KR102091753B1 - Surface treatment method of Concrete Structure with strengthened durability by means of reactive self recovery concrete face modifier, marble shaped protective material, and chemical resistance crack repairing of high tensile nano short fibers - Google Patents

Abstract

The present invention relates to a surface treatment method for increasing the durability of a concrete structure by means of chemical-resistant cross-section repair of a reactive self-recovery concrete surface modifier, a marble-shaped protective material, and high-tensile short nanofibers. The surface treatment method comprises a process of forming, on the surface of a concrete structure, a protection film including a topcoat for improving durability, a primer coat for realizing a marble texture, and a bottom coat and a chemical-resistant cross-section repair layer for waterproofing and preventing contamination. According to the present invention, the lifespan of the concrete structure can be extended.

Description

Reactive self-recovery Surface treatment method to increase the durability of a concrete structure through a concrete surface modifier and a chemical-resistant cross-section repair of a marble-like protective material and high-tensile nano short fibers {Surface treatment method of Concrete Structure with strengthened durability by means of reactive self recovery concrete face modifier, marble shaped protective material, and chemical resistance crack repairing of high tensile nano short fibers}

The present invention relates to a surface treatment method for increasing the durability of a concrete structure, and having a medium containing a reactive self-recovering concrete surface modifier to protect the surface even if a crack occurs due to surface coating damage, thereby increasing durability. It relates to a surface treatment method to increase the durability of the concrete structure.

The cracks on the surface of the concrete structure become a rapid penetration passage for the penetration of deteriorating factors such as chlorine ions, carbon dioxide, and water, and durability is deteriorated. In order to solve this problem, it is common to use a surface coating method of a concrete structure. However, the surface coating method known so far cannot fill the inside of the crack, and as the crack grows, it is difficult to estimate its movement, so improvement is required.

The technical problem of the present invention is to not only extend the life of the concrete structure by self-healing the crack even if a crack occurs in the concrete structure, but also to repair and protect the surface of the concrete structure deteriorated by the crack and express the stone texture. It is to provide a surface treatment method to increase the durability of the concrete structure to improve the aesthetics.

In order to solve this technical problem, in the present invention, a top coat for increasing durability on a surface of a concrete structure; Medium to implement marble texture; A self-healing base surface adjustment layer containing a reactive self-healing concrete surface modifier, while forming a protective film containing a water-repellent and highly-tensile nano-single-fiber resistant cross-section repair layer for waterproofing and contamination prevention, based on the total top coat weight As 50 to 70 parts by weight of the ceramic resin, 15 to 25 parts by weight of cellulose acetate butyrate and 10 to 25 parts by weight of polyethylene glycol, the middle is 23 to 28 parts by weight of the modified acrylic emulsion based on the total middle weight, 40 to 56 parts by weight of the filler Part, 5-8 parts by weight of diatomaceous earth, 5-10 parts by weight of titanium dioxide, 10-15 parts by weight of water, and 1-10 parts by weight of pigment, wherein the primer is 35 to 55 parts by weight of calcium aluminate cement based on the total primer weight Part, 5 to 20 parts by weight of the mixture of blast furnace slag and fly ash, 40 to 45 parts by weight of general aggregate, and silicon organic-inorganic composite and reactive self-healing concrete 5 to 10 parts by weight of a mixture of adjusting agents, the cross-section repair layer is 40 to 55 parts by weight of calcium aluminate cement, 0.1 to 5 parts by weight of polyvinyl alcohol fibers, which are high tensile nano short fibers, and 5 to 5 parts of blast furnace slag and fly ash A surface treatment method for increasing the durability of a concrete structure including 20 parts by weight is provided.

The reactive self-healing concrete surface modifier is a urea-formaldehyde polymer coating film and a core material made of siloxane resin self-recovering silicate micronanotube, and the total content of the silicone organic-inorganic composite and the reactive self-recovering concrete surface modifier is total. 5 to 10 parts by weight based on the medium weight. And the silicone organic-inorganic composite is a product of hydrolysis and dehydration condensation of silicone alkoxide and siloxane resin, and the content of the silicone organic-inorganic composite is based on 100 parts by weight of the total content of the silicone organic-inorganic composite and the self-repairing silicate tube. And 30 to 70 parts by weight. And the siloxane resin is polydimethylsiloxane, dimethylsiloxane-diphenylsiloxane copolymer, dimethylsiloxane-methylphenylsiloxane copolymer or polydimethylsiloxane having silanol end groups, polydimethylsiloxane having silanol end groups, or a combination thereof.

By using the surface treatment method to increase the durability of the concrete structure of the present invention, if a crack occurs in the concrete structure, a surface protection system that self-recovers the crack width can be built to extend the life of the concrete structure, and the durability of the concrete structure In addition to improving augmentation, prevention of carbonation and salt damage, and weather resistance, it is possible to effectively improve the aesthetics by realizing the texture and color of the stone without using actual stone.

