing an intermediate having a stable pH of 12 to 13 in terms of chemical structure by replacing aluminum ions and potassium ions with functional groups of nanoparticles of the sol;

Alkali metal comprising a third step of reacting for 10 to 100 minutes by adding 3 to 7 parts by weight of organoalkoxysilane and 3 to 7 parts by weight of organoaminosilane to 100 parts by weight of the intermediate of the second step It provides a method of preparing a liquid nanocomposite silicate-based waterproofing agent.

Step 1

i) Silicon dioxide solid content is 30 to 35 parts by weight, particle size is 10 to 20 nm, sodium oxide content is 25 to 30 parts by weight, pH 9.0 to 10.5 aqueous colloidal nanometal oxide A 20 to 40 parts by weight ;

ii) 10 to 15 parts by weight of an aqueous colloidal nanometal oxide B having a silicon dioxide solid content of 30 to 35 parts by weight, a particle size of 10 to 20 nm, a lithium oxide content of 25 to 30 parts by weight, and a pH of 8.5 to 9.0; And

iii) 15 to 25 parts by weight of an aqueous colloidal nanometal oxide C having a silicon dioxide solid content of 30 to 35 parts by weight, a particle size of 10 to 20 nm, a potassium oxide content of 25 to 35 parts by weight, and a pH of 9.0 to 10.0; Mix and stir.

A diluted solution (potassium hydroxide: ethanol = 1:4 by weight) consisting of potassium hydroxide (KOH)) and ethanol (ethanol; (C ₂ H ₃ OH)) was added to the thus prepared complex, so that the pH of the total complex solution was 12 to 13 , To prepare a composite colloidal nano-metal oxide sol (composite alkali sol) using a homomix so that the content of the metal oxide is 25 to 30 parts by weight.

If only one of the above aqueous colloidal nanometal oxides A, B, C is used, the storage stability of the waterproofing agent is poor and the coating film becomes rough and the water resistance is also poor. Therefore, all three types of aqueous colloidal nanometal oxides A, B, and C are used. It is preferable to use.

Here, in order to ensure that the pH of the composite colloidal nanometal oxide sol (compound alkali sol) is 12 to 13 and the metal oxide content is 25 to 30 parts by weight, the content of the aqueous colloidal nano metal oxide A is 20 to 40 parts by weight B The content of is preferably 10 to 15 parts by weight. Most preferably, the content of the aqueous colloidal nanometal oxide A may be 30 parts by weight and the content of B may be 13 parts by weight.

Likewise, the content of the aqueous colloidal nanometal oxide C is preferably 15 to 25 parts by weight. Most preferably, the content of the aqueous colloidal nanometal oxide C may be 20 parts by weight.

Step 2

15 to 25 parts by weight of pure water, 10 to 18 parts by weight of potassium hydroxide (KOH) and aluminum hydroxide (Al(OH) ₃ ) 0.2 to 80 parts by weight of the composite colloidal nanometal oxide sol of the first step By adding 0.6 parts by weight and stirring sufficiently, aluminum ions (Al ³⁺ ) and potassium ions (k ⁺ ) are substituted with the functional groups of the nanoparticles of the composite colloidal nanometal oxide sol to prepare an intermediate having a stable pH of 12 to 13 in terms of chemical structure. do.

Colloidal particles obtained by substituting metal ions of potassium and aluminum into the silicate nanoparticles of the composite alkali sol are 10 to 20 nm in size and have a pH of 12 to 13 to be used as a raw material for a nanocomposite silicate-based permeable waterproofing agent.

Here, in order to ensure that the pH of the intermediate is 12 to 13 and to facilitate substitution of aluminum and potassium ions, the content of pure water is 15 to 25 parts by weight based on 80 parts by weight of the composite colloidal nanometal oxide sol of the first step. It is desirable to disclaim it. Most preferably, the content of pure water may be 40 parts by weight.

Likewise, the content of the potassium hydroxide is preferably 10 to 18 parts by weight based on 80 parts by weight of the composite colloidal nano-metal oxide sol in the first step. Most preferably, the content of potassium hydroxide may be 14 parts by weight.

Likewise, the content of the aluminum hydroxide is preferably 0.2 to 0.6 parts by weight based on 80 parts by weight of the composite colloidal nano-metal oxide sol in the first step. Most preferably, the content of aluminum hydroxide may be 0.4 parts by weight.

Step 3

Alkali metal liquid nanocomposite silicate system by adding 3 to 7 parts by weight of organoalkoxysilane and 3 to 7 parts by weight of organoaminosilane to 100 parts by weight of the intermediate of the second step and reacting at 80°C for 10 to 100 minutes at 3000 rpm Prepare a permeable waterproofing agent.

The present invention also provides 10 to 15 parts by weight of aluminum oxide, 7 to 10 parts by weight of calcium carbonate, 3 to 5 parts by weight of titanium dioxide, 0.5 to 1 parts by weight of carbon black based on 100 parts by weight of the alkali metal liquid nanocomposite silicate-based permeable waterproofing agent. It provides a concrete structure concrete penetration waterproofing method, characterized in that after preparing a uniform waterproofing solution by adding it to the concrete surface.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings so that those of ordinary skill in the art can easily implement them. In addition, in describing the present invention, when it is determined that a detailed description of a related known function or a known configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted. In addition, certain features presented in the drawings are enlarged or reduced or simplified for ease of description, and the drawings and their components are not necessarily drawn to scale. However, those skilled in the art will readily understand these details.

Example 1

Step 1

i) 30 parts by weight of an aqueous colloidal nanometal oxide A having a silicon dioxide solid content of 32 parts by weight, a particle size of 10 nm, a sodium oxide content of 28 parts by weight, and a pH of 10;

ii) 13 parts by weight of an aqueous colloidal nano-metal oxide B having a silicon dioxide solid content of 32 parts by weight, a particle size of 10 nm, a lithium oxide content of 28 parts by weight, and a pH of 8.3; And

iii) The silicon dioxide solid content is 33 parts by weight, the particle size is 10 nm, the potassium oxide content is 30 parts by weight, and the mixture is stirred in a ratio of 20 parts by weight of the aqueous colloidal nanometal oxide C having a pH of 9.5, followed by potassium hydroxide and ethanol. A diluted solution consisting of (potassium hydroxide: ethanol = 1:4) was added to adjust the pH of the entire composite to be 12 to 13, and 100 g of a composite colloidal nano-metal oxide sol (composite alkali sol) was prepared using a homomix. At this time, the content of the metal oxide contained in the total composite colloidal nanometal oxide sol (composite alkali sol) was made to be 28 parts by weight.

Step 2

With respect to 80 g of the complex colloidal nano-metal oxide sol of the first step, 20 g of pure water, 14 g of potassium hydroxide and 0.4 g of aluminum hydroxide are added and sufficiently stirred to obtain aluminum ions and potassium in the functional groups of the nanoparticles of the complex colloidal nano-metal oxide sol. By substituting ions, 114 g of intermediates having a stable pH of 12 to 13 were prepared.

Step 3

To 100 g of the intermediate in the second step, 5 g of methyltrimethoxysilane and 5 g of N-2-(aminoethyl)-3-aminopropyl-trimethoxysilane were added and reacted at 80° C. at 3000 rpm for 1 hour to finally make an alkali. A metal liquid nanocomposite silicate-based waterproofing agent was prepared.

Example 2

In Example 1, 20 parts by weight of the nano metal oxide A, 5 parts by weight of the nano metal oxide B, and 15 parts by weight of the nano metal oxide C were used in the same manner.

Example 3

In Example 1, 40 parts by weight of the nano metal oxide A, 5 parts by weight of the nano metal oxide B, and 15 parts by weight of the nano metal oxide C were used in the same manner.

Example 4

The same procedure was performed except that 20 parts by weight of the nano metal oxide A, 15 parts by weight of the nano metal oxide B, and 15 parts by weight of the nano metal oxide C were used.

Example 5

The same procedure was performed except that 20 parts by weight of the nano-metal oxide A, 5 parts by weight of the nano-metal oxide B, and 25 parts by weight of the nano-metal oxide C were used.

Comparative Example 1

Except that the nano-metal compound B was not used in Example 1, it was carried out in the same manner.

Comparative Example 2

In Example 1, except that the nanometal compound C was not used, it was carried out in the same manner.

Test Example 1

Chloride ion penetration resistance over time of the specimen formed according to the method of the present invention was measured by KSF-4930. Since concrete structures are rapidly deteriorated by chloride ions, the concrete penetration resistance test against chloride ions is used as a measure to improve durability and prevent deterioration of concrete structures.Therefore, the better resistance to chloride penetration, the better the durability. can do.

The KSF-4930 standard stipulates that the chloride ion penetration resistance is less than 3.0㎜.

It was found that there was no abnormality in the deterioration of the coating film even after 3000 hours of the salt spray test by KSD-9502, which is a more severe condition, and an energization test was performed on KSF-4936 to obtain quantitative data on chloride penetration resistance.

The results are shown in Table 1.