Figure 1 shows the state of the middle in the concrete structure when the surface treatment according to Example 1.
Figure 2 shows the state of the middle in the concrete structure when the surface treatment according to Example 4.

Hereinafter, a surface treatment method for increasing the durability of a concrete structure through a chemical-resistant cross-section repair of a high-tensile nano short fiber and a protective material of a marble shape including a reactive self-healing concrete surface modifier of the present invention will be described.

Top coat for increasing durability on the surface of the concrete structure; Self-healing base layer and midway to realize marble texture; To form a protective coating film containing a water-repellent and highly chemically resistant cross-section repair layer of high-tensile nano short fibers to prevent contamination and

The top coat includes 50 to 70 parts by weight of ceramic resin, 15 to 25 parts by weight of cellulose acetate butyrate, and 10 to 25 parts by weight of polyethylene glycol based on the total top coat weight, and the middle coat is 23 to 28 wt. Parts, 40-40 parts by weight of filler, 5-8 parts by weight of diatomaceous earth, 5-10 parts by weight of titanium dioxide, 10-15 parts by weight of water, and 1-10 parts by weight of pigment, wherein the primer is calcium based on the total primer weight 35 to 55 parts by weight of aluminate cement, 5 to 20 parts by weight of a mixture of blast furnace slag and fly ash, 40 to 45 parts by weight of general aggregate, and 5 to 10 parts by weight of a mixture of a silicone organic-inorganic composite and a reactive self-healing concrete surface modifier And, the section repair layer is 40 to 55 parts by weight of calcium aluminate cement, 0.1 to 5 parts by weight of polyvinyl alcohol fibers, which are high tensile nano short fibers, and blast furnace slag. A surface treatment method for increasing the durability of a concrete structure including 5 to 20 parts by weight of a mixture of fly ash is provided.

In the protective coating film of the present invention, the undercoat serves as a base adjustment layer of the concrete structure and also creates an embossed surface for expressing the texture of the stone. When forming a primer, 5 to 10 parts by weight of a mixture of a silicone organic-inorganic composite and a reactive self-healing concrete surface modifier is used. The content of the reactive self-healing concrete surface modifier is, for example, 6 to 9 parts by weight, for example 7 to 8 parts by weight, for example 7 parts by weight.

Primer forms a primary waterproof layer as the base layer to protect the surface of the deteriorated structure, block the penetration of moisture, carbonate, etc., which degrades the performance of the concrete, and is integrated with the structure because cement is the main component in the same way as the concrete structure.

The primer of the present invention is based on the total weight of the primer, 35 to 55 parts by weight of calcium aluminate cement, 5 to 20 parts by weight of a mixture of blast furnace slag and fly ash, 40 to 45 parts by weight of general aggregate, and silicon organic-inorganic composite and reactive magnetic It contains 5 to 10 parts by weight of the mixture of the recovery concrete surface conditioner.

The reactive self-healing concrete surface modifier is a self-healing stiffener, a self-healing silicate micronanotube composed of a urea-formaldehyde polymer coating film and a siloxane resin core material.

The coating film protects the core material by shielding it from the external environment, and when cracks are generated, it breaks and plays a role of allowing the self-healing material to flow out. It is required that the coating film does not break easily while the microtube is in operation and has mechanical properties to be easily broken when cracking occurs. In addition, it should have excellent thermal stability and be able to effectively prevent external moisture and the like from entering the interior.

The coating film may further include at least one selected from crosslinked polyurethane resins, melamine-formaldehyde resins, melamine-urea-formaldehyde resins, polyamide resins, polyurea resins, and polyvinyl alcohol resins in addition to the above-described polymers. The thickness of the coating film is 0.05 to 20 μm, for example 0.5 to 10 μm.

The content of the urea-formaldehyde polymer is 60 to 90 parts by weight, for example, 65 to 80 parts by weight, for example 70 to 75 parts by weight, based on 100 parts by weight of the core material of siloxane resin.

Micro nanotubes have an aspect ratio of 1: 1 to 1:10, and the aspect ratio is a ratio of a short axis to a long axis. The long axis length of the micronanotube is preferably 0.1 μm to 10 μm, 0.1 μm to 3 μm, the short axis length is preferably 100 nm to 500 nm, and more preferably 100 nm to 300 nm.

The silicone organic-inorganic composite is a hydrolysis and dehydration condensation reaction product of silicone alkoxide and siloxane resin, and the content of the silicone organic-inorganic composite is based on 100 parts by weight of the total content of the silicone organic-inorganic composite and the self-repairing silicate tube. To 70 parts by weight. When the content of the silicone organic-inorganic composite is in the above range, a reactive self-healing concrete surface modifier can be obtained that is uniform, hard, and has excellent adhesion to the self-healing silicate microtubes. The product of hydrolysis and dehydration condensation of silicone alkoxide and siloxane resin refers to a product obtained by hydrolysis of a mixture of silicone alkoxide and siloxane resin, followed by dehydration condensation reaction of the hydrolysis product.