Test Items Chloride ion penetration resistance Test Methods KSF-4930 KSD-9502 KSF-4936 standard 3.0mm or less Nothing wrong 1000 coulombs or less Test result Uncoated 7.2mm or more Corrosion of specimen 3400coulombs Example 1 0 clear 0coulombs Example 2 0.2mm or less clear 120coulombs Example 3 0.1mm or less clear 210coulombs Example 4 0.2mm or less clear 180coulombs Example 5 0.2mm or less clear 170coulombs Comparative Example 1 2.9mm or less Partial corrosion of the specimen 1250coulombs Comparative Example 2 2.7mm or less Partial corrosion of the specimen 1100coulombs

As shown in Table 1, in the case of Example 1 of the present invention, it was found that not only had complete penetration resistance to chloride ions, but also did not show corrosion of the test specimen, thereby improving the durability of concrete. In the case of Example 2 in which the content of the nanometal compound was minimized and Examples 3 to 5 in which only a portion of each nanometal compound was used in an excessive amount, it was found that some chloride ion penetration occurred, but it was less than the test standard, so there was a problem in use. Appeared to be missing. However, in the case of Comparative Examples 1 and 2 in which the nanometal compound B or C was not used, it was confirmed that chloride ions penetrated close to the reference value, and accordingly, it was confirmed that a part of the test specimen was corroded.

Test Example 2

The water permeability test was measured according to KSF-4930, and the amount of absorption was measured according to KSF-4919.

As for the water-permeable test specimen, the strength of the test specimen of KSF-4930, KSF-4919 and the concrete (28-day curing) specimen of KSF-4009 was 40.4 N/㎟, and the coating thickness was 100㎛ or less.

The purpose of the water permeability test is to reduce the durability of the structure when factors that deteriorate the concrete structure (acid ratio, salt water, CO ₂ , nitrogen oxides in the air, sulfur oxides, etc.) are dissolved through water and penetrated. This is to measure the permeability resistance of water, which is a mediating factor.

The results are shown in Table 2.

Test Items Water permeability Test Methods KSF-4930
Pitching ratio KSF-4919
Absorption KSF-4919
Water permeability standard 0.1 or less 2.0 or less Not pitched Test result Uncoated One 8.0 or less Pitched Example 1 0.01 or less 0.01 or less Not pitched Example 2 0.05 or less 0.8 or less Not pitched Example 3 Less than 0.03 0.5 or less Not pitched Example 4 0.04 or less 0.4 or less Not pitched Example 5 Less than 0.02 0.4 or less Not pitched Comparative Example 1 0.28 or less 1.9 or less Not pitched Comparative Example 2 0.27 or less 2.7 or less Not pitched

As shown in Table 2, in the case of Example 1 of the present invention, it was confirmed that durability could be improved by blocking the penetration of water, which is a deterioration medium. In the case of Examples 2 to 5 and Comparative Examples 1 and 2, the water permeability was not confirmed as a result of testing according to the water permeability test method of KSF-4919, but in the experiment according to the absorption amount of KSF-4930 and KSF-4919, some It was found to absorb moisture, and in particular, in the case of Comparative Examples 1 and 2 in which some nanometal compounds were not used, the absorption amount and the water permeability ratio were found to be difficult to perform as a waterproofing agent beyond the reference value.

Test Example 3

Carbonation depth was measured using the KSF-2584 concrete accelerated carbonation test method and the KSF 2596 concrete carbonation depth measurement method.

The concrete structure absorbs carbon dioxide in the air and reacts with calcium hydroxide, which is a cement hydrate, Ca(OH) ₂ + CO ₂ → CaCO ₃ +H ₂ O, becomes calcium carbonate, and is neutralized, resulting in whitening and deteriorating the concrete structure. Therefore, by forming a coating film having permeation resistance to carbon dioxide, deterioration of concrete can be suppressed and durability can be improved.

Therefore, this accelerated carbonation test is a test to prevent corrosion of reinforcing bars in concrete structures by reducing the pH of concrete due to carbonation of concrete, and to block the source of cracks in structures due to corrosion of reinforcing bars.

The experiment was conducted under conditions of a waterproof coating thickness of 100 μm or less, a temperature of 20±2° C., a relative humidity of 50±5%, and a carbon dioxide concentration of 5±0.2%.

The results are shown in Table 3.

Test Items Accelerated carbonation experiment Test Methods KSF-2584, KSF-2596 standard 0.8 or more of standard concrete Test result Uncoated 10.3mm Example 1 0mm Example 2 0.2mm Example 3 0.1mm Example 4 0.1mm Example 5 0.1mm Comparative Example 1 1.3mm Comparative Example 2 1.4mm

As shown in Table 3, in the case of uncoated concrete, it was confirmed that carbonation proceeded to a depth of 10.3 mm, whereas in the case of Example 1 of the present invention, carbonation did not appear. This means that the process of preventing carbonation by restoring the pH of the nanometallic compound included in the waterproofing agent of the present invention is being performed normally, and although some carbonation occurred in Examples 2 to 5, it was at a very low level compared to the reference value. It was confirmed that only carbonation was occurring and the pH was being restored. Therefore, when the alkali metal liquid nanocomposite silicate-based permeable waterproofing agent according to the present invention is used, the permeation resistance to carbon dioxide is very excellent, and even if carbonation by some permeated carbon dioxide occurs, the pH recovery phenomenon by the nanometal compound appears and carbonation is prevented. I could see what can be minimized.