Examples of the siloxane resin include polydimethylsiloxane, dimethylsiloxane-diphenylsiloxane copolymer, dimethylsiloxane-methylphenylsiloxane copolymer, and polydimethylsiloxane having silanol end groups or combinations thereof. Hydroxy groups are present at both ends of the molecular chain of these siloxane-based resins, and when the dehydration-condensation reaction of the silicon alkoxide occurs, they participate in the reaction together to form a matrix polymer. In the dimethylsiloxane-diphenylsiloxane copolymer, the mixing molar ratio of the dimethylsiloxane repeating unit and the diphenylsiloxane repeating unit is 99: 1 to 70:30, for example, 8: 2 to 2: 1.

The siloxane resin is, for example, a polydimethylsiloxane having silanol end groups.

Examples of the silicon alkoxide include tetraethoxysilane (TEOS), tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane, or combinations thereof.

The concrete structure is a structure formed by using cement as a main material, and forms a protective coating made of top, middle, and bottom on the surface of the concrete structure of the present invention. The concrete structures are various, such as simple concrete structures such as retaining walls, reinforced concrete structures, underground structures, bridges exposed to acid deposits, and ports.

In the present invention, a reactive self-healing concrete modifier is used when forming a primer and a marble-shaped protective material is used when forming a middle coat. If such a primer is used, the surface protection system of the concrete structure is self-healing if the crack width is 0.5 mm or less, for example, 0.3 mm or less, even if cracks occur due to surface coating damage. Therefore, the lifespan of the concrete structure can be extended to reduce maintenance costs.

Calcium aluminate cement is usually portland cement (OPC) by adding an additive to improve adhesion, and because it has a high affinity with cement, the main component of a concrete structure, it seeks to be integral with the surface to be formed to form a dense base adjustment layer. And calcium aluminate cement plays a very important role in making acid-resistant mortar. Calcium aluminate cement may have a CaO content of 37-40% by weight, an Al ₂ O ₃ content of 39-42% by weight, and a specific surface area of 4000 cm ² / g.

To the composition for forming the primer, one or more additives among thickeners, fluidizing agents and antifoaming agents may be further added. For example, as an additive, a thickening agent such as fused silica, a polyacrylic emulsion thickener, a polyurethane thickener, an antifoaming agent such as polyethylene oxide, polypropylene oxide, or the like, a naphthalene sulfonic acid-based fluidizing agent, or a combination thereof may be used. The content of the thickener is 0.3 to 0.7% by weight, the content of the antifoaming agent is 0.1 to 1% by weight, and the content of the fluidizing agent is 0.3 to 1% by weight. When the content of the thickener, antifoaming agent and fluidizing agent is within the above range, air bubbles can be effectively prevented without deteriorating toughness and elasticity.

The primer of the present invention can be applied to, for example, a brush, a roller, or a mortar gun by using a known method on a surface of a concrete structure or on a cross-section repair layer formed on a surface of a concrete structure to be described later. The thickness of the primer is preferably about 500 to 1500 μm, for example, 700 to 1000 μm. In particular, the undercoat layer of the present invention contributes to expressing the texture of the stone because it can produce an embossing effect without a separate puttying operation.

In the present invention, a cross-section repair layer using a repair mortar may be further formed between the surface of the concrete structure and the undercoat layer. The construction method is to chip the defective part of the concrete structure, wash it with water, and then form at least a 20mm to 100mm cross-section repair layer with a repair mortar. Apply a single color or colorful pattern to form the middle.

In the protective coating layer, the intermediate layer protects the surface while realizing stone texture and color by mixing functional particles. Intermediate is based on the total intermediate weight 23-28 parts by weight of modified acrylic emulsion, 40-56 parts by weight of filler, 5-8 parts by weight of diatomaceous earth, 5-10 parts by weight of titanium dioxide, 10-15 parts by weight of water, and pigment 1-10 Includes parts by weight.

As the pigment, an inorganic pigment or an organic pigment may be used. As the inorganic pigment, titanium dioxide or the like may be used, and one or more selected from azo-based, phthalocyan-based, condensed polycyclic organic pigment, and red oxide iron oxide may be used. Organic pigments are selected and used according to the color to be realized. When titanium dioxide is used as a pigment, titanium dioxide is a main raw material that realizes white color and is mixed with other colors to realize a mixed color of stone.

The center of the present invention is very important for realizing stone texture and color, and can be implemented in two types, a single color type and a multicolor pattern environment improvement type. The desired color can be realized according to the color expression method by the multi-color capsule. The multi-colored capsules include various pigments and the like, and it is possible to realize a neutrality having various colors and patterns.

 For medium application, spraying through a mortar gun or bone tile gun can be used. In one specific embodiment, a raw material in which a spherical pigment capsule is dispersed in a one-component water-soluble emulsion of a modified acrylic emulsion can be used. In this case, do not use the equipment when stirring, and stir slowly, avoiding breaking the spherical pigment capsule as much as possible, then apply it using a medium pressure spraying equipment. If the colloidal state of the pigment is poor in fluidity, it is possible to add water within 5% as a diluent and stir slowly after addition.

In order to produce the texture of the stone, it is important to mix the stone color raw materials during the middle application. To realize the color of natural stone, first analyze the number of colors and the ratio of each color of the natural stone, prepare the paint for each color, compare the final color through spouting with the gemstone, go through several feedback processes, It is desirable to determine the mixing ratio of colors that have a feeling similar to that of a gemstone. The feedback process for color determination is first to disperse the inorganic pigment in water in a colloidal state (for example, 5 mm in diameter) (for example, using a sieve) and then mix it by weight. The weight of the individual pigments is compared with each other, divided by ratio, and then mixed with each other. The colloidal state between the pigments must be maintained even after the individual pigments are mixed. If the individual pigments are combined with each other in the solvent, it is very important to maintain their color for each pigment because the result is a completely different integrated color and it is impossible to realize the unique color tone of the gemstone.

When the individual pigments mixed in the colloidal water dispersion medium are stirred in a stirrer, the size of the capsule can be adjusted by adjusting the stirring speed. For example, if the stirring speed is stirred at a minimum of 200 to 1500 RPM, spherical capsules having a shape of 200 to 3000 μm can be obtained.

In the middle, if the total thickness is about 500 to 1500 µm, for example, 700 to 1000 µm, a film having a desired thickness is formed by dividing it once or twice when necessary.

The modified acrylic emulsion is an emulsion of an acrylic resin having improved water repellency through silicone modification. The modified acrylic emulsion serves as a binder to maintain the adhesion between the middle and the top, and an additive for improving weather resistance and strength can be mixed. Since the acrylic resin is transparent, it is suitable for blending with a pigment to realize the color of the stone, and has excellent water resistance, weather resistance and adhesion.

Fillers are components that increase the volume by replacing expensive components such as pigments. In addition, the filler may evenly adjust the background surface, function to maintain a moderate drying characteristic even when the ambient environment conditions change rapidly when the coating material is dried due to a moisture-moist effect, or may inhibit the pigment components from sticking. The filler may be calcium carbonate, silica or a mixture thereof, for example, a mixture of 25 to 34% by weight of calcium carbonate and 15 to 22% by weight of silica.

In the middle, diatomaceous earth has a low density and a high porosity, so that it has a large surface area, which prevents peeling while promoting drying of the coating film, increases adhesion between the middle layer and the rest of the layers, and reduces gloss and glare. In addition, titanium dioxide is the main raw material that realizes white, and it is mixed with other colors to realize the mixed color of stone.

The midway may further include nanoparticles of silicate. Silica nanoparticles fill the voids in the concrete matrix surface to even the ground surface.

The primer of the present invention contains a reactive self-healing concrete surface modifier, and when damage such as cracks occurs in the concrete structure, the microtube located at the damaged part of the reactive self-healing concrete surface modifier on the surface of the structure is broken and the microtube is broken. The recovery material contained in the core of the is provided to fill the damaged area.

In forming the primer, a reactive self-healing concrete surface modifier, a silicon organic-inorganic composite, and a ruthenium catalyst may be further added. The catalyst is preferably 0.1 to 0.5 parts by weight based on 100 parts by weight of the total weight of the self-healing concrete surface modifier and the silicone organic-inorganic composite, but is not limited thereto. When the primary crack occurs in the middle containing the silicon organic-inorganic composite, a crack occurs in the micronanotube, the micronanotube bursts, the adhesive material flows out, and after contact with the catalyst, polymerization proceeds and self-recovery may occur. have.

As described above, the reactive self-healing concrete surface modifier has a microtube shape. In this way, the microtube shape has an advantage of easy dispersibility and strong external impact compared to other shapes such as a spherical shape.

The above-described section repair layer will be described in more detail.

The section repair layer includes 40 to 55 parts by weight of calcium aluminate cement, 0.1 to 5 parts by weight of polyvinyl alcohol fibers, which are high tensile nano short fibers, and 5 to 20 parts by weight of a mixture of blast furnace slag and fly ash. The mixing weight ratio of blast furnace slag and fly ash is 1: 1.

As the present polyvinyl alcohol fiber, an amine-modified epoxy or a rubber-modified epoxy can be used, which is commonly used in the field of concrete protective coating. For example, polyvinyl alcohol fibers using a modified aromatic amine as a curing agent can be used. When the content of the polyvinyl alcohol fiber is within the above range, physical properties such as acid resistance and alkali resistance are excellent, while physical properties and workability are good.