Test Example 4

The permeable waterproofing agent produced by the method of Examples 1 to 5 and Comparative Examples 1 and 2 was applied to a concrete specimen (10cmX10cmX10cm), and then dried for 48 hours. At this time, the common concrete formulation used in Examples 1 to 5 and Comparative Examples 1 to 2 had a nominal strength of 180 and an average porosity (%) of 13.9%. Thereafter, the specimen was cut into a size of 4 to 5 mm, and then the porosity was measured up to a maximum pressure of 60,000 psi using Auto Pore IV 9520 of Micromeritics, USA.

Average porosity (%) Example 1 8.7 Example 2 9.3 Example 3 8.9 Example 4 9.4 Example 5 9.8 Comparative Example 1 12.8 Comparative Example 2 11.4

As shown in Table 4, in the case of the specimens treated with the permeable waterproofing material of Examples 1 to 5 of the present invention, it was confirmed that the porosity was reduced to the level of high-strength concrete. In general, the porosity of ordinary concrete is 10-20%, the porosity of high-strength concrete is 5-8%, and the porosity of high-performance concrete is 3% or less. In the case of applying the permeable waterproofing material of the present invention, it was confirmed that the porosity was greatly reduced even when ordinary concrete was used, and thus it had a porosity close to that of high strength concrete. However, in the case of Comparative Examples 1 and 2, the reduction in porosity was not noticeable, but it was confirmed to have a porosity comparable to that of ordinary concrete.

As described above, specific parts of the present invention have been described in detail, and it will be apparent to those of ordinary skill in the art that these specific techniques are only preferred embodiments, and the scope of the present invention is not limited thereby. will be. Accordingly, it will be said that the substantial scope of the present invention is defined by the appended claims and their equivalents.

Claims (9)

delete delete delete delete delete delete delete Silicon dioxide solid content is 30 to 35 parts by weight, particle size is 10 to 20 nm, sodium oxide content is 25 to 30 parts by weight, pH 9.0 to 10.5 aqueous colloidal nanometal oxide A 20 to 40 parts by weight, dioxide Silicon solid content is 30 to 35 parts by weight, particle size size is 10 to 20 nm, lithium oxide content is 25 to 30 parts by weight, pH 8.5 to 9.0 aqueous colloidal nanometal oxide B 10 to 15 parts by weight and silicon dioxide solid content A composite prepared by mixing and stirring 15 to 25 parts by weight of an aqueous colloidal nanometal oxide C with a content of 30 to 35 parts by weight, a particle size of 10 to 20 nm, a potassium oxide content of 25 to 35 parts by weight, and a pH of 9.0 to 10.0 A diluted solution consisting of potassium hydroxide and ethanol (potassium hydroxide: ethanol = 1:4 weight ratio) is added to the mixture so that the pH of the total complex solution is 12 to 13 and the metal oxide content is 25 to 35 parts by weight. A first step of preparing a nano metal oxide sol;
With respect to 80 parts by weight of the composite colloidal nanometal oxide sol of the first step, 15 to 25 parts by weight of pure water, 10 to 18 parts by weight of potassium hydroxide, and 0.2 to 0.6 parts by weight of aluminum hydroxide are added and stirred, A second step of preparing an intermediate having a stable pH of 12 to 13 in terms of chemical structure by replacing aluminum ions and potassium ions with functional groups of nanoparticles of the sol;
Alkali metal comprising a third step of reacting for 10 to 100 minutes by adding 3 to 7 parts by weight of organoalkoxysilane and 3 to 7 parts by weight of organoaminosilane to 100 parts by weight of the intermediate of the second step Method for producing a liquid nanocomposite silicate-based waterproofing agent.
The method of claim 8,
The organoalkoxysilane is any one of tetramethoxysilane, methyltrimethoxysilane, trimethylmethoxysilane, dimethyldimethoxysilane, triethylmethoxysilane, ethyltrimethoxysilane, and diethyldimethoxysilane,
The organo aminosilane is N-2-(aminoethyl)-3-aminopropyl-trimethoxysilane, aminoethylaminopropyltriethoxysilane, N-2-(benzylamino)-ethyl-3-aminopropyl- Trimethoxysilane, N-2-(vinylbenzylamino)-ethyl-3-aminopropyl-trimethoxysilane, characterized in that any one of the alkali metal liquid nanocomposite silicate-based permeable waterproofing method.