Polyvinyl alcohol fiber is a high-tensile nanofiber, and a concrete structure having a cross-section repair layer containing it exhibits an effect in reducing cracking. For the polyvinyl alcohol fiber, a specific gravity of 1260 kg / cm 3, a length of 12 mm, a melting temperature of 220 ° C., a tensile strength of 700 MPa, and an elastic modulus of 11 GPa are used. And blast furnace slag and fly ash helps calcium aluminate cement reduce the variability that appears over time and have a stable structure. The density of the blast furnace slide is 2.80 kg / m ³ and the specific surface area is 6,000 to 8,000 cm ² / g. The fly ash has a SiO2 content of 45% by weight or more, a specific gravity of 1.95 or more, and a specific surface area of 2400 cm2 / g or more.

In the protective coating film of the present invention, the top coat is a transparent finish that prevents contamination and yellowing of the surface of the concrete structure and imparts impact resistance. Such a top coat includes 50 to 70 wt% of ceramic resin, 15 to 25 wt% of cellulose acetate butyrate and 10 to 25 wt% of polyethylene glycol, based on the total top coat weight. The thickness of the top coat is 30 to 180 μm, for example 50 to 150 μm, for example 80 to 100 μm.

The ceramic resin is obtained by dispersing ceramic particles such as metal oxide on a transparent resin to improve the hardness of the surface. As the ceramic resin, a mixture of a transparent resin, an epoxy resin and a melamine resin, and a silane coupling agent are used. As an example, a transparent resin mixture containing an alkoxysilane coupling agent and a metal oxide having a size of 10 to 30 nm is hydrolyzed and then used as a ceramic resin. At this time, an amine catalyst such as trimethylamine can be used as a curing agent, and various types such as aluminasol, silicasol, and titaniumsol can be used as ceramic particles for wear resistance.

Cellulose acetate inhibits and stabilizes the plastic shrinkage balance of the top coat, and improves the mechanical properties by improving toughness, impact resistance and tensile strength, thereby improving the resistance of the top coat to fatigue behavior, thereby increasing the durability of the protective film.

Polyethylene glycol protects the triple layers of concrete structures or protective coatings from thermal expansion or contraction, and the number average molecular weight of polyethylene glycol (PEG) is 800 to 1,500.

When forming the protective coating film of the present invention, it is preferable to adjust the surface of the concrete structure (bottom surface) first. Treatment of the lower surface may include background treatment of the surface of the concrete structure and cleaning of the lower surface. Concrete surface treatment is a process that removes foreign substances through washing and, if necessary, a portion of the surface of the deteriorated concrete structure. In the case of a new concrete structure, foreign matter, dust or oil on the surface is removed by washing with high pressure water (300 bar or more). If there are water droplets on the surface, oil remains, so remove them through grinding. After determining the demolition thickness of deteriorated concrete, the site conditions of the concrete structure are reviewed for removal, and chipping, sandblasting, high pressure water surface treatment and rock drilling chipping, and other appropriate construction methods are adopted and implemented.

After removing the deteriorated part of the surface of the concrete structure, foreign substances such as dust are completely removed using a high pressure water washer or vacuum cleaner to increase adhesion. At this time, in order to prevent the concrete structure from rapidly absorbing the moisture of the mortar, soak a sufficient amount of water so that the concrete surface becomes saturated if not done before work. Watering can be done, for example, 24 hours in advance. Then, 1 hour before the start of work, moisture or dust (latency), etc., which are inhibited from the adhesion increase, is removed using high-pressure air.

After treatment of the bottom surface, check for the presence of damaged concrete, cement latencies, corrosive substances, dust, emulsions, and other substances that reduce the adhesion between the bottom surface and the repair material, and take appropriate action immediately if there is a problem. . Subsequently, the adhesion strength of the lower surface is measured. In one specific embodiment, the average adhesion is set to 1.0 MPa or more. In addition, after checking whether there is a water film that reduces the adhesion, high-pressure air is injected to the surface.

Subsequently, the primer is painted. Stirring of each component constituting the primer composition is, for example, agitation using a stirrer for at least 2-3 minutes. The application of primer can be done manually (plastering) using a brush, roller, etc., or it is possible to cast a machine using equipment such as a mortar gun.

Subsequently, the thickness is applied at a thickness of 100 to 150 μm. For medium application, [a mortar gun spraying work or a bone tile gun can be used.

The top coat may be applied to a thickness of 10 to 20 μm using a brush, roller, spray, or the like over the above-described middle.

Within 24 hours after the entire process for forming the protective film is completed, be careful not to be exposed to rainfall and snow, and allow a curing period of at least 3 days.

Using the surface treatment method to increase the durability of the concrete structure of the present invention, a concrete structure is constructed by constructing a surface protection system that self-recovers the crack width when a crack occurs in a concrete structure using a reactive self-healing concrete surface modifier when forming a primer. It is possible to extend the lifespan and form a protective coating on the surface of the concrete structure to increase the durability of the concrete structure, prevent carbonation and salt damage, and improve weather resistance. In addition, the surface of the concrete structure effectively realizes the texture and color of the stone, improving the aesthetics, and producing a similar aesthetics without using actual stone. Instead, it can be applied to structures where secondary damage can occur due to cracking. For example, it can be used for structures such as bridges, roads, subways, railway facilities, and underground facilities with frequent crack leaks.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited to them.

Manufacturing example  1: Self recovery Silicate  Preparation of tubes

5 mL of an aqueous solution of 2.5 wt% ethylene-maleic anhydride copolymer and 20 mL of distilled water were put in a thermostat and mixed while stirring at 300 rpm at 25 ° C using a digital mixer. The beaker was dissolved by adding 0.503 g of urea, 0.050 g of ammonium chloride, and 0.050 g of resorcinol. The pH of the beaker contents was adjusted to 3.5 while adding an aqueous sodium hydroxide solution and an aqueous hydrochloric acid solution. Foam was removed by adding 2-3 drops of 1-octanol, an antifoaming agent, to the resultant product. 8 mL of polydimethylsiloxane with silanol end groups as core material was slowly added to the beaker to form an emulsion. For the stable formation of the emulsion, the reaction mixture was left for about 10 minutes and then 1.456 g of a 37% by weight aqueous formaldehyde solution was added.

Thereafter, the temperature of the beaker was slowly raised to 60 ° C, and then a reaction was performed to form a capsule film for 4.5 hours from the start of the temperature increase. After the reaction was completed, the beaker was taken out of the thermostat, cooled to 25 ° C., filtered, and washed with water and ethanol to obtain a microtube. By self-drying for 24 hours or more, a self-healing silicate microtube having a coating film made of a urea-formaldehyde polymer and a core material made of siloxane resin was obtained, the long axis length of the microtube is 2 μm, and the short axis length is 200 nm. The thickness of the coating film is about 5 μm in a self-healing silicate microtube having a coating material made of a urea-formaldehyde polymer and a core material made of a siloxane resin,

The content of the urea-formaldehyde polymer was 75 parts by weight based on 100 parts by weight of the siloxane resin.

Manufacturing example  2

69.60 g of isopropanol and 20.91 g of tetrahydrofuran were mixed and 60.00 g of tetraethoxysilane and 40.00 g of poly (dimethylsiloxane-co-methylphenylsiloxane) were dissolved therein. 15.76 g of distilled water and 3.65 g of an aqueous hydrochloric acid solution were slowly added to the resultant product (this is referred to as a first product product) to form a mixed solution, and the mixed solution was heated to 80 ° C. for 30 minutes under a nitrogen atmosphere. Subsequently, the mixture was mixed in a weight ratio of 2: 1 (mixture: adhesion enhancer). The resulting silicone organic-inorganic composite (matrix polymer) and the self-healing silicate microtube prepared in Preparation Example 1 were mixed at a weight ratio of 6: 4 (silicone organic-inorganic composite: microtube) to form a self-healing silicate microtube composition. (A mixture of a silicon organic-inorganic composite and a reactive self-healing concrete surface modifier) was prepared. To this composition, 0.2 parts by weight of a ruthenium catalyst was added based on 100 parts by weight of the self-healing concrete surface modifier and the silicone organic-inorganic composite.

( Protective film  Having concrete structures)

Example  One

Prepare concrete specimen according to KS standard F 4936 concrete surface protection agent, 50 parts by weight of calcium aluminate cement, 3 parts by weight of polyvinyl alcohol fiber, which is a high tensile nano short fiber, and a mixture of blast furnace slag and fly ash (blast furnace slag and Mixing weight ratio of fly ash = 1: 1: 10 parts by weight of the mixture was applied to form a cross-section repair layer. Here, the specific gravity of the polyvinyl alcohol fiber was 1.26, length 3-12 mm, diameter 15 µm, tensile strength 890 Mpa, modulus of elasticity 14.7 Gpa) and the required amount was 1.2-1.3 kg / m 2.

A mixture of 55 parts by weight of calcium aluminate cement, 20 parts by weight of a 1: 1 weight ratio of blast furnace slag and fly ash, and 8 parts by weight of a composition containing a self-healing silicate tube of Preparation Example 2 were applied to the cross-section repair layer and at 20 ° C. After drying for 4 hours or more, a primer was formed to a thickness of about 600 μm. Here, the specific gravity of the polyvinyl alcohol fiber was 1.26, length 3-12 mm, diameter 15 µm, tensile strength 890 Mpa, modulus of elasticity 14.7 Gpa) and the required amount was 1.2-1.3 kg / m 2.

On the upper coat, 25 parts by weight of a modified acrylic emulsion, 42 parts by weight of calcium carbonate as a filler, 5 parts by weight of diatomaceous earth, 10 parts by weight of water, 5 parts by weight of titanium dioxide, and 10 parts by weight of water were applied to the composition and 24 hours at 20 ° C. During drying, the intermediate thickness was formed to a thickness of about 700 μm. The moderate requirement was 0.55 kg / m 2.

As a ceramic resin, a mixture of 65 parts by weight of a mixed resin of 1: 1 parts by weight of epoxy resin and melamine resin, 20 parts by weight of cellulose acetate butyrate, and 15 parts by weight of polyethylene glycol is applied to the middle part and dried at 20 ° C. for 24 hours. Formed to form a protective coating on the surface of the concrete structure. The topcoat had a thickness of 100 µm and a required amount of 0.09 kg / m 2.

Example  2-3

When the primer was formed, it was carried out in the same manner as in Example 1, except that the contents of the self-recovering silicate tube-containing composition were changed to 10 parts by weight and 5 parts by weight, respectively.

Example  4

It was carried out according to the same method as in Example 1, except that 5 parts by weight of the multi-colored capsules were further used in the middle formation. The middle coating operation using the multi-colored capsules was carried out using Bluetech R8318H, an air pressure tank with a mult coat pressure gun. Multi-color capsules contain a mixture of titanium dioxide and iron oxide, and these mixing ratios are 1: 0, 0: 1, 1: 1, 2: 1, 1: 2, 0.5: 1, or 0.1: 2 depending on the color you want to implement. Was controlled by.

Comparative example  One

It was carried out according to the same method as in Example 1, except that the polyvinyl fiber was not used when forming the cross-section repair layer without adding the self-repairing silicate tube-containing composition when forming the primer.

Comparative example  2

It was carried out in the same manner as in Example 1, except that the self-healing silicate tube containing composition was not added when forming the undercoat, but the self-healing silicate tube containing composition was added when forming the top coat.

Comparative example  3

It was carried out in the same manner as in Example 1, except that the self-healing silicate tube-containing composition was added during the formation of the primer and the self-healing silicate tube-containing composition was added during the middle formation.

Comparative example  4

When the cross-section repair layer was formed, it was carried out according to the same method as in Example 1, except that a composition without adding polyvinyl alcohol fibers, which are high tensile nano short fibers, was used.

Evaluation example  One

For the protective coatings of the concrete structures prepared according to Examples 1 to 3 and Comparative Examples 1-4, chloride ion penetration resistance, moisture permeability, neutralization depth and adhesion strength were evaluated by the KSF 4042 method and the evaluation results are shown in Table 1 below. It is shown in.

division Example
One Example
2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Chloride ion penetration resistance (coulombs) 45 40 42 428 536 624 551 Bond strength (N / mm2) 1.9 1.8 1.85 1.1 1.3 1.2 1.35 Neutralization depth (mm) 0.3 0.3 0.31 0.8 1.2 1.0 0.9 Moisture permeability (g / m2) One One 0 32 26 18 22

From the test results in Table 1, it can be seen that the protective coating films of the concrete structures of Examples 1 to 3 satisfy the reference values of chloride ion penetration resistance, adhesion strength, neutralization depth, and moisture permeability. In addition, as can be seen from Table 1, the compressive strength is increased when the test is cured, and the initial strength is expressed at 7 days.

Evaluation example  2: Investigation of corrosion and water permeability of damaged parts

Damage to the protective coating of the concrete structures prepared according to Examples 1 to 3 and Comparative Examples 1 to 3, and after applying about 20 HZ of vibration for 2 hours, sprinkle about 5% by weight of brine to cause corrosion on the damaged parts. It was investigated in accordance with the KS F 4042 method and the amount of salt water absorption is shown in Table 2.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Corrosion No corrosion No corrosion No corrosion Corrosion Some corrosion Some corrosion - Permeability (g) 15 20 18 100 85 88 - Compressive strength (N / mm2) Normal curing 7 days 34.5 32.1 34.9 20.0 21.0 22.0 30.0 Compressive strength (N / mm ² ) Normal curing 28 days 48.2 46.4 52.2 29.2 32.3 28.2 33

As shown in Table 2, when carried out according to Examples 1 to 3, the permeation amount was less than 20 g, so the reference value was satisfied and the self-recovery material was supplied from the self-repairing silicate tube, and the result of the next recovery occurred Comparative Example 1-3 In contrast, there was little corrosion. In addition, when it was carried out according to Examples 1 to 3, the compressive strength was improved compared to that of Comparative Examples 1-4.

In addition, as a result of confirming whether or not salt water was generated at the damaged site, it was confirmed that the salt water permeability was significantly reduced as compared with Comparative Example 1-3. In contrast, in the case of Comparative Example 2 in which the self-healing material was added during the formation of the top coat and in Comparative Example 3 in which the self-healing material was added during the formation of the middle, the occurrence of corrosion was suppressed compared to the case of the Comparative Example 1, but the effect of inhibiting the corrosion occurrence was lower than that of the lower coat. The result was reduced.

When the water permeability is 100, the relative amount of salt water absorbed at the damaged parts of the concrete structures of Examples 1 to 3 and Comparative Examples 2-3 is 100. will be.

Evaluation example  3

When the primers were formed on the concrete structures according to Examples 1 and 4, the crack generation and crack lengths were investigated by investigating the effect of crack generation according to the presence or absence of polyvinyl fiber, which is a high tensile nanoshort fiber, according to the KSF 4936 method. It was investigated, and the results are shown in Table 3 below.

Crack width (mm) Crack length (cm) Example 1 0 0 Comparative Example 1 1.0 9.1 3.0 18 Comparative Example 4 1.0 7.9 3.0 14.2

As shown in Table 3, when the polyvinyl alcohol was added to the cross-section repair layer, as in the case of Example 1, it was found that the crack control effect is very excellent, unlike in the case of Comparative Example 1 and Comparative Example 4.

Evaluation example  5: mid color evaluation

In the concrete structure obtained according to Example 1 and Example 4, the state of the intermediate was investigated through photographs, and the results are shown in FIGS. 1 and 2, respectively.

1 and 2 show the intermediate state in the concrete structure carried out according to Example 1 and Example 4, respectively.

Referring to FIG. 1, it was found that according to Example 1, it is possible to form a neutrality having a single color, and when implemented according to Example 4 as shown in FIG. 2, it is possible to realize a multi-colored environment-enhanced moderation.

As described above, the present invention has been described with specific contents and some examples, but it is revealed that this is only a description given as a specific example in order to help the overall understanding of the present invention. The present invention is not limited only to the above-described embodiments, and those skilled in the art to which the present invention pertains can make various modifications and variations to these embodiments, and such modifications and variations are also within the technical spirit of the present invention. It is covered in. Accordingly, the embodiments described above and the claims to be described later, as well as all equivalents or equivalent modifications of the claims, fall within the scope of the technical spirit of the present invention.

Claims (3)

Top coat for increasing durability on the surface of the concrete structure; Midway for realizing marble texture; It forms a protective film containing a self-healing base surface adjustment layer containing a reactive self-healing concrete surface modifier, and a chemically resistant cross-section repair layer of primer and high-tensile nano short fibers for waterproofing and contamination prevention.
The top coat includes 50 to 70 parts by weight of ceramic resin, 15 to 25 parts by weight of cellulose acetate butyrate and 10 to 25 parts by weight of polyethylene glycol based on the total top coat weight,
The middle is 23 to 28 parts by weight of the modified acrylic emulsion based on the total medium weight, 40 to 56 parts by weight of the filler, 5 to 8 parts by weight of diatomaceous earth, 5 to 10 parts by weight of titanium dioxide, 10 to 15 parts by weight of water, and pigment 1 to 10 parts by weight,
The primer is 35 to 55 parts by weight of calcium aluminate cement based on the total primer weight, 5 to 20 parts by weight of a mixture of blast furnace slag and fly ash, 40 to 45 parts by weight of general aggregate, and a silicone organic-inorganic composite and reactive self-healing concrete surface 5 to 10 parts by weight of the mixture of the adjusting agent,
The section repair layer includes 40 to 55 parts by weight of calcium aluminate cement, 0.1 to 5 parts by weight of polyvinyl alcohol fibers, which are high tensile nano short fibers, and 5 to 20 parts by weight of a mixture of blast furnace slag and fly ash,
The reactive self-healing concrete surface modifier is a self-healing silicate tube containing a coating film of urea-formaldehyde polymer and a core material of siloxane resin, and silicone organic in a mixture of the silicone organic-inorganic composite and the reactive self-healing concrete surface modifier. -The inorganic composite is a product of hydrolysis and dehydration of silicone alkoxide and siloxane resin, and the content of the silicone organic-inorganic composite is 30 to 70 based on 100 parts by weight of the total content of the silicone organic-inorganic composite and the self-repairing silicate tube. Surface treatment method to increase the durability of the concrete structure, which is the weight part. delete According to claim 1, wherein the siloxane resin is polydimethylsiloxane, dimethylsiloxane-diphenylsiloxane copolymer, dimethylsiloxane-methylphenylsiloxane copolymer or polydimethylsiloxane having silanol end groups, polydimethylsiloxane having silanol end groups Or a combination of the surface treatment method to increase the durability of the concrete structure.

